CN113736403B - Single-component heat-resistant epoxy resin composition and preparation method and application thereof - Google Patents
Single-component heat-resistant epoxy resin composition and preparation method and application thereof Download PDFInfo
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- CN113736403B CN113736403B CN202111153663.3A CN202111153663A CN113736403B CN 113736403 B CN113736403 B CN 113736403B CN 202111153663 A CN202111153663 A CN 202111153663A CN 113736403 B CN113736403 B CN 113736403B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention belongs to the field of adhesives and sealants, and relates to a single-component heat-resistant epoxy resin composition, and a preparation method and application thereof. The single-component heat-resistant epoxy resin composition comprises 20-30 parts of first epoxy resin, 20-30 parts of second epoxy resin, 30-50 parts of polythiol compound, 1-5 parts of latent curing agent and 0.1-10 parts of auxiliary agent; the first epoxy resin is a bisphenol a epoxy resin and the second epoxy resin is an epoxy resin including at least one rigid ring. The invention adopts the reasonable collocation of the traditional bisphenol A type epoxy resin and the epoxy resin with at least one rigid ring, and the matching with the isocyanurate type polythiol compound with a unique structure, can realize the low-temperature rapid curing, improve the heat resistance, the damp-heat resistance and the hot bonding strength of the cured resin composition, and reduce the water absorption rate of the resin composition. The one-component heat-resistant epoxy resin composition with excellent performance and low cost is particularly suitable for being used as an adhesive or a sealant for manufacturing an image sensor module.
Description
Technical Field
The invention belongs to the field of adhesives and sealants, and particularly relates to a single-component heat-resistant epoxy resin composition, and a preparation method and application thereof.
Background
Due to excellent mechanical properties, electrical properties, heat resistance, chemical resistance, high bonding strength and low shrinkage rate, epoxy resin is widely used as matrix resin of coatings, electrical and electronic insulating materials, composite materials, adhesives and the like. In view of the recent requirements in the field of electronic circuits for protecting semiconductor devices, making circuits highly centralized and improving connection reliability, thermosetting epoxy adhesives often have problems of high curing temperature and slow curing speed while satisfying one-component storage stability, and thus are difficult to apply to the assembly of some precise electronic components, particularly to the use in image sensor modules. If the temperature is too high or the heat time is too long in the assembling process of the image sensor, the components such as the lens and the like can be degraded.
An epoxy resin system cured by mercaptan is an effective alternative for meeting the requirements of low-temperature short-time curing epoxy adhesives. For example, CN200480034851.2 realizes low-temperature fast curing of epoxy glue by using ester thiol compounds or dimercapto aliphatic polythiols or aromatic polythiols with obvious sulfur odor and low functionality. However, in the manufacture of electronic image sensor modules, high temperature and high humidity resistance and high heat resistance are also required to ensure long-term use stability of electronic components. After the CN200480034851.2 technology is repeated, the ester thiol compound adopted by the technology contains an ester bond easy to hydrolyze, and the bonding of the adhesive to the image sensor module is almost completely failed after a continuous high-temperature and high-humidity resistance experiment at 85 ℃/85% RH; when dimercapto aliphatic polythiol or aromatic polythiol without ester bond is adopted, the bonding strength is obviously reduced and the heat resistance is extremely poor after high temperature and high humidity resistance experiments. In other prior art, there is also a one-component resin composition using a thiol compound without an ester bond, but there is a problem that the heat resistance of the cured product is not sufficient in some cases. In addition, in the manufacture of the image sensor module, the water absorption rate of the used adhesive is required to be low, so that moisture in the air can be prevented from permeating into the module and interfering with a lens system after the module is bonded, assembled and sealed. However, the water absorption of the existing one-component resin composition is generally high, and it is difficult to satisfy this requirement.
Therefore, how to prepare a resin composition which is low in cost, can be rapidly cured at a low temperature, has excellent heat resistance after curing, low water absorption rate, and has good adhesive strength retention after moisture and heat resistance by using a suitable host resin combination and a thiol compound has become a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects that the existing one-component heat-resistant epoxy resin composition cannot simultaneously have excellent heat resistance, low water absorption and good bonding strength retention after moisture and heat resistance after being cured, and provides a novel one-component heat-resistant epoxy resin composition which can realize low-temperature rapid curing and has high heat resistance, low water absorption and outstanding moisture and heat resistance and thermal bonding strength after being cured.
