CN114989759B - Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof - Google Patents
Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof Download PDFInfo
- Publication number
- CN114989759B CN114989759B CN202111295820.4A CN202111295820A CN114989759B CN 114989759 B CN114989759 B CN 114989759B CN 202111295820 A CN202111295820 A CN 202111295820A CN 114989759 B CN114989759 B CN 114989759B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- parts
- diglycidyl ether
- modified epoxy
- bisphenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 160
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 160
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 spiro orthoester Chemical class 0.000 claims abstract description 49
- 239000007822 coupling agent Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 30
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 29
- 239000004593 Epoxy Substances 0.000 claims description 20
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 9
- DXOOXDXAWNMFOE-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxy)cyclopentyl]oxymethyl]oxirane Chemical compound C1OC1COC1(OCC2OC2)CCCC1 DXOOXDXAWNMFOE-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- LUSCNZBJFBNVDT-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxy)cyclohexyl]oxymethyl]oxirane Chemical compound C1OC1COC1(OCC2OC2)CCCCC1 LUSCNZBJFBNVDT-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004988 m-phenylenediamines Chemical class 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 20
- 239000000853 adhesive Substances 0.000 abstract description 17
- 230000008602 contraction Effects 0.000 abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- WPYCRFCQABTEKC-UHFFFAOYSA-N Diglycidyl resorcinol ether Chemical compound C1OC1COC(C=1)=CC=CC=1OCC1CO1 WPYCRFCQABTEKC-UHFFFAOYSA-N 0.000 description 4
- 241000218378 Magnolia Species 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical class CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The invention relates to the field of C08L7/00, in particular to a modified epoxy resin with low shrinkage, high toughness and low stress and a preparation method thereof. The invention adopts 30 to 50 parts of epoxy resin, 10 to 15 parts of diluent, 10 to 20 parts of spiro orthoester, 10 to 15 parts of curing agent, 1 to 3 parts of coupling agent and 1 to 3 parts of accelerator, and the modified epoxy resin with low shrinkage, high toughness and low stress is obtained through a specific preparation process, thus not only having excellent mechanical properties, but also effectively improving the heat resistance and weather resistance of the modified epoxy resin, and the mass ratio of the epoxy resin to the spiro orthoester is controlled to be (2.5 to 5): 1 effectively improves the volume expansion rate of the modified epoxy resin, reduces the thermal expansion and cold contraction stress, is particularly suitable for the field of preparing low-stress electronic adhesives, and meets the reliable bonding requirement of high-end electronic components.
Description
Technical Field
The invention relates to the field of C09J163/00, in particular to a modified epoxy resin with low shrinkage, high toughness and low stress and a preparation method thereof.
Background
In modern electronic technology, in order to ensure stability of electronic circuits and their optoelectronic components, adhesive packaging is an indispensable link, and epoxy resin adhesives and organic silica gels are widely used in the field of electronic packaging. The volume shrinkage rate is about 5% when the epoxy resin adhesive is cured, the bonding strength is reduced or even degummed due to the residual stress generated by volume shrinkage when the epoxy resin is cured, and if the epoxy resin adhesive is applied to the potting material of the stress sensitive electronic component, the performance of the electronic component is deteriorated and the parameters are drifted. Because the viscosity of the epoxy resin and the curing agent is very high, even part of the epoxy resin exists in a solid state, a large amount of diluent is usually added in the use process to reduce the viscosity of the material, and an aldol condensation dilution system is most commonly used at present, so that the dilution effect is good and the cost is low. However, the raw materials of the aldol condensation dilution system are inflammable and explosive, are extremely volatile and have high toxicity, so that a plurality of hidden troubles are brought to the production and use processes; in addition, as the aldol condensation dilution system is extremely volatile and the characteristic of curing shrinkage of the epoxy system, the shrinkage rate of the material after curing is high, and the adhesive property and filling and reinforcing effects of the material are seriously affected.
Chinese patent CN108485187B discloses a modified epoxy resin material, a preparation method, application and fan blades thereof, wherein the modified epoxy resin with certain heat resistance and weather resistance is obtained by adopting hydrogenated bisphenol A epoxy resin, bisphenol A epoxy resin and hydantoin epoxy resin in the presence of a curing agent, a modifying agent and other auxiliary agents, and the modified epoxy resin is especially suitable for the field of fan blades of wind driven generators, but has certain difference in the requirements of the field of electronic adhesive on low stress, mechanical property and electrical resistance. Chinese patent CN106281171B discloses an epoxy resin soldering flux, a preparation method and application thereof, wherein epoxy resin with high mechanical strength and high cohesiveness is obtained by adopting epoxy resin, rosin resin, curing agent and other auxiliary agents, and the epoxy resin can be stored at room temperature, but the reduction of mechanical property and cohesiveness caused by curing shrinkage of the epoxy resin in the field of electronic adhesive is not fully considered in the actual application of the epoxy resin, and the requirements of practical application cannot be continuously met;
therefore, the modified epoxy resin which has low shrinkage, high toughness and low stress and meets the practical application requirements in the field of electronic adhesives is provided, and has important practical research and application significance.
