KR101819785B1 - Resin composition - Google Patents
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- KR101819785B1 KR101819785B1 KR1020137020502A KR20137020502A KR101819785B1 KR 101819785 B1 KR101819785 B1 KR 101819785B1 KR 1020137020502 A KR1020137020502 A KR 1020137020502A KR 20137020502 A KR20137020502 A KR 20137020502A KR 101819785 B1 KR101819785 B1 KR 101819785B1
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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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
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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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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- Polymers & Plastics (AREA)
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- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides an epoxy resin composition which is excellent in low-temperature curability, low in Tg (glass transition point) of a cured product, and hardly changes in Tg of a cured product even after prolonged time after curing. The resin composition of the present invention contains (A) an epoxy resin containing no benzene ring, (B) a thiol compound having two or more thiol groups in the molecule, and (C) a latent curing agent. It is preferable that the component (B) is blended in a proportion of 1.0 to 2.0 in terms of the thiol equivalent ratio to the epoxy equivalent of the component (A).
Description
The present invention relates to an epoxy resin composition having excellent low-temperature curability, low Tg (glass transition point) of a cured product, and hardly changing the Tg of a cured product even after prolonged lapse of time after curing.
A resin composition comprising an epoxy resin, a thiol compound and a curing accelerator is a resin composition excellent in low temperature curability that can be cured within a short time even at 0 캜 to -20 캜 and is used for various applications such as adhesives and sealing agents for electronic parts. As examples of such resin compositions, Patent Documents 1 and 2 disclose (1) an epoxy resin having two or more epoxy groups in the molecule, (2) a polythiol compound having two or more thiol groups in the molecule, and (3) A resin composition containing a latent curing accelerator is disclosed. Patent Document 3 discloses an epoxy resin composition containing a bisphenol A type epoxy resin having a flexible skeleton and a polar coupler and a polythiol having two or more thiol groups.
However, when two parts having different thermal expansion coefficients are bonded to each other with an adhesive, thermal stress may be applied to the joint part due to a change in ambient temperature, resulting in cracks or the like. For this reason, adhesives for bonding these components are required to have flexibility enough to follow the thermal deformation of the components, and have low Tg (glass transition point) after curing of the adhesive, that is, low elastic modulus Is required.
However, the epoxy resin compositions described in Patent Documents 1 and 2 have excellent low-temperature curability and storage stability, but have a problem that Tg can not be sufficiently low. The epoxy resin composition described in Patent Document 3 described above can be cured at a low temperature, and since the cured product has some degree of flexibility and flexibility, the epoxy resin composition can absorb stress, but the cured product hardens more There is a problem that flexibility and flexibility are gradually lost.
SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an epoxy resin composition which has excellent low temperature curability, low Tg (glass transition point) of a cured product, and hardly changes Tg of a cured product even after prolonged time And to provide the above objects.
As a result of various experiments to solve the above problems, the present inventors have found that a resin composition containing an epoxy resin not containing a benzene ring, a thiol compound having two or more thiol groups in a molecule, and a latent curing agent has a low temperature curability , The Tg of the cured product is low, and the Tg of the cured product hardly changes even after prolonged time after curing.
The present invention is a resin composition containing (A) an epoxy resin not containing a benzene ring, (B) a thiol compound having two or more thiol groups in the molecule, and (C) a latent curing agent.
In the resin composition of the present invention, the component (A) is preferably a compound represented by the following formula (1).
In the resin composition of the present invention, the component (A) is preferably a compound represented by the following formula (2).
In the resin composition of the present invention, the component (A) is preferably a compound represented by the following formula (3).
In the resin composition of the present invention, the component (A) is preferably a compound represented by the following formula (4).
In the resin composition of the present invention, it is preferable that the component (B) is blended with the epoxy equivalent weight of the component (A) at a ratio of 1.0 to 2.0 in terms of the thiol equivalent ratio.
In the resin composition of the present invention, the component (B) is preferably selected from tetraethylene glycol bis 3-mercaptopropionate, trimethylolpropane tris 3-mercaptopropionate, pentaerythritol tetrakis 3-mercaptopropionate , And dipentaerythritol tetrakis (3-mercaptopropionate).
The resin composition of the present invention preferably further contains at least one additive selected from the group consisting of a silica filler, a silane coupling agent, an ion trap agent, a leveling agent, an antioxidant, a defoaming agent, and a thixotropic agent Do.
Further, the present invention provides an electronic part sealed by a sealing agent containing any one of the above resin compositions.