The second object of the present invention is to provide a method for preparing the above one-pack heat-resistant resin composition.
The third object of the present invention is to provide a use of the above one-pack heat-resistant epoxy resin composition.
The purpose of the invention is realized as follows:
the invention provides a single-component heat-resistant epoxy resin composition, which comprises the following components in parts by weight:
the first epoxy resin is a bisphenol a epoxy resin and the second epoxy resin is an epoxy resin comprising at least one rigid ring;
the polythiol compound is represented by the general formula (I):
in the general formula (I), R1、R2And R3Each independently selected from the group consisting of substituents represented by the general formula (II):
in the general formula (II), R4Selected from sulfur atoms, methylene or ester bonds, R5Selected from a hydrogen atom, a methyl group or a hydroxyl group, and m and n are each independently selected from 0, 1 or 2.
In a preferred embodiment, in the formula (II), if R is4When it is a sulfur atom, then R5Is a hydrogen atom, m is 2, n is 1 or 2; if R is4When it is methylene, then R5Is a hydrogen atom, m is 0 or 1, n is 0; if R is4In the case of an ester bond, then R5Is hydrogen atom or methyl, m is 2, and n is 0 or 1.
In a preferred embodiment, the polythiol compound is selected from one or more of tris (3-mercaptoethyl) isocyanurate, tris (3-mercaptopropyl) isocyanurate, tris (2-mercaptoacetoxyethyl) isocyanurate, tris (3-mercaptopropionyloxyethyl) isocyanurate, and tris (3-mercaptobutyryloxyethyl) isocyanurate.
In a preferred embodiment, the weight ratio of the first epoxy resin to the second epoxy resin is 1 (0.8-1.2).
In a preferred embodiment, the second epoxy resin is a combination of isosorbide diglycidyl ether and triglycidyl isocyanurate in a weight ratio of 1 (0.1-0.5).
In a preferred embodiment, the latent curing agent is selected from one or more of dicyandiamide, hydrazide, guanidine compound, modified imidazole, modified amine, urea adduct, amine-epoxy adduct, and microcapsule type curing agent.
In a preferred embodiment, the auxiliary agent is selected from one or more of a stabilizer, a polymerization inhibitor, an antioxidant, a flame retardant, a diluent, an adhesion promoter, a silane coupling agent, a dye, a pigment, an antifoaming agent, a leveling agent and an ion trapping agent.
In a preferred embodiment, the one-part heat-resistant epoxy resin composition further includes a filler; the filler is selected from one or more of silicon dioxide, alumina, talc, calcium carbonate, glass microspheres, metal powder and polytetrafluoroethylene filler; the content of the filler is 0 to 10 parts by weight.
The invention also provides a preparation method of the single-component heat-resistant epoxy resin composition, wherein the method comprises the following steps:
(1) preparing raw materials according to the following components in parts by weight:
(2) and (2) stirring and mixing the first epoxy resin, the second epoxy resin, the polythiol compound, the auxiliary agent and the optional filler prepared in the step (1) for 0.5 to 2 hours at the temperature of 20 to 30 ℃ and the vacuum degree of-0.05 to-0.1 MPa, adding the latent curing agent, stirring and mixing for 0.1 to 1 hour at the temperature of 20 to 30 ℃ and the vacuum degree of-0.05 to-0.1 MPa, and immediately sealing and packaging.
The invention also provides application of the single-component heat-resistant epoxy resin composition as an adhesive or a sealant.
In a preferred embodiment, the adhesive is used for bonding of a sensor or a camera.
The key point of the invention is that the reasonable collocation of the resin system is adopted and simultaneously matched with hydrolysis-resistant polythiol compound for use, wherein, the contained resin adopts epoxy resin comprising at least one rigid ring besides the traditional bisphenol A epoxy resin, and the bisphenol A epoxy resin is matched with the epoxy resin comprising at least one rigid ring structure cooperatively, so that the main resin system is ensured to have enough rigidity and crosslinking degree, and on the basis, the isocyanurate type polythiol compound with a specific structure is added, the isocyanurate type polythiol compound does not contain ester bond and has unique rigid stable hexatomic ring and multiple functionality, thus not only realizing low-temperature rapid curing, but also the resin composition has the advantages of excellent heat resistance, low water absorption, high hot bonding strength, outstanding bonding strength retention after damp-heat resistance experiment and the like after curing, the adhesive is particularly suitable for being used as an adhesive or a sealant for manufacturing an image sensor module.