Disclosure of Invention
The invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, which is prepared from the following raw materials in parts by weight: 30-50 parts of epoxy resin, 10-15 parts of diluent, 10-20 parts of spiro orthoester, 10-15 parts of curing agent, 1-3 parts of coupling agent and 1-3 parts of accelerator.
The epoxy resin is at least one of bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, organic silicon epoxy resin and phenolic epoxy resin.
In order to reduce the viscosity of the bisphenol A epoxy resin and the curing agent, reduce the consumption of the diluent and improve the production benefit, as a preferable technical scheme, the epoxy resin at least comprises bisphenol A epoxy resin and hydrogenated bisphenol F epoxy resin; preferably, the mass ratio of the bisphenol A type epoxy resin to the hydrogenated bisphenol F type epoxy resin is (2-4): (2-5) not only preventing the processing difficulty and unnecessary potential safety hazards caused by the overhigh viscosity of the system, but also effectively improving the mechanical property and weather resistance of the modified epoxy resin, facilitating the subsequent processing and meeting the actual application requirements in the field of electronic adhesive packaging;
because the molecular structure and the molecular weight of the epoxy resin have a certain influence on the stress, in order to reduce the thermal expansion and cold contraction stress of the modified epoxy resin as much as possible, as a preferable technical scheme, the viscosity of the bisphenol A type epoxy resin is 9000-15000mPa.s (25 ℃); the viscosity of the hydrogenated bisphenol F type epoxy resin is 180-250mPa.s (25 ℃);
the epoxy equivalent of the epoxy resin shows the reaction degree of the epoxy resin and the curing agent to a certain extent, and as a preferable technical scheme, the epoxy equivalent of the bisphenol A type epoxy resin is 180-200g/eq; the epoxy equivalent of the hydrogenated bisphenol F type epoxy resin is 160-220g/eq;
the bisphenol A type epoxy resin is at least one selected from jER827, jER828EL, jER828US and jER828 XA; preferably, the bisphenol A type epoxy resin is jER828, the epoxy equivalent is 184-194g/eq, the viscosity is 12000-15000mPa.s (25 ℃), and the bisphenol A type epoxy resin is purchased from Shanghai mass company, inc.;
the hydrogenated bisphenol F type epoxy resin is YL6753, the epoxy equivalent is 180g/eq, the viscosity is 200mPa.s (25 ℃), and the hydrogenated bisphenol F type epoxy resin is purchased from Shanghai mass company, inc.;
the spiro orthoester is at least one of homemade spiro orthoester or homemade modified unsaturated spiro orthoester.
The spiro orthoester is self-made spiro orthoester;
the self-made spiro orthoester is synthesized by the following steps:
(1) Dissolving dihydric alcohol and di-n-butyltin oxide in toluene solvent, and heating and refluxing for 10-15h to obtain a cyclic condensate of di-n-butyltin oxide and dihydric alcohol;
(2) Directly transferring the cyclic condensate generated in the step (1) into a reaction vessel, adding carbon disulfide, and continuously reacting for 5-7 hours at 80-100 ℃ to obtain the self-made spiro orthoester.
As a preferable technical scheme, the heating temperature in the step (1) is 100-130 ℃; preferably, the heating temperature is 120 ℃;
as a preferable technical scheme, the dihydric alcohol in the step (1) is C2-C4 dihydric alcohol; preferably, the dihydric alcohol in the step (1) is ethylene glycol, so that the yield of the self-made spiro orthoester can be improved to the greatest extent;
the carbon disulfide is analytically pure and purchased from Nanjing chemical reagent limited company; the di-n-butyltin oxide is of industrial grade and is purchased from Shanghai Beihe chemical industry Co., ltd; the toluene and the ethylene glycol are analytically pure and purchased from chemical reagent company of national medicine group;
the diluent is at least one selected from diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, cyclohexanediol diglycidyl ether, cyclopentanediol diglycidyl ether and resorcinol diglycidyl ether; preferably, the diluent is a combination of diglycidyl ether, cyclopentanediol diglycidyl ether and resorcinol diglycidyl ether, and preferably, the mass ratio of diglycidyl ether, polyethylene glycol diglycidyl ether and resorcinol diglycidyl ether is 1: (1.2-1.6): (1.5-2), is nontoxic, environment-friendly and efficient, and can reduce the viscosity of the modified epoxy resin in cooperation with the hydrogenated bisphenol F type epoxy resin of the system, effectively improve the weather resistance, heat resistance and toughness of the modified epoxy resin, and meet the higher requirements of the subsequent application in the field of electronic adhesives;
the diglycidyl ether has a CAS number of 2238-07-5 and a purity of 95% and is purchased from Shanghai meyer chemical technologies limited; the CAS number of the polyethylene glycol diglycidyl ether is 39443-66-8, the epoxy value is 0.70-0.80mol/100g, the viscosity is 5-25mPa.s (25 ℃), and the polyethylene glycol diglycidyl ether is purchased from Shanghai Michelia Biochemical technology Co., ltd; the resorcinol diglycidyl ether has a CAS number of 101-90-6 and a purity of 99% and is purchased from Wuhan Rong and Brilliant Biotechnology Co., ltd;