The present invention also provides an adhesive containing any one of the above resin compositions.
According to the present invention, it is possible to provide an epoxy resin composition having excellent low-temperature curability, low Tg (glass transition point) of a cured product, and hardly changing Tg even after prolonged lapse of time after curing.
Hereinafter, the present invention will be described in detail.
The resin composition according to the embodiment of the present invention contains (A) an epoxy resin containing no benzene ring, (B) a thiol compound having two or more thiol groups in the molecule, and (C) a latent curing agent.
The epoxy resin of the component (A) is preferably a compound represented by the following formula (1), for example.
The compound represented by the formula (1) is preferably a compound represented by the following formula (2) and / or formula (3), for example.
The compound represented by the formula (1) is preferably a compound represented by the following formula (4), for example.
In the following formula (4), R 2 to R 5 are preferably a methyl group.
The thiol compound of component (B) may be any compound having two or more thiol groups per molecule. From the standpoint of storage stability, it is preferable that the basic impurity content is as small as possible. Examples of such thiol compounds include trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (? -Thiopropionate), pentaerythritol A polyol such as ritol tetrakis (? -Thiopropionate), dipentaerythritol poly (? -Thiopropionate) and tris- [(3-mercaptopropionyloxy) -ethyl] -isocyanurate and And thiol compounds obtained by an esterification reaction of a mercapto organic acid.
Examples of thiol compounds include 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9- Alkylpolythiol compounds such as decanedithiol; Terminal thiol group-containing polyethers; Terminal thiol group-containing polythioethers; A thiol compound obtained by the reaction of an epoxy compound with hydrogen sulfide; A thiol compound having a terminal thiol group obtained by reaction of a polythiol compound with an epoxy compound; And the like. In the case of using a basic substance as a reaction catalyst in the production process thereof, a thiol compound having two or more thiol groups in a molecule in which alkali metal ion concentration is adjusted to 50 ppm or less by performing a dealkalization treatment is preferable.
The latent curing agent of the component (C) is a compound which is solubilized at room temperature by heating with a solid insoluble in the epoxy resin, and functions as a curing accelerator. The latent curing agent is a solid imidazole compound at room temperature, A curing accelerator such as a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct system), a reaction product of an amine compound and an isocyanate compound or a urea compound (urea type adduct system), and the like.
Examples of the imidazole compound which is solid at room temperature used in the present invention include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-methylimidazolyl - (1)) ethyl-S-triazine, 2,4-diamino-6- (2'-methylimidazolyl- Phenylimidazole, 2-phenylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N, N ' (1) -ethyl) -adipoyldiamide, and the like, but the present invention is not limited thereto.
Examples of the epoxy compound used as one of raw materials for the production of the solid dispersion type amine duct type latent curing accelerator (amine-epoxy adduct system) used in the present invention include bisphenol A, bisphenol F, catechol, Polyglycidyl ethers obtained by reacting polyhydric phenols such as ricinole, or polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting epoxycarboxylic acid such as p-hydroxybenzoic acid and? -hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; A glycidylamine compound obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol or the like with epichlorohydrin; Polyfunctional epoxy compounds such as epoxidized phenol novolak resins, epoxidized cresol novolak resins and epoxidized polyolefins; monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether and glycidyl methacrylate; But the present invention is not limited thereto.
The amine compound used as a raw material for the production of the other one of the solid dispersed amine duct type latent curing accelerators used in the present invention is a compound having at least one active hydrogen capable of addition reaction with an epoxy group, A secondary amino group and a tertiary amino group at least in the molecule. Examples of such amine compounds are shown below, but are not limited thereto. That is, for example, aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine and 4,4'-diamino-dicyclohexylmethane; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; Heterocyclic compounds containing a nitrogen atom such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine; And the like.
Among them, a compound having a tertiary amino group in the molecule is a raw material for providing a latent curing accelerator having an excellent curing promoting ability, and examples of such a compound include dimethylaminopropylamine, diethylaminopropylamine , Amine compounds such as di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine and N-methylpiperazine, 2-methylimidazole, 2-ethylimidazole Primary or secondary amines having tertiary amino groups in the molecule such as imidazole compounds such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-dimethylaminoethanol, (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2- Hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy- 2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4,6-trimethylphenoxyphenyl) imidazoline, But are not limited to, 6-tris (dimethylaminomethyl) phenol, N -? - hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzoimidazole, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N-dimethylaminobenzoic acid, Methyl-glycine hydrazide, N, N- dimethyl propionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide Drew if alcohols, phenols, thiols, carboxylic acids, and Hydra having a tertiary amino group in the molecule such as; And the like.