Detailed Description
The one-component heat-resistant epoxy resin composition provided by the invention contains a first epoxy resin, a second epoxy resin, a polythiol compound, a latent curing agent, an auxiliary agent and an optional filler. Wherein, the content of the first epoxy resin is 20-30 parts by weight, such as 20, 22, 25, 28, 30 parts by weight. The second epoxy resin is present in an amount of 20 to 30 parts by weight, such as 20, 22, 25, 28, 30 parts by weight. The polythiol compound is contained in an amount of 30 to 50 parts by weight, such as 30, 32, 35, 38, 40, 42, 45, 48, 50 parts by weight. The content of the latent curing agent is 1-5 parts by weight, such as 1, 2,3, 4 and 5 parts by weight. The content of the auxiliary agent is 0.1-10 parts by weight, such as 0.1, 0.5, 1, 2,3, 4, 5, 6, 7, 8, 9 and 10 parts by weight. The content of the filler is 0 to 10 parts by weight, such as 0, 0.1, 0.5, 1, 2,3, 4, 5, 6, 7, 8, 9 and 10 parts by weight.
The polythiol compound has a structure represented by general formula (I):
in the general formula (I), R1、R2And R3Each independently selected from the group consisting of substituents represented by the general formula (II); in the general formula (II), R4Selected from sulfur atoms, methylene or ester bonds, R5Selected from a hydrogen atom, a methyl group or a hydroxyl group, and m and n are each independently selected from 0, 1 or 2. Preferably, in the formula (II), if R4When it is a sulfur atom, then R5Is a hydrogen atom, m is 2, n is 1 or 2; if R is4When it is methylene, then R5Is a hydrogen atom, m is 0 or 1, n is 0; if R is4In the case of an ester bond, then R5Is hydrogen atom or methyl, m is 2, and n is 0 or 1. The polythiol compound does not contain ester bonds which are easy to hydrolyze, and has a rigid and stable six-membered heterocyclic ring structure, and the specific structure can endow a cured product with extremely high heat resistance and moisture resistance.
Specific examples of the polythiol compound include, but are not limited to: one or more of tris (3-mercaptoethyl) isocyanurate, tris (3-mercaptopropyl) isocyanurate, tris (2-mercaptoacetoxyethyl) isocyanurate, tris (3-mercaptopropionyloxyethyl) isocyanurate and tris (3-mercaptobutanoyloxyethyl) isocyanurate.
The first epoxy resin is bisphenol A epoxy resin. The second epoxy resin is an epoxy resin including at least one rigid ring, wherein the rigid ring may be a diheterocycle, a hexatomic heterocycle, or the like. The weight ratio of the first epoxy resin to the second epoxy resin is preferably 1 (0.8-1.2). The synergistic compounding of the first epoxy resin and the second epoxy resin under the action of the isocyanurate polythiol compound with a specific structure can ensure that a resin system has extremely high rigidity and crosslinking degree, so that a cured product has excellent heat and moisture resistance, thermal bonding strength and low water absorption.
In a preferred embodiment, the second epoxy resin is a combination of isosorbide diglycidyl ether and triglycidyl isocyanurate, more preferably, the weight ratio of isosorbide diglycidyl ether to triglycidyl isocyanurate is 1 (0.1-0.5). That is, the one-component heat-resistant epoxy resin composition preferably contains bisphenol a epoxy resin, isosorbide diglycidyl ether, and triglycidyl isocyanurate together, in which case the one-component heat-resistant epoxy resin composition has more excellent heat resistance and thermal bonding strength and lower water absorption rate. Specifically, the triglycidyl isocyanurate is contained in an amount of 0.1 to 0.5 parts by weight, for example, 0.1, 0.2, 0.3, 0.4, 0.5 parts by weight based on 1 part by weight of the isosorbide diglycidyl ether.