as a preferable technical scheme, the curing agent is at least one selected from polyetheramine, hydrogenated m-phenylenediamine and hydrogenated o-methyl-m-phenylenediamine; preferably, the curing agent is polyetheramine, and fully matches with self-made spiro orthoester modified bisphenol A epoxy resin and hydrogenated bisphenol F epoxy resin of the system, so that the mechanical property and the electrical property of the modified epoxy resin are effectively improved, and the prepared modified epoxy resin is better suitable for the preparation and the application of subsequent electronic adhesives;
the viscosity of the polyetheramine is 8-110mPa.s (25 ℃); the polyetheramine is selected from at least one of Baxxodur EC301, baxxodur EC302 and Baxxodur EC 310;
the CAS number of the polyether amine is 9046-10-0, the model is Baxxodur EC310, and the polyether amine is purchased from Shenzhen Jiadieda New Material technology Co., ltd;
the coupling agent is at least one selected from silane coupling agent and titanate coupling agent;
the coupling agent is an aminosilane coupling agent; the aminosilane coupling agent is selected from at least one of KH 550, KH 560 and KH 570; the aminosilane coupling agent is KH 550, purchased from Shanghai Haique chemical industry Co., ltd;
the accelerator is an organic urea accelerator; the particle size of the organic urea type accelerator is 8-12um;
the organic urea type accelerator is at least one selected from Anyhard 2020P, dyhard UR200, dyhard UR300 and Dyhard UR 500; the organic urea type accelerator is Dyhard UR300, has no halogen, has higher activity and stability, and improves the reaction speed; the Dyhard UR300 was purchased from Shanghai mass industry limited.
The invention also provides a preparation method of the modified epoxy resin with low shrinkage, high toughness and low stress, which at least comprises the following steps:
s1, stirring the epoxy resin, the coupling agent and the diluent for 20-40min at the temperature of 50-70 ℃ and the rotating speed of 600-1000rpm according to parts by weight, then continuously heating to 80-120 ℃, controlling the rotating speed to 500-800rpm, and adding spiro orthoester to react for 2-5h to obtain a modified epoxy resin material A component;
s2, stirring the accelerator and the curing agent for 10-20min at the temperature of 120-150 ℃ and the rotating speed of 400-600rpm according to parts by weight to obtain a component B of the modified epoxy resin material;
s3, mixing the component A of the modified epoxy resin material in the step S1 and the component B of the modified epoxy resin material in the step S2 at 50-70 ℃ for 2-3 hours to obtain the modified epoxy resin.
As a preferable technical scheme, the mass ratio of the epoxy resin to the spiro orthoester in the S1 is (2.5-5): 1, a step of;
the third aspect of the invention provides an application of the modified epoxy resin with low shrinkage, high toughness and low stress, which is particularly suitable for preparing the low-stress electronic adhesive to ensure reliable bonding of high-end electronic devices.
The beneficial effects are that:
1. the invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, which is particularly suitable for preparing a low-stress electronic adhesive to ensure reliable adhesion of high-end electronic devices;
2. bisphenol A epoxy resin and hydrogenated bisphenol F epoxy resin are adopted, and the mass ratio of the bisphenol A epoxy resin to the hydrogenated bisphenol F epoxy resin is (2-4): (2-5) not only preventing the processing difficulty and unnecessary potential safety hazards caused by the overhigh viscosity of the system, but also effectively improving the mechanical property and weather resistance of the modified epoxy resin, facilitating the subsequent processing and meeting the actual application requirements in the field of electronic adhesive packaging; the method comprises the steps of carrying out a first treatment on the surface of the
3. Compounding a bisphenol A epoxy resin with the viscosity of 9000-15000mPa.s (25 ℃) and a hydrogenated bisphenol F epoxy resin with the viscosity of 180-250mPa.s (25 ℃), and further reducing the thermal expansion and contraction stress of the modified epoxy resin and improving the mechanical property and the processability of the modified epoxy resin by controlling the epoxy equivalent of the bisphenol A epoxy resin to be 180-200g/eq and the epoxy equivalent of the hydrogenated bisphenol F epoxy resin to be 160-220g/eq;
4. the spiro orthoester is prepared by adopting a specific preparation process, the epoxy resin is modified by adopting the preparation process of the spiro orthoester, and the mass ratio of the epoxy resin to the spiro orthoester is controlled to be (2.5-5): 1, the volume expansion rate of the modified epoxy resin is effectively improved, the thermal expansion and cold contraction stress is reduced, and the influence on the mechanical property and the adhesive property of the electronic adhesive prepared subsequently is avoided;
5. the preparation of the spiro orthoester modified epoxy resin is realized by a specific preparation process in the presence of a diluent, a curing agent, a coupling agent and an accelerator, so that the prepared modified epoxy resin has excellent heat resistance and weather resistance while the modified epoxy resin has higher adhesive property, mechanical property and low stress, and is better used as a raw material of an electronic adhesive.