In order to further improve the storage stability of the epoxy resin composition of the present invention, when the latent curing accelerator used in the present invention is produced by the addition reaction of the epoxy compound and the amine compound, the active hydrogen in the molecule An active hydrogen compound having at least one hydrogen atom may be added. Examples of such active hydrogen compounds are shown below, but the present invention is not limited thereto. That is, for example, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol and phenol novolak resin, polyhydric alcohols such as trimethylolpropane, adipic acid, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid and the like.
Examples of the isocyanate compound used as a further raw material for the solid dispersion type ammine duct system latent curing accelerator used in the present invention include n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, etc. A functional isocyanate compound; Hexamethylene diisocyanate, tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylenediisocyanate, 1,3,6 Polyfunctional isocyanate compounds such as hexamethylene triisocyanate and bicycloheptane triisocyanate; Also, a terminal isocyanate group-containing compound obtained by reacting these polyfunctional isocyanate compound with an active hydrogen compound; Can also be used. Examples of such a terminal isocyanate group-containing compound include an addition compound having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, an addition product having a terminal isocyanate group obtained by the reaction of tolylene diisocyanate with pentaerythritol Compounds, and the like, but the present invention is not limited thereto.
As the urea compound, for example, urea, thiourea and the like can be exemplified, but are not limited thereto.
The solid dispersed latent curing accelerator used in the present invention can be obtained by, for example, (a) two components of an amine compound and an epoxy compound, (b) three components of two components and an active hydrogen compound, or (c) The components are mixed and mixed with two or three components of an isocyanate compound and / or a urea compound, reacted at a temperature from room temperature to 200 ° C, cooled and solidified, and then pulverized or mixed with methyl ethyl ketone, dioxane , Tetrahydrofuran, or the like, followed by removing the solvent, and then pulverizing the solid content.
Representative examples of commercially available solid dispersion type latent curing accelerators are shown below, but the present invention is not limited thereto. Namely, for example, "Amicure PN-23" (product name of Ajinomoto Co., Ltd.) and "Amicure PN-40" (product name of Ajinomoto Co., Ltd.) Quot;), " Hardener X-3661S " (product name of ECR Co.), "Hardener X-3670S" -3721 "(product name of Asahi Kasei Co., Ltd.), and the urea type duct system includes" Ajiquer FXE-1000 "(product name of Fuji Kasei Co., Ltd.) Note)).
There is no particular difficulty in producing the resin composition of the present invention using the above-described components (A) to (C) as raw materials, and it can be conformed to conventionally known methods. For example, a mixer such as a Henschel mixer, to prepare the resin composition of the present invention.
In addition, there is no particular difficulty in curing the resin composition of the present invention, and conventionally known methods can be used. For example, the resin composition of the present invention can be cured by heating at 50 to 120 ° C.
The resin composition of the present invention is characterized by containing the above components (A) to (C). As a result, a resin composition having excellent low temperature curability and low Tg (glass transition point) of the cured product can be obtained. Further, a resin composition in which the Tg of the cured product hardly changes even after a long period of time after the resin composition is cured by heating to be a cured product can be obtained.
The reason why such a resin composition is obtained is considered to be that the benzene ring is not included in the molecule of the epoxy resin of the component (A). Or the epoxy equivalents of the compounds represented by the above formulas (2) and (3) are relatively high. Or the presence of a silicon skeleton in the molecule of the compound represented by the above formula (4).
In the resin composition of the present invention, it is preferable that the component (B) is blended in an amount of 1.0 to 2.0 (1.0 to 2.0) in terms of the equivalent ratio of thiol to the epoxy equivalent of the component (A). The term "epoxy equivalent" as used herein refers to a numerical value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule. "Thiol equivalent" refers to a numerical value obtained by dividing the molecular weight of a thiol compound by the number of thiol groups in one molecule. That is, when the component (B) is 1.0 to 2.0 equivalents relative to the epoxy equivalent of the component (A), it means that the number of thiol groups is 1.0 to 2.0 with respect to the number of epoxy groups.