The latent curing accelerator is a compound which is inactive at room temperature and is activated by heating to function as a curing accelerator, and examples thereof include: one or more of dicyandiamide, hydrazide, guanidine compound, modified imidazole, modified amine, urea adduct, amine-epoxy adduct and microcapsule type curing agent.
The kind of the assistant in the present invention is not particularly limited, and may be various additives conventionally used in the art, for example, one or more selected from a stabilizer, a polymerization inhibitor, an antioxidant, a flame retardant, a diluent, an adhesion promoter, a silane coupling agent, a dye, a pigment, an antifoaming agent, a leveling agent, and an ion scavenger.
The stabilizer is preferably one or more selected from liquid borate compounds, aluminum chelating agents and barbituric acid. Specific examples of the liquid borate compounds include, but are not limited to: 2,2 '-oxybis (5, 5' -dimethyl-1, 3, 2-oxahexaborane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, pentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, trihexadecyl borate, trioctadecyl borate, triphenyl borate, tricresyl borate, triethanolamine borate, and the like. The liquid boric acid ester compound is preferable because it is liquid at room temperature (25 ℃) and the viscosity of the complex is suppressed to be low. The aluminum chelate compound may be, for example, aluminum chelate compound A (available from Chuangmo Seiki chemical Co., Ltd.).
Specific examples of the silane coupling agent include, but are not limited to: one or more of gamma-methacryloxypropyltrimethoxysilane, vinyl tri (beta-methoxyethoxy) silane, vinyl trimethoxysilane, vinyl triethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, anilinomethyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and gamma-ureidopropyltriethoxysilane.
The pigment may be any of various pigments that can impart color to the resin composition and do not affect other properties, and may be one selected from carbon black, titanium black, copper-iron-manganese metal oxides, and black organic colorants.
In addition, the polymerization inhibitor, antioxidant, flame retardant, diluent, adhesion promoter, dye, defoamer, leveling agent and ion scavenger can be selected conventionally in the field, and those skilled in the art can know the selection and do not need to describe any further.
The one-component heat-resistant epoxy resin composition provided by the invention can also comprise a filler. When a one-component heat-resistant epoxy resin composition is used as an adhesive or sealant, if a filler is added thereto, the heat resistance, moisture resistance, particularly heat cycle resistance of the bonded portion can be improved. The reason why the heat cycle resistance is improved by adding the filler is that the linear expansion coefficient of the cured product is reduced, that is, expansion-contraction of the cured product due to heat cycle is suppressed. The filler is not particularly limited as long as it has an effect of reducing the linear expansion coefficient, and specific examples thereof include, but are not limited to: at least one of silica, alumina, talc, calcium carbonate, glass microspheres, metal powder, and Polytetrafluoroethylene (PTFE).
The preparation method of the one-component heat-resistant epoxy resin composition provided by the invention comprises the following steps:
(1) preparing raw materials according to the following components in parts by weight:
(2) and (2) stirring and mixing the first epoxy resin, the second epoxy resin, the polythiol compound, the auxiliary agent and the optional filler prepared in the step (1) for 0.5 to 2 hours at the temperature of 20 to 30 ℃ and the vacuum degree of-0.05 to-0.1 MPa, adding the latent curing agent, stirring and mixing for 0.1 to 1 hour at the temperature of 20 to 30 ℃ and the vacuum degree of-0.05 to-0.1 MPa, and immediately sealing and packaging.
The invention also provides application of the single-component heat-resistant epoxy resin composition as an adhesive or a sealant.
In a preferred embodiment, the adhesive is used for bonding of a sensor or a camera.
The present invention will be further described with reference to the following examples.
In the following examples and comparative examples, the parts of each raw material are parts by weight.