Detailed Description
Example 1
In one aspect, embodiment 1 of the present invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, which is prepared from the following raw materials in parts by weight: 40 parts of epoxy resin, 12 parts of diluent, 15 parts of spiro orthoester, 13 parts of curing agent, 2 parts of coupling agent and 2 parts of accelerator.
The epoxy resin comprises bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin; the mass ratio of the bisphenol A type epoxy resin to the hydrogenated bisphenol F type epoxy resin is 3:4, a step of;
the bisphenol A type epoxy resin is jER828, the epoxy equivalent is 184-194g/eq, the viscosity is 12000-15000mPa.s (25 ℃), and the bisphenol A type epoxy resin is purchased from Shanghai mass company, inc.;
the hydrogenated bisphenol F type epoxy resin is YL6753, the epoxy equivalent is 180g/eq, the viscosity is 200mPa.s (25 ℃), and the hydrogenated bisphenol F type epoxy resin is purchased from Shanghai mass company, inc.;
the spiro orthoester is self-made spiro orthoester; the self-made spiro orthoester is synthesized by the following steps:
(1) Dissolving dihydric alcohol and di-n-butyltin oxide in toluene solvent, and heating and refluxing for 12 hours to obtain a cyclic condensate of di-n-butyltin oxide and dihydric alcohol;
(2) And (3) directly transferring the cyclic condensate generated in the step (1) into a reaction container, adding carbon disulfide, and continuously reacting for 6 hours at 90 ℃ to obtain the self-made spiro orthoester.
The heating temperature in the step (1) is 120 ℃; the dihydric alcohol is ethylene glycol;
the carbon disulfide is analytically pure and purchased from Nanjing chemical reagent limited company; the di-n-butyltin oxide is of industrial grade and is purchased from Shanghai Beihe chemical industry Co., ltd; the toluene and the ethylene glycol are analytically pure and purchased from chemical reagent company of national medicine group;
the diluent is a combination of diglycidyl ether, cyclopentanediol diglycidyl ether and resorcinol diglycidyl ether, and the mass ratio of diglycidyl ether to polyethylene glycol diglycidyl ether to resorcinol diglycidyl ether is 1:1.4:1.8;
the diglycidyl ether has a CAS number of 2238-07-5 and a purity of 95% and is purchased from Shanghai meyer chemical technologies limited; the CAS number of the polyethylene glycol diglycidyl ether is 39443-66-8, the epoxy value is 0.70-0.80mol/100g, the viscosity is 5-25mPa.s (25 ℃), and the polyethylene glycol diglycidyl ether is purchased from Shanghai Michelia Biochemical technology Co., ltd; the resorcinol diglycidyl ether has a CAS number of 101-90-6 and a purity of 99% and is purchased from Wuhan Rong and Brilliant Biotechnology Co., ltd;
the curing agent is polyetheramine; the CAS number of the polyether amine is 9046-10-0, the model is Baxxodur EC310, and the polyether amine is purchased from Shenzhen Jiadieda New Material technology Co., ltd;
the coupling agent is an aminosilane coupling agent; the aminosilane coupling agent is KH 550, purchased from Shanghai Haique chemical industry Co., ltd;
the accelerator is an organic urea accelerator; the organic urea type accelerator is Dyhard UR300; the Dyhard UR300 was purchased from Shanghai mass industry limited.
In another aspect, embodiment 1 of the present invention provides a method for preparing a modified epoxy resin with low shrinkage, high toughness and low stress, comprising the steps of:
s1, stirring the epoxy resin, the coupling agent and the diluent for 30min at the temperature of 60 ℃ and the rotating speed of 800rpm according to parts by weight, then continuously heating to 100 ℃, controlling the rotating speed to 600rpm, and adding spiro orthoester to react for 3.5h to obtain a modified epoxy resin material A component;
s2, stirring the accelerator and the curing agent for 15min at the temperature of 135 ℃ and the rotating speed of 500rpm according to parts by weight to obtain a component B of the modified epoxy resin material;
s3, mixing the component A of the modified epoxy resin material in the step S1 and the component B of the modified epoxy resin material in the step S2 at the temperature of 60 ℃ for 2.5 hours to obtain the modified epoxy resin.
The mass ratio of the epoxy resin to the spiro orthoester in the S1 is 8:3.