By setting the mixing ratio of the component (A) and the component (B) to this range, it is possible to obtain a resin composition in which the Tg of the cured product hardly changes even after elapse of a long time after the resin composition is cured and becomes a cured product have. The reason why such a resin composition is obtained is considered to be that the thiol equivalence ratio of the component (B) to the epoxy equivalent of the component (A) is set in an appropriate range. That is, when the ratio of the thiol equivalent of the component (B) to the epoxy equivalent of the component (A) is less than 1.0, part of the epoxy group remains unreacted with the thiol group and the remaining epoxy group causes the curing of the cured product It is thought that it proceeds further. On the other hand, when the ratio of the thiol equivalent of the component (B) to the epoxy equivalent of the component (A) is larger than 2.0, part of the thiol group remains unreacted with the epoxy group and the remaining thiol group causes the curing Is more likely to proceed.
The resin composition of the present invention may further contain at least one additive selected from the group consisting of a silica filler, a silane coupling agent, an ion trap agent, a leveling agent, an antioxidant, a defoaming agent, and a thixotropic agent, if necessary. It may also contain a viscosity adjusting agent, a flame retardant, a solvent, or the like.
The resin composition of the present invention can be used as an adhesive for bonding parts together or as a raw material thereof.
The resin composition of the present invention can be used as a sealing agent for electronic parts or as a raw material thereof.
The elastic modulus of the adhesive using the resin composition of the present invention is preferably 0.01 to 1.5 GPa, more preferably 0.4 to 0.8 GPa.
When the modulus of elasticity is less than 0.01 GPa, the cured portion of the adhesive becomes brittle. When the modulus of elasticity is larger than 1.5 GPa, cracks may occur in the cured product due to the shrinkage stress of the adhesive.
The Tg of the adhesive using the resin composition of the present invention is preferably -20 to -55 캜, more preferably -30 to -38 캜.
When the Tg is larger than -20 占 폚, cracks may occur in the cured portion of the adhesive. Further, depending on the bonding strength with an adherend, cracks may occur in the adherend. When the Tg is smaller than -55 占 폚, the cured portion becomes brittle.
[Example]
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
(Preparation of resin composition)
The components shown in Tables 1 and 2 below were mixed to prepare the resin compositions of Examples 1 to 20.
The components shown in Table 3 below were mixed to prepare resin compositions of Comparative Examples 1 to 4.
In Tables 1 to 3, the numbers indicating the mixing ratios of the components (A) to (F) are all parts by weight.
Specific names of the components in Tables 1 to 3 are as follows.
(A1) Epoxy resin 1: "YDF8170" manufactured by Shinnittsu Chemical Co., Ltd., bisphenol F type epoxy resin, weight average molecular weight 165
(A2) Epoxy resin 2: "YL7410" (epoxy resin of the above formula (2)) manufactured by Japan Epoxy Resin Co., Ltd., a weight average molecular weight of 435
(A3) Epoxy resin 3: "PP300P" (epoxy resin of the above formula (3)) manufactured by Sanyo Chemical Industries, Ltd., a weight average molecular weight of 181.3
(A4) Epoxy resin 4: "TSL9906" (epoxy resin in which R 2 to R 5 are methyl groups in the above formula (4)) manufactured by Momentive Performance Materials Ltd., a weight average molecular weight of 296
(B1) Thiol compound 1: "PEMP" pentaerythritol tetrakis (3-mercaptopropionate) manufactured by SC Zukagaku Kabushiki Kaisha, weight average molecular weight 489
(B2) Thiol compound 2: SC "TMMP" trimethylolpropane tris (3-mercaptopropionate) manufactured by Yuki Kagaku Co., Ltd., weight average molecular weight 398
(B3) Thiol compound 3: SC "DPMP" manufactured by Yuki Kagaku Co., Ltd., dipentaerythritol hexacis (3-mercaptopropionate), weight average molecular weight 783
(C) Latent hardener: "PN40J" manufactured by Ajinomoto Fine Techno Co., Ltd., epoxy resin amine duct
(D) Stabilizer: "L07N" manufactured by Shikoku Kasei Kogyo Co., Ltd., bisphenol A type epoxy resin / phenol resin / boric acid ester
(E) Turpentine: "R805" manufactured by Nippon Aerosil Co., Ltd., fumed silica
(F) Coupling agent: "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane
(Preparation of Cured Product)
The resin compositions of Examples 1 to 20 and Comparative Examples 1 to 4 were heated at 80 캜 for 10 minutes. As a result, for Examples 1 to 20 and Comparative Example 1, a cured product obtained by curing the resin composition was obtained. In Comparative Examples 2 to 4, no cured product was obtained because the resin composition did not cure.