The raw materials and sources used in the following examples and comparative examples are as follows:
bisphenol A type epoxy resin is selected from YD-128 of Korea KUKDO company, the epoxy equivalent is 184-190g/eq, and the structural formula is shown as the formula (VI):
isosorbide diglycidyl ether selected from DENACO GSR-101 from Nagase ChemteX, Japan, having an epoxy equivalent weight of 129g/eq and a structural formula as shown in formula (VII):
triglycidyl isocyanurate is selected from electronic grade TGIC in Sandeli chemical engineering of Yangzhou, the epoxy equivalent is 99g/eq, and the structural formula is shown as a formula (VIII):
tris (3-mercaptopropyl) isocyanurate having a thiol equivalent weight of 117g/eq selected from Amitychem's TTTSH and having the formula shown in formula (iii):
trimethylolpropane tri (3-mercaptopropionate) ester having a thiol equivalent of 133g/eq, selected from TMMP of SC for Japan and having a structural formula as shown in formula (IV):
a polyether polythiol selected from QE-340M, Toray corporation, Japan, having a thiol equivalent weight of 275g/eq and a structural formula represented by formula (V):
a latent curing agent selected from NOVACURE HXA-3922HP of asahi chemicals, japan;
the stabilizer is triethyl borate selected from B0520 of TCI corporation of Japan;
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane selected from KBM-403 of Shin-Etsu Chemical company of Japan;
the pigment is Titanium black selected from Balck Titanium Oxide 12S from Mitsubishi Materials, Japan;
the filler is fumed silica selected from AEROSIL R202 from Evonik corporation.
Example 1
Accurately weighing the raw materials according to the dosage of table 1, adding 20 parts of bisphenol A type epoxy resin (YD-128), 16 parts of isosorbide diglycidyl ether (DENACOL GSR-101), 4 parts of triglycidyl isocyanurate (TGIC), 32 parts of polythiol compound tris (3-mercaptopropyl) isocyanurate (TTTSH), 0.3 part of stabilizer triethyl borate (B0520), 1 part of silane coupling agent gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KBM-403), 2 parts of pigment Titanium black (Balck Titanium Oxide 12S) and 2 parts of filler fumed silica (AEROSIL R202) into a dispersing and mixing device, controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, and stirring and mixing for 1 hour; then adding 3 parts of latent curing agent (NOVACURE HXA-3922HP), controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, stirring and mixing for 30 minutes, and immediately sealing and packaging to obtain the single-component heat-resistant epoxy resin composition.
Example 2
Accurately weighing each raw material according to the dosage of table 1, adding 30 parts of bisphenol A type epoxy resin (YD-128), 24 parts of isosorbide diglycidyl ether (DENACOL GSR-101), 6 parts of triglycidyl isocyanurate (TGIC), 50 parts of polythiol compound tris (3-mercaptopropyl) isocyanurate (TTTSH), 0.3 part of stabilizer triethyl borate (B0520), 1 part of silane coupling agent gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KBM-403), 2 parts of pigment Titanium black (Balck Titanium Oxide 12S) and 2 parts of filler fumed silica (AEROSIL R202) into a dispersing and mixing device, controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, and stirring and mixing for 1 hour; then adding 3 parts of latent curing agent (NOVACURE HXA-3922HP), controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, stirring and mixing for 30 minutes, and immediately sealing and packaging to obtain the single-component heat-resistant epoxy resin composition.
Example 3
Accurately weighing the raw materials according to the dosage of table 1, adding 25 parts of bisphenol A type epoxy resin (YD-128), 20 parts of isosorbide diglycidyl ether (DENACOL GSR-101), 5 parts of triglycidyl isocyanurate (TGIC), 40 parts of polythiol compound tris (3-mercaptopropyl) isocyanurate (TTTSH), 0.3 part of stabilizer triethyl borate (B0520), 1 part of silane coupling agent gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KBM-403), 2 parts of pigment Titanium black (Balck Titanium Oxide 12S) and 2 parts of filler fumed silica (AEROSIL R202) into a dispersing and mixing device, controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, and stirring and mixing for 1 hour; then adding 3 parts of latent curing agent (NOVACURE HXA-3922HP), controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, stirring and mixing for 30 minutes, and immediately sealing and packaging to obtain the single-component heat-resistant epoxy resin composition.