Example 2
In one aspect, embodiment 2 of the present invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, which is prepared from the following raw materials in parts by weight: 50 parts of epoxy resin, 15 parts of diluent, 20 parts of spiro orthoester, 15 parts of curing agent, 3 parts of coupling agent and 3 parts of accelerator.
The epoxy resin comprises bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin; the mass ratio of the bisphenol A type epoxy resin to the hydrogenated bisphenol F type epoxy resin is 4:5, a step of;
the bisphenol A type epoxy resin is jER828, the epoxy equivalent is 184-194g/eq, the viscosity is 12000-15000mPa.s (25 ℃), and the bisphenol A type epoxy resin is purchased from Shanghai mass company, inc.;
the hydrogenated bisphenol F type epoxy resin is YL6753, the epoxy equivalent is 180g/eq, the viscosity is 200mPa.s (25 ℃), and the hydrogenated bisphenol F type epoxy resin is purchased from Shanghai mass company, inc.;
the spiro orthoester is self-made spiro orthoester; the self-made spiro orthoester is synthesized by the following steps:
(1) Dissolving dihydric alcohol and di-n-butyltin oxide in toluene solvent, and heating and refluxing for 12 hours to obtain a cyclic condensate of di-n-butyltin oxide and dihydric alcohol;
(2) And (3) directly transferring the cyclic condensate generated in the step (1) into a reaction container, adding carbon disulfide, and continuously reacting for 6 hours at 90 ℃ to obtain the self-made spiro orthoester.
The heating temperature in the step (1) is 130 ℃; the dihydric alcohol is propylene glycol;
the carbon disulfide is analytically pure and purchased from Nanjing chemical reagent limited company; the di-n-butyltin oxide is of industrial grade and is purchased from Shanghai Beihe chemical industry Co., ltd; the toluene and the propylene glycol are analytically pure and purchased from chemical reagent company of national medicine group;
the diluent is a combination of diglycidyl ether, cyclopentanediol diglycidyl ether and resorcinol diglycidyl ether, and the mass ratio of diglycidyl ether to polyethylene glycol diglycidyl ether to resorcinol diglycidyl ether is 1:1.6:2;
the diglycidyl ether has a CAS number of 2238-07-5 and a purity of 95% and is purchased from Shanghai meyer chemical technologies limited; the CAS number of the polyethylene glycol diglycidyl ether is 39443-66-8, the epoxy value is 0.70-0.80mol/100g, the viscosity is 5-25mPa.s (25 ℃), and the polyethylene glycol diglycidyl ether is purchased from Shanghai Michelia Biochemical technology Co., ltd; the resorcinol diglycidyl ether has a CAS number of 101-90-6 and a purity of 99% and is purchased from Wuhan Rong and Brilliant Biotechnology Co., ltd;
the curing agent is polyetheramine; the CAS number of the polyether amine is 9046-10-0, the model is Baxxodur EC310, and the polyether amine is purchased from Shenzhen Jiadieda New Material technology Co., ltd;
the coupling agent is an aminosilane coupling agent; the aminosilane coupling agent is KH 550, purchased from Shanghai Haique chemical industry Co., ltd;
the accelerator is an organic urea accelerator; the organic urea type accelerator is Dyhard UR300; the Dyhard UR300 was purchased from Shanghai mass industry limited.
In another aspect, embodiment 2 of the present invention provides a method for preparing a modified epoxy resin with low shrinkage, high toughness and low stress, comprising the steps of:
s1, stirring the epoxy resin, the coupling agent and the diluent for 30min at the temperature of 60 ℃ and the rotating speed of 800rpm according to parts by weight, then continuously heating to 120 ℃, controlling the rotating speed of 800rpm, and adding spiro orthoester to react for 2h to obtain a modified epoxy resin material A component;
s2, stirring the accelerator and the curing agent for 15min at the temperature of 135 ℃ and the rotating speed of 500rpm according to parts by weight to obtain a component B of the modified epoxy resin material;
s3, mixing the component A of the modified epoxy resin material in the step S1 and the component B of the modified epoxy resin material in the step S2 at the temperature of 60 ℃ for 2.5 hours to obtain the modified epoxy resin.
The mass ratio of the epoxy resin to the spiro orthoester in the S1 is 5:2.
example 3
In one aspect, embodiment 3 of the present invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, which is prepared from the following raw materials in parts by weight: 30 parts of epoxy resin, 10 parts of diluent, 10 parts of spiro orthoester, 10 parts of curing agent, 1 part of coupling agent and 1 part of accelerator.