(Measurement of Tg and elastic modulus)
The elastic modulus [GPa], the glass transition temperature Tg [占 폚] after standing for 48 hours at a temperature condition of 120 占 폚 after curing, and a temperature condition of 120 占 폚 after curing were measured for the cured product obtained by curing the resin composition for 48 hours after being allowed to stand a glass transition point Tg [℃] and the adhesive strength [N / mm 2] were measured. The measurement results are shown in Tables 1 to 3.
With regard to the elastic modulus, the elastic modulus at -40 ° C was measured using dynamic thermomechanical measurement (DMA), manufactured by Seiko Instruments Inc., according to Japanese Industrial Standard JIS C6481.
The Tg was measured using a dynamic thermomechanical measurement (DMA) manufactured by Seiko Instruments Inc. according to Japanese Industrial Standard JIS C6481.
The adhesive strength was measured by the following test method.
(1) A sample is stencil printed on a glass epoxy substrate to a size of 2 mm ?.
(2) Place a 2 mm x 2 mm Si chip on the printed sample. This is cured at 180 ° C for 60 minutes using a blow dryer.
(3) The shear strength is measured with a tabletop universal testing machine (1605HTP manufactured by Aiko Engineering Co., Ltd.).
Assessment Methods
When the change of Tg after leaving the cured product at 120 ° C for 48 hours was within ± 5 ° C, the change of Tg was evaluated as "none".
When the change in the modulus of elasticity after the cured product was left at 120 占 폚 for 48 hours was within ± 0.1 GPa, the change in the modulus of elasticity was evaluated as "none".
As can be seen from the results of Examples 1 to 20, all of the resin compositions of the present invention were found to be curable in a short time even under the heating condition of 80 캜 and excellent in low-temperature curability. On the other hand, as can be seen from the results of Comparative Examples 2 to 4, the resin composition according to the comparative example had a thiol equivalent ratio to the epoxy equivalent of 0.5, which was too small, I could.
As can be seen from the results of Examples 1 to 20, it was found that the resin composition of the present invention can obtain a cured product having a modulus of elasticity at -40 ° C of 0.1 to 0.8 [Gpa] and a small modulus of elasticity . On the other hand, the resin composition according to the comparative example had a modulus of elasticity of 4.0 GPa at -40 캜 and a cured product having a small modulus of elasticity, as can be seen from the results of Comparative Example 1.
As can be seen from the results of Examples 1 to 20, it was found that the resin composition of the present invention had a Tg of -50 ° C to -30 ° C and a lower Tg of the cured product. On the contrary, as can be seen from the results of Comparative Example 1, the resin composition of the comparative example did not have a cured product having a Tg of 40 占 폚 and a low Tg.
As can be seen from the results of Examples 1 to 17, the elastic modulus and Tg of the cured product were hardly changed even after the resin composition of the present invention was left at 120 캜 for 48 hours after curing. Thus, it was demonstrated that the resin composition of the present invention hardly changes Tg even after prolonged lapse of time after curing.
Claims (10)
(A) an epoxy resin not containing a benzene ring
(B) a thiol compound having two or more thiol groups in the molecule
(C) Latent hardener
The component (B) is blended in a proportion of 1.0 to 2.0 in terms of thiol equivalent ratio to the epoxy equivalent of the component (A)
When the mass ratio of the component (C) to the component (B) is 10.5% to 85.3%
Resin composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2011-000465 | 2011-01-05 | ||
| JP2011000465 | 2011-01-05 | ||
| PCT/JP2011/070917 WO2012093510A1 (en) | 2011-01-05 | 2011-09-14 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20140047574A KR20140047574A (en) | 2014-04-22 |
| KR101819785B1 true KR101819785B1 (en) | 2018-01-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020137020502A KR101819785B1 (en) | 2011-01-05 | 2011-09-14 | Resin composition |
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|---|---|
| KR (1) | KR101819785B1 (en) |
| CN (1) | CN103282401A (en) |
| TW (1) | TWI629291B (en) |
| WO (1) | WO2012093510A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160002439A1 (en) * | 2013-03-07 | 2016-01-07 | Sumitomo Bakelite Co., Ltd. | Apparatus, composition for adhesive, and adhesive sheet |
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| TW201229080A (en) | 2012-07-16 |
| CN103282401A (en) | 2013-09-04 |
| TWI629291B (en) | 2018-07-11 |
| KR20140047574A (en) | 2014-04-22 |
| WO2012093510A1 (en) | 2012-07-12 |
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