Example 4
Accurately weighing the raw materials according to the dosage of table 1, adding 22.5 parts of bisphenol A type epoxy resin (YD-128), 18 parts of isosorbide diglycidyl ether (DENANOL GSR-101), 4.5 parts of triglycidyl isocyanurate (TGIC), 36 parts of polythiol compound tris (3-mercaptopropyl) isocyanurate (TTTSH), 0.3 part of stabilizer triethyl borate (B0520), 1 part of silane coupling agent gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KBM-403), 2 parts of pigment Titanium black (Balck Titanium Oxide 12S) and 2 parts of filler fumed silica (AEROSIL R202) into a dispersion mixing device, controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, and stirring and mixing for 1 hour; then adding 3 parts of latent curing agent (NOVACURE HXA-3922HP), controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, stirring and mixing for 30 minutes, and immediately sealing and packaging to obtain the single-component heat-resistant epoxy resin composition.
Example 5
Accurately weighing the raw materials according to the dosage of table 1, adding 27.5 parts of bisphenol A type epoxy resin (YD-128), 22 parts of isosorbide diglycidyl ether (DENANOL GSR-101), 5.5 parts of triglycidyl isocyanurate (TGIC), 45 parts of polythiol compound tris (3-mercaptopropyl) isocyanurate (TTTSH), 0.3 part of stabilizer triethyl borate (B0520), 1 part of silane coupling agent gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KBM-403), 2 parts of pigment Titanium black (Balck Titanium Oxide 12S) and 2 parts of filler fumed silica (AEROSIL R202) into a dispersion mixing device, controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, and stirring and mixing for 1 hour; then adding 3 parts of latent curing agent (NOVACURE HXA-3922HP), controlling the temperature at 25 ℃, vacuumizing to-0.07 MPa, stirring and mixing for 30 minutes, and immediately sealing and packaging to obtain the single-component heat-resistant epoxy resin composition.
Example 6
A one-component heat-resistant epoxy resin composition was prepared by following the procedure of example 3, except that isosorbide diglycidyl ether was replaced with triglycidyl isocyanurate (TGIC) having the same epoxy equivalent weight, and the remaining conditions were the same as in example 3, to obtain a one-component heat-resistant epoxy resin composition.
Comparative example 1
A one-component heat-resistant epoxy resin composition was prepared by following the procedure of example 3 except that isosorbide diglycidyl ether (DENACOL GSR-101) and triglycidyl isocyanurate (TGIC) were replaced with bisphenol A type epoxy resin (YD-128) having the same epoxy equivalent weight and the other conditions were the same as in example 3 to obtain a one-component heat-resistant epoxy resin composition.
Comparative example 2
A one-part heat-resistant epoxy resin composition was prepared by following the procedure of example 3, except that the polythiol compound tris (3-mercaptopropyl) isocyanurate (TTTSH) was replaced with the polythiol compound trimethylolpropane tris (3-mercaptopropionic acid) ester (TMMP) having the same thiol functional group equivalent, and the remaining conditions were the same as in example 3, to obtain a one-part heat-resistant epoxy resin composition.
Comparative example 3
A one-component heat-resistant epoxy resin composition was prepared by following the procedure of example 3, except that the polythiol compound tris (3-mercaptopropyl) isocyanurate (TTTSH) was replaced with the same thiol functional group equivalent of polyether polythiol (QE-340M), and the remaining conditions were the same as in example 3, to obtain a one-component heat-resistant epoxy resin composition.
Comparative example 4
A one-component heat-resistant epoxy resin composition was prepared by following the procedure of example 3 except that the bisphenol A type epoxy resin (YD-128) was replaced with isosorbide diglycidyl ether (DENACOL GSR-101) having the same epoxy equivalent weight and the other conditions were the same as in example 3 to obtain a one-component heat-resistant epoxy resin composition.
TABLE 1
Test example
(1) Hot bonding strength: respectively coating the single-component heat-resistant epoxy resin composition obtained in each example and each comparative example on a stainless steel sheet, overlapping and pressing the stainless steel sheets by using toughened glass sheets to manufacture a test sample, wherein the bonding area is 25.4mm multiplied by 5mm, and the thickness of a glue layer is ensured to be 0.1 mm; placing the sample in an oven at 80 ℃ for heat curing for 60 minutes; pulling the two sheets apart in opposite directions by using a universal testing machine, testing under the condition that the environmental temperature is 85 ℃, and recording the measured force value by using strength (MPa); after the cured sample is treated under the conditions of heating and humidifying at 85 ℃/85% RH/120h, the shear bonding strength (MPa) of the sample is tested again under the condition that the ambient temperature is 85 ℃ and the result is recorded as shown in Table 2.