The epoxy resin comprises bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin; the mass ratio of the bisphenol A type epoxy resin to the hydrogenated bisphenol F type epoxy resin is 1:1, a step of;
the bisphenol A type epoxy resin is jER828, the epoxy equivalent is 184-194g/eq, the viscosity is 12000-15000mPa.s (25 ℃), and the bisphenol A type epoxy resin is purchased from Shanghai mass company, inc.;
the hydrogenated bisphenol F type epoxy resin is YL6753, the epoxy equivalent is 180g/eq, the viscosity is 200mPa.s (25 ℃), and the hydrogenated bisphenol F type epoxy resin is purchased from Shanghai mass company, inc.;
the spiro orthoester is self-made spiro orthoester; the self-made spiro orthoester is synthesized by the following steps:
(1) Dissolving dihydric alcohol and di-n-butyltin oxide in toluene solvent, and heating and refluxing for 12 hours to obtain a cyclic condensate of di-n-butyltin oxide and dihydric alcohol;
(2) And (3) directly transferring the cyclic condensate generated in the step (1) into a reaction container, adding carbon disulfide, and continuously reacting for 6 hours at 90 ℃ to obtain the self-made spiro orthoester.
The heating temperature in the step (1) is 110 ℃; the dihydric alcohol is butanediol;
the carbon disulfide is analytically pure and purchased from Nanjing chemical reagent limited company; the di-n-butyltin oxide is of industrial grade and is purchased from Shanghai Beihe chemical industry Co., ltd; the toluene and the ethylene glycol are analytically pure and purchased from chemical reagent company of national medicine group;
the diluent is a combination of diglycidyl ether, cyclopentanediol diglycidyl ether and resorcinol diglycidyl ether, and the mass ratio of diglycidyl ether to polyethylene glycol diglycidyl ether to resorcinol diglycidyl ether is 1:1.2:1.5;
the diglycidyl ether has a CAS number of 2238-07-5 and a purity of 95% and is purchased from Shanghai meyer chemical technologies limited; the CAS number of the polyethylene glycol diglycidyl ether is 39443-66-8, the epoxy value is 0.70-0.80mol/100g, the viscosity is 5-25mPa.s (25 ℃), and the polyethylene glycol diglycidyl ether is purchased from Shanghai Michelia Biochemical technology Co., ltd; the resorcinol diglycidyl ether has a CAS number of 101-90-6 and a purity of 99% and is purchased from Wuhan Rong and Brilliant Biotechnology Co., ltd;
the curing agent is polyetheramine; the CAS number of the polyether amine is 9046-10-0, the model is Baxxodur EC310, and the polyether amine is purchased from Shenzhen Jiadieda New Material technology Co., ltd;
the coupling agent is an aminosilane coupling agent; the aminosilane coupling agent is KH 550, purchased from Shanghai Haique chemical industry Co., ltd;
the accelerator is an organic urea accelerator; the organic urea type accelerator is Dyhard UR300; the Dyhard UR300 was purchased from Shanghai mass industry limited.
In another aspect, embodiment 3 of the present invention provides a method for preparing a modified epoxy resin with low shrinkage, high toughness and low stress, comprising the steps of:
s1, stirring the epoxy resin, the coupling agent and the diluent for 30min at the temperature of 60 ℃ and the rotating speed of 800rpm according to parts by weight, then continuously heating to 90 ℃, controlling the rotating speed to 500rpm, and adding spiro orthoester to react for 5h to obtain a modified epoxy resin material A component;
s2, stirring the accelerator and the curing agent for 15min at the temperature of 135 ℃ and the rotating speed of 500rpm according to parts by weight to obtain a component B of the modified epoxy resin material;
s3, mixing the component A of the modified epoxy resin material in the step S1 and the component B of the modified epoxy resin material in the step S2 at 50 ℃ for 3 hours to obtain the modified epoxy resin.
The mass ratio of the epoxy resin to the spiro orthoester in the S1 is 3:1.
comparative example 1
Comparative example 1 of the present invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, and its specific embodiment is the same as example 1, except that the epoxy resin is bisphenol a type epoxy resin.
Comparative example 2
The embodiment of the invention, comparative example 2, provides a modified epoxy resin with low shrinkage, high toughness and low stress, which is similar to example 1, wherein the dihydric alcohol in the spiro orthoester preparation step (1) is neopentyl alcohol, and is purchased from national pharmaceutical chemicals company, inc.
Comparative example 3
Comparative example 3 of the present invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, which is embodied as in example 1, except that the curing agent is polyamide, CAS number 63428-84-2, and viscosity (40 ℃ C.). 15000-35000mpa.s, purchased from Shanghai microphone Biochemical technologies Co.
Comparative example 4
Comparative example 4 of the present invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, and its specific embodiment is the same as example 1, except that the modified epoxy resin preparation step S1 is: and stirring the epoxy resin, the coupling agent and the diluent for 20min at the temperature of 70 ℃ and the rotating speed of 1000rpm, then continuously heating to 150 ℃, controlling the rotating speed to 1000rpm, and adding spiro orthoester for reaction for 1h to obtain a component A of the modified epoxy resin material.