(2) Glass transition temperature (Tg): testing by using a Q-800 type dynamic thermomechanical analysis tester (DMA) of a American TA instrument, preparing the completely cured resin composition into a film of 42mm multiplied by 8mm multiplied by 0.3mm, and measuring the change rule of a loss factor (tan delta) with the temperature in a liquid nitrogen atmosphere and a film stretching mode within the temperature range of-40 to 250 ℃, wherein the temperature rise rate is 10 ℃/min, the testing frequency is 10Hz, so as to determine the glass transition temperature T of the cured resin compositiongIn degrees centigrade. The results are shown in Table 2.
(3) Water absorption: preparing a sample of 3mm multiplied by 1.5mm from the completely cured resin composition, weighing and recording the sample, immersing the sample into deionized water at the temperature of 100 ℃, and carrying out constant temperature treatment for 2 hours; taking the sample out of the water, carefully absorbing the water attached to the surface of the sample by using filter paper, weighing the sample again and recording; the weight percentage increase of the sample before and after boiling was calculated as the water absorption (%). The results are shown in Table 2.
TABLE 2
As can be seen from the results in table 2, the conventional bisphenol a epoxy resin and the epoxy resin having at least one rigid ring are used in combination according to a specific amount, and an isocyanurate-type polythiol compound having a unique rigid structure and multiple functionalities is used, so that the obtained one-component heat-resistant epoxy resin composition has an extremely high glass transition temperature and thermal bonding strength after curing, and can maintain most of the thermal bonding strength after heating and humidifying experiments, reflecting that the heat resistance is excellent, and the cured product has a low water absorption rate and good moisture barrier property. As can be seen from a comparison of example 3 and example 6, when the second epoxy resin is a combination of isosorbide diglycidyl ether and triglycidyl isocyanurate, the one-component heat-resistant epoxy resin composition has more excellent heat resistance and hot tack strength and lower water absorption rate. As can be seen from the comparison of example 3 with comparative example 1, when the second epoxy resins used in the present invention were all replaced with conventional liquid bisphenol A epoxy resins, the glass transition temperature and the thermal bonding strength of the one-component heat-resistant epoxy resin composition after curing were greatly reduced as compared with example 3, and the water absorption of the cured product was also increased to 5.06%, indicating that the present invention, in which the conventional bisphenol A epoxy resin was compounded with an epoxy resin including at least one rigid ring, has a crucial effect on the improvement of heat resistance, bonding properties and moisture barrier properties. As can be seen from the comparison between example 3 and comparative examples 2 to 3, when the polythiol compound used in the present invention was changed from tris (3-mercaptopropyl) isocyanurate to trimethylolpropane tris (3-mercaptopropionate) or polyether polythiol, the glass transition temperature of the resin composition after curing was greatly reduced, and the thermal bond strength was also reduced to some extent, and it was particularly apparent that the thermal bond strength of the composition after the heat and moisture tests was reduced by more than 85% and the water absorption rate was also significantly increased, indicating that the heat resistance, the wet heat resistance and the water absorption rate of the resin composition in comparative examples 2 to 3 were significantly inferior to those of example 3. As can be seen from the comparison between example 3 and comparative example 4, when all of the liquid bisphenol A epoxy resins used in the present invention were replaced with isosorbide diglycidyl ether, the glass transition temperature and the thermal bonding strength of the one-component heat-resistant epoxy resin composition after curing were reduced to some extent as compared with example 3, and the water absorption of the cured product was increased to 3.58%, indicating that the present invention has a crucial effect on the improvement of heat resistance, bonding property and moisture barrier property when the conventional bisphenol A epoxy resin is compounded with the epoxy resin including at least one rigid ring.