Comparative example 5
Comparative example 5 of the present invention provides a modified epoxy resin with low shrinkage, high toughness and low stress, and its specific embodiment is the same as example 1, except that the mass ratio of epoxy resin to spiro orthoester in the modified epoxy resin preparation step S1 is 1.8:1.
performance test method
(1) Adhesive strength: the modified epoxy resin parallel samples in 3 examples and comparative examples are respectively taken, uniformly coated on the polished smooth 45# steel surface, the two samples are glued together and fixed, the two samples are placed in a 60 ℃ oven for solidification for 3 hours, and are placed on a universal material testing machine for testing the tensile strength and the shearing strength after being cooled to room temperature, wherein the distance between chucks is 50+/-3 mm, and the stretching speed is 5mm/min.
(2) 180 ° peel strength: referring to GB/T2792-2014, 180-degree peel strength of the modified epoxy resins prepared in examples and comparative examples was measured;
(3) Volume shrinkage rate: the modified epoxy resins prepared in examples and comparative examples were subjected to density ρ before and after curing at 25℃using a ZMD-2 electron densitometer 1 And ρ 2 Calculating the volume shrinkage delta of the modified epoxy resin according to a formula;
the modified epoxy resins prepared in examples 1 to 3 and comparative examples 1 to 5 were subjected to performance evaluation.
Referring to Table 1, table 1 shows the performance test data of the modified epoxy resins prepared in examples 1 to 3 and comparative examples 1 to 5.
Claims (3)
1. The modified epoxy resin with low shrinkage, high toughness and low stress is characterized by comprising the following preparation raw materials in parts by weight: 30-50 parts of epoxy resin, 10-15 parts of diluent, 10-20 parts of spiro orthoester, 10-15 parts of curing agent, 1-3 parts of coupling agent and 1-3 parts of accelerator;
the epoxy resin is a combination of bisphenol A epoxy resin and hydrogenated bisphenol F epoxy resin, and the mass ratio of the bisphenol A epoxy resin to the hydrogenated bisphenol F epoxy resin is (2-4): (2-5); the viscosity of the bisphenol A type epoxy resin at 25 ℃ is 9000-15000mPa.s; the viscosity of the hydrogenated bisphenol F type epoxy resin at 25 ℃ is 180-250mPa.s; the epoxy equivalent of the bisphenol A type epoxy resin is 180-200g/eq; the epoxy equivalent of the hydrogenated bisphenol F type epoxy resin is 160-220g/eq;
the spiro orthoester is self-made spiro orthoester; the self-made spiro orthoester is synthesized by the following steps: (1) Dissolving dihydric alcohol and di-n-butyltin oxide in toluene solvent, and heating and refluxing for 10-15h to obtain a cyclic condensate of di-n-butyltin oxide and dihydric alcohol; (2) Directly transferring the cyclic condensate generated in the step (1) into a reaction container, adding carbon disulfide, and continuously reacting for 5-7 hours at 80-100 ℃ to obtain the self-made spiro orthoester, wherein dihydric alcohol in the step (1) is C2-C4 dihydric alcohol;
the preparation method of the modified epoxy resin with low shrinkage, high toughness and low stress at least comprises the following steps:
s1, stirring the epoxy resin, the coupling agent and the diluent for 20-40min at the temperature of 50-70 ℃ and the rotating speed of 600-1000rpm according to parts by weight, then continuously heating to 80-120 ℃, controlling the rotating speed to 500-800rpm, and adding spiro orthoester to react for 2-5h to obtain a modified epoxy resin material A component;
s2, stirring the accelerator and the curing agent for 10-20min at the temperature of 120-150 ℃ and the rotating speed of 400-600rpm according to parts by weight to obtain a component B of the modified epoxy resin material;
s3, mixing the component A of the modified epoxy resin material in the step S1 and the component B of the modified epoxy resin material in the step S2 at 50-70 ℃ for 2-3 hours to obtain the modified epoxy resin;
the mass ratio of the epoxy resin to the spiro orthoester in the S1 is (2.5-5): 1, a step of;
the curing agent is at least one selected from polyetheramine, hydrogenated m-phenylenediamine and hydrogenated o-methyl m-phenylenediamine.
2. The modified epoxy resin of claim 1, wherein said diluent is at least one selected from the group consisting of diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, cyclohexanediol diglycidyl ether, cyclopentanediol diglycidyl ether, resorcinol diglycidyl ether.