In conclusion, the invention adopts the reasonable collocation of the traditional bisphenol A type epoxy resin and the epoxy resin with at least one rigid ring, and the traditional bisphenol A type epoxy resin is matched with the isocyanurate type polythiol compound with a unique structure, thereby realizing the low-temperature rapid curing, improving the heat resistance, the damp-heat resistance and the hot bonding strength of the cured resin composition, and reducing the water absorption rate of the resin composition.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (11)
1. The one-component heat-resistant epoxy resin composition is characterized by comprising the following components in parts by weight:
20-30 parts of first epoxy resin;
20-30 parts of second epoxy resin;
30-50 parts of polythiol compound;
1-5 parts of a latent curing agent;
0.1-10 parts of an auxiliary agent;
the first epoxy resin is bisphenol A epoxy resin, and the second epoxy resin is the combination of isosorbide diglycidyl ether and triglycidyl isocyanurate in a weight ratio of 1 (0.1-0.5);
the polythiol compound is represented by the general formula (I):
in the general formula (I), R1、R2And R3Each independently selected from the group consisting of substituents represented by the general formula (II):
in the general formula (II), R4Selected from sulfur atoms, methylene or ester bonds, R5Selected from a hydrogen atom, a methyl group or a hydroxyl group, and m and n are each independently selected from 0, 1 or 2.
2. The one-component heat-resistant epoxy resin composition according to claim 1, wherein in the general formula (II), if R is4When it is a sulfur atom, then R5Is a hydrogen atom, m is 2, n is 1 or 2; if R is4When it is methylene, then R5Is a hydrogen atom, m is 0 or 1, n is 0; if R is4In the case of an ester bond, then R5Is hydrogen atom or methyl, m is 2, and n is 0 or 1.
3. The one-component heat-resistant epoxy resin composition according to claim 1, wherein the polythiol compound is one or more selected from the group consisting of tris (3-mercaptoethyl) isocyanurate, tris (3-mercaptopropyl) isocyanurate, tris (2-mercaptoacetoxyethyl) isocyanurate, tris (3-mercaptopropionyloxyethyl) isocyanurate and tris (3-mercaptobutyryloxyethyl) isocyanurate.
4. The one-component heat-resistant epoxy resin composition according to any one of claims 1 to 3, wherein the weight ratio of the first epoxy resin to the second epoxy resin is 1 (0.8 to 1.2).
5. The one-part heat-resistant epoxy resin composition according to any one of claims 1 to 3, wherein the latent curing agent is one or more selected from dicyandiamide, hydrazide, guanidine compound, modified imidazole, modified amine, urea adduct and microcapsule type curing agent.
6. The one-part heat-resistant epoxy resin composition according to any one of claims 1 to 3, wherein the latent curing agent comprises an amine-epoxy adduct.
7. The one-component heat-resistant epoxy resin composition according to any one of claims 1 to 3, wherein the auxiliary agent is one or more selected from the group consisting of a stabilizer, a polymerization inhibitor, an antioxidant, a flame retardant, a diluent, an adhesion promoter, a silane coupling agent, a dye, a pigment, an antifoaming agent, a leveling agent and an ion scavenger.
8. The one-component heat-resistant epoxy resin composition according to any one of claims 1 to 3, further comprising a filler; the filler is selected from one or more of silicon dioxide, alumina, talc, calcium carbonate, glass microspheres, metal powder and polytetrafluoroethylene filler; the content of the filler is 0 to 10 parts by weight.
9. The method for preparing a one-part heat-resistant epoxy resin composition according to any one of claims 1 to 8, comprising the steps of:
(1) preparing raw materials according to the following components in parts by weight:
20-30 parts of first epoxy resin;
20-30 parts of second epoxy resin;
30-50 parts of polythiol compound;
1-5 parts of a latent curing agent;
0.1-10 parts of an auxiliary agent;
0-10 parts of a filler;
(2) and (2) stirring and mixing the first epoxy resin, the second epoxy resin, the polythiol compound, the auxiliary agent and the optional filler prepared in the step (1) for 0.5 to 2 hours at the temperature of 20 to 30 ℃ and under the vacuum degree of-0.05 MPa to-0.1 MPa, then adding the latent curing agent, stirring and mixing for 0.1 to 1 hour at the temperature of 20 to 30 ℃ and under the vacuum degree of-0.05 MPa to-0.1 MPa, and immediately sealing and packaging.
10. Use of the one-part heat-resistant epoxy resin composition according to any one of claims 1 to 8 as an adhesive or sealant.
11. The use of claim 10, wherein the adhesive is used for bonding of sensors or cameras.
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