3. The modified epoxy resin with low shrinkage, high toughness and low stress according to claim 1, wherein the diluent is a combination of diglycidyl ether, cyclopentanediol diglycidyl ether and resorcinol diglycidyl ether, and the mass ratio of diglycidyl ether, polyethylene glycol diglycidyl ether and resorcinol diglycidyl ether is 1: (1.2-1.6): (1.5-2).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111295820.4A CN114989759B (en) | 2021-11-03 | 2021-11-03 | Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111295820.4A CN114989759B (en) | 2021-11-03 | 2021-11-03 | Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114989759A CN114989759A (en) | 2022-09-02 |
CN114989759B true CN114989759B (en) | 2024-01-26 |
Family
ID=83018377
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111295820.4A Active CN114989759B (en) | 2021-11-03 | 2021-11-03 | Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114989759B (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11302358A (en) * | 1998-04-22 | 1999-11-02 | Tomoegawa Paper Co Ltd | Photosetting resin composition |
CN104530921A (en) * | 2014-12-30 | 2015-04-22 | 厦门双瑞船舶涂料有限公司 | Method for preparing epoxy heavy corrosion-resistant paint with toughness |
CN107057038A (en) * | 2017-05-12 | 2017-08-18 | 瑞派尔(宜昌)科技集团有限责任公司 | A kind of microdilatancy modified epoxy grouting material and preparation method |
CN107586504A (en) * | 2016-07-07 | 2018-01-16 | 株洲飞鹿高新材料技术股份有限公司 | Color sand self-leveling floor coating of one kind floating and preparation method thereof |
CN109337627A (en) * | 2018-10-17 | 2019-02-15 | 烟台德邦科技有限公司 | A kind of high-performance epoxy adhesive of lower shrinkage low stress |
CN113046008A (en) * | 2021-03-29 | 2021-06-29 | 湖南瑞弗斯科技发展有限公司 | Special epoxy elastic adhesive for high-mechanical-property steel bar sleeve |
-
2021
- 2021-11-03 CN CN202111295820.4A patent/CN114989759B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11302358A (en) * | 1998-04-22 | 1999-11-02 | Tomoegawa Paper Co Ltd | Photosetting resin composition |
CN104530921A (en) * | 2014-12-30 | 2015-04-22 | 厦门双瑞船舶涂料有限公司 | Method for preparing epoxy heavy corrosion-resistant paint with toughness |
CN107586504A (en) * | 2016-07-07 | 2018-01-16 | 株洲飞鹿高新材料技术股份有限公司 | Color sand self-leveling floor coating of one kind floating and preparation method thereof |
CN107057038A (en) * | 2017-05-12 | 2017-08-18 | 瑞派尔(宜昌)科技集团有限责任公司 | A kind of microdilatancy modified epoxy grouting material and preparation method |
CN109337627A (en) * | 2018-10-17 | 2019-02-15 | 烟台德邦科技有限公司 | A kind of high-performance epoxy adhesive of lower shrinkage low stress |
CN113046008A (en) * | 2021-03-29 | 2021-06-29 | 湖南瑞弗斯科技发展有限公司 | Special epoxy elastic adhesive for high-mechanical-property steel bar sleeve |
Also Published As
Publication number | Publication date |
---|---|
CN114989759A (en) | 2022-09-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108892929B (en) | Toughened and reinforced epoxy resin composition | |
CN107652933B (en) | Nanoscale single-component tough epoxy compound for bonding magnetic cores and preparation method thereof | |
US20060135723A1 (en) | Silicon compound containing epoxy group and thermosetting resin composition | |
EP2550310A2 (en) | Toughening agent for epoxy resin compositions | |
CN113881192A (en) | Low-smoke flame-retardant epoxy resin composite material and preparation method thereof | |
CN111876116A (en) | Polyimide modified epoxy resin composite conductive adhesive and preparation method thereof | |
CN115232589A (en) | High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof | |
US6180723B1 (en) | Epoxy resin prepared by reacting poly-p-hydroxystyrene with epichlorohydrin | |
CN114031896A (en) | Epoxy resin composition for carbon fiber winding and preparation method thereof | |
CN114989759B (en) | Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof | |
CN109679284B (en) | Silicon-based imidazole modified high-strength heat-resistant epoxy resin composition and preparation method thereof | |
CN114437657B (en) | Preparation method of high-strength metal epoxy AB glue | |
CN111732871A (en) | Light high-heat-resistance coating and preparation method thereof | |
CN115449211A (en) | Flexible corrosion-resistant PPO resin-based copper-clad plate and preparation method thereof | |
JP2006022146A (en) | Curable resin composition | |
CN115418188A (en) | Composite modified epoxy resin adhesive and preparation method thereof | |
JPH06184131A (en) | Epoxy resin, its production, epoxy resin composition and semiconductor sealing material | |
CN112592666B (en) | 360-DEG C-resistant high-temperature epoxy adhesive and preparation method and application thereof | |
CN113929874A (en) | Epoxy resin composition and preparation method thereof | |
CN114989762A (en) | Conductive adhesive for single-component semiconductor and preparation method thereof | |
CN109370156B (en) | Electronic-grade epoxy resin composition | |
CN108250396B (en) | Environment-friendly high-strength impact-resistant molding compound and preparation method thereof | |
CN111138637A (en) | Anti-aging epoxy resin curing agent and preparation method thereof | |
CN117025149B (en) | Aldehyde-free adhesive for non-stick steel plate and preparation method thereof | |
CN112341756B (en) | Organic silicon modified epoxy resin for robot insulating clothes and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |