CN105567145B - Double-component structural adhesive and preparation method thereof - Google Patents
Double-component structural adhesive and preparation method thereof Download PDFInfo
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- CN105567145B CN105567145B CN201610145818.1A CN201610145818A CN105567145B CN 105567145 B CN105567145 B CN 105567145B CN 201610145818 A CN201610145818 A CN 201610145818A CN 105567145 B CN105567145 B CN 105567145B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 52
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 86
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 86
- 239000012745 toughening agent Substances 0.000 claims abstract description 58
- 239000004593 Epoxy Substances 0.000 claims abstract description 55
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 42
- 229920000768 polyamine Polymers 0.000 claims abstract description 38
- 239000003085 diluting agent Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 229920001971 elastomer Polymers 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 10
- 239000000806 elastomer Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000008240 homogeneous mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 6
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 claims description 3
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims 1
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- -1 amine compounds Chemical class 0.000 description 3
- HVOCVPNSEYAYFS-UHFFFAOYSA-N 1,13-diaminotridecane-4,7,10-trione Chemical compound NCCCC(=O)CCC(=O)CCC(=O)CCCN HVOCVPNSEYAYFS-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a two-component structural adhesive and a preparation method thereof, wherein the two-component structural adhesive comprises the following raw material components in percentage by mass: the component A comprises the following components in percentage by mass of 100 percent: 40-90% of epoxy resin, 5-35% of toughening agent, 3-25% of diluent, 0.1-3% of cross-linking agent and 1-10% of reinforcing filler; the component B comprises the following components in percentage by mass of 100 percent: 20-60% of aliphatic amine polyamine, 10-40% of epoxy resin-aliphatic amine copolymer, 5-20% of toughening agent, 1-10% of ternary amine accelerator and 3-15% of reinforcing filler; wherein the mass ratio of the component A to the component B is 1-10: 1. the adhesive has high bonding strength, can be effectively filled into a slit, effectively prevents the problems of proportion imbalance and incomplete curing, and has the advantages of low curing temperature, long applicable period, simple process, high stability and convenient transportation.
Description
Technical Field
The invention relates to the technical field of application of high polymer materials, in particular to a two-component structural adhesive and a preparation method thereof.
Background
With the continuous development of the precision machinery industry, various novel precision equipment continuously emerge, and the driving force of the precision equipment mainly comes from the application in the fields of the automobile industry and the consumer electronics industry, such as the frequent new development of new energy automobiles, hard disk drives, notebook computers, tablet computers, smart phones and the like. The functions of these devices are becoming more powerful, the operation speed is becoming faster and faster, and the size is becoming smaller and smaller, which leads to the development of the assembly process toward miniaturization. Therefore, how to effectively bond these precision parts during the assembly process to meet the requirements of high efficiency and high yield process becomes a problem to be solved at present. The single-component structural adhesive has wide application in the field of bonding application, is a system with low-temperature storage, no solvent and convenient use, does not need a complex dispensing metering device unlike a double-component structural adhesive, and ensures accurate mixing proportion in a dynamic process, thereby ensuring the design requirement of bonding strength. The single-component structural adhesive can achieve excellent bonding performance after heating and curing only by simple air pressure or mechanical adhesive pressing equipment. The most typical example is epoxy one-component construction glue. In general, dicyandiamide or latent amine compounds are used as the aliphatic amine type polyamine in the one-component epoxy resin structural adhesive. The common characteristic of these aliphatic amine polyamines is that they exist in solid form at normal temperature, have particle sizes in the order of microns, and are uniformly dispersed in the epoxy resin liquid phase. Because of its activity, in order to avoid premature curing, it must be stored in a temperature environment lower than-20 ℃, which brings great inconvenience to transportation and storage, thus limiting its application range. Taking the replacement of a hard disk drive as an example, the fixing of the spindle motor bearing and the fixing of the voice coil motor bearing, which are internal assembly components, are conventionally completed by using single-component epoxy structural adhesive. But with the advent of the new generation of ultra-thin small hard disk drives, the fixed bit gap is as small as only 1-2 microns. The conventional single-component epoxy resin structural adhesive uses solid aliphatic amine polyamine, has wide particle size distribution and most of particles larger than 2 microns, so that in the dispensing process, a large-particle solid curing agent cannot penetrate into a slit to be fixed, the proportion of the structural adhesive is disordered, the bonding performance is seriously influenced, and a hard disk drive cannot normally operate. In view of the above, there is a need to provide a new structural adhesive and a new process for bonding micro-scale slits.
Disclosure of Invention
The invention aims to provide a two-component structural adhesive and a preparation method thereof, the two-component structural adhesive has high bonding strength, can be effectively filled into a slit, effectively prevents the problems of proportion imbalance and incomplete curing, has low curing temperature, long service life, simple process and high stability, and is convenient to transport, and the technical scheme provided by the invention is as follows:
the two-component structural adhesive is characterized by comprising the following raw material components in percentage by mass:
the component A comprises the following components in percentage by mass of 100 percent:
40-90% of epoxy resin, 5-35% of toughening agent, 3-25% of diluent, 0.1-3% of cross-linking agent and 1-10% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
20-60% of aliphatic amine polyamine, 10-40% of epoxy resin-aliphatic amine copolymer, 5-20% of toughening agent, 1-10% of ternary amine accelerator and 3-15% of reinforcing filler;
wherein the mass ratio of the component A to the component B is 1-10: 1.
preferably, in the two-component structural adhesive, the epoxy resin is any one or a mixture of more of the following epoxy resins:
an epoxy resin having an epoxy equivalent of 185-192g/eq and a viscosity of 11000-15000cps at 25 ℃;
an epoxy resin having an epoxy equivalent of 182-192g/eq and a viscosity of 11000-15000cps at 25 ℃;
an epoxy resin having an epoxy equivalent of 165-185g/eq and a viscosity of 3000-7000cps at 25 ℃;
an epoxy resin with an epoxy equivalent of 200-210g/eq and a viscosity of 1600-2000cps at 25 ℃;
epoxy resin with the epoxy equivalent of 280-300g/eq and the viscosity of 8000-10000cps at 25 ℃;
an epoxy resin with an epoxy equivalent of 165-185g/eq and a viscosity of 2500-4500cps at 25 ℃;
epoxy resin with the epoxy equivalent of 210-220g/eq and the viscosity of 1800-2500cps at 25 ℃;
an elastomer modified epoxy resin having an epoxy equivalent of 325-375g/eq and a viscosity of 3000-8000cps at 25 ℃;
an elastomer modified epoxy resin with the epoxy equivalent of 275-305g/eq and the viscosity of 4000-8000cps at 25 ℃;
the epoxy equivalent is 220-240g/eq, and the viscosity at 25 ℃ is 2000-4000 cps;
the epoxy equivalent is 232-254g/eq, and the viscosity at 25 ℃ is 6000-8000 cps;
the epoxy equivalent is 285-310g/eq, and the viscosity at 50 ℃ is 16000-20000 cps.
Preferably, in the two-component structural adhesive, the toughening agent is any one or a mixture of more of the following toughening agents:
carboxyl-terminated liquid nitrile rubber with the average molecular weight of 2500-4500 and the viscosity of 30,000mPa.s at 40 ℃;
amino-terminated liquid nitrile rubber with the average molecular weight of 2500-4500 and the viscosity of 200,000mPa.s at 27 ℃;
core-shell structure methyl methacrylate-butadiene-styrene terpolymer microparticle.
Preferably, in the two-component structural adhesive, the aliphatic amine polyamine is any one or more of the following:
triethylene tetramine with active hydrogen equivalent of 24.3g/eq and viscosity of 40-50mPa.s at 25 ℃;
tetraethylenepentamine with 27g/eq of active hydrogen equivalent and 50-60mPa.s of viscosity at 25 ℃;
2,2, 4-trimethylhexamethylenediamine having an active hydrogen equivalent of 39.6g/eq and a viscosity of 6mPa.s at 25 ℃;
isophoronediamine having an active hydrogen equivalent of 42.6g/eq and a viscosity of 16mPa.s at 25 ℃;
m-xylylenediamine having an active hydrogen equivalent of 34g/eq and a viscosity of 6.8mPa.s at 25 ℃;
4,7, 10-trioxa-1, 13-tridecanediamine having an active hydrogen equivalent of 56g/eq and a viscosity of 13-14.4mPa.s at 25 ℃;
a polyether diamine having an active hydrogen equivalent of 57g/eq and a viscosity of 13.1mPa.s at 25 ℃;
a polyamine having an active hydrogen equivalent of 120g/eq and a viscosity of 40000mPa.s at 25 ℃;
a polyamine having an active hydrogen equivalent of 100g/eq and a viscosity of 11000mPa.s at 25 ℃;
a polyamine having an active hydrogen equivalent of 230g/eq and a viscosity of 6000mPa.s at 25 ℃;
polyetheramine having an active hydrogen equivalent of 60g/eq and a viscosity of 9.5mPa.s at 25 ℃;
an etherdiamine having an active hydrogen equivalent of 26g/eq and a viscosity of 3.2mPa.s at 25 ℃;
a cycloalkylamine having an active hydrogen equivalent of 43g/eq and a viscosity of 19 to 20mPa.s at 25 ℃.
Preferably, in the two-component structural adhesive, the viscosity of the tertiary amine accelerator at 25 ℃ is 190-250 mPa.s.
Preferably, in the two-component structural adhesive, the reinforcing filler is one or a mixture of two of fumed silica and modified fumed silica.
A preparation method of a two-component structural adhesive comprises the following steps:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and uniformly stirring and mixing to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight part, heating to 80 ℃, gradually adding epoxy resin under the protection of nitrogen and stirring to form an epoxy resin-aliphatic amine copolymer, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the flexibilizer and the aliphatic amine polyamine, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of claim 1 to obtain the two-component structural adhesive.
Compared with the prior art, the technical scheme of the invention has the outstanding advantages that the adhesive has high viscosity strength, can be effectively filled into the slit, effectively prevents the problems of proportion imbalance and incomplete curing, has low curing temperature, long service life, simple process, high stability and is convenient to transport.
Detailed Description
The present invention will be described with reference to the following examples, but the scope of the present invention should not be limited thereto.
Example 1
The two-component structural adhesive comprises the following raw material components in percentage by mass:
the component A comprises the following components in percentage by mass of 100 percent:
40% of epoxy resin, 30% of toughening agent, 25% of diluent, 1% of crosslinking agent and 4% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
20% of aliphatic amine polyamine, 40% of epoxy resin-aliphatic amine copolymer, 20% of toughening agent, 10% of tertiary amine accelerator and 10% of reinforcing filler;
wherein the mass ratio of the component A to the component B is 1: 1. the epoxy resin is a mixture of an epoxy resin with the epoxy equivalent of 200-210g/eq, the viscosity at 25 ℃ of 1600-2000cps and an elastomer modified epoxy resin with the epoxy equivalent of 325-375g/eq, the viscosity at 25 ℃ of 3000-8000cps, the aliphatic amine polyamine is a mixture of isophorone diamine with the active hydrogen equivalent of 42.6g/eq, the viscosity at 25 ℃ of 16mPa.s and m-xylylenediamine with the active hydrogen equivalent of 34g/eq and the viscosity at 25 ℃ of 6.8mPa.s, the toughening agent is amino-terminated liquid nitrile rubber with the viscosity at 27 ℃ of 200,000mPa.s, the ternary amine accelerator is a ternary amine accelerator with the viscosity at 25 ℃ of 190-250mPa.s, and the reinforcing filler is fumed silica. The preparation method of the two-component structural adhesive comprises the following steps:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and stirring and mixing uniformly to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight parts, heating to 80 ℃, gradually adding epoxy resin for copolymerization under the protection of nitrogen and stirring, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the toughening agent, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of 1:1 to obtain the double-component structural adhesive.
Example 2
A two-component structural adhesive comprises the following raw material components in parts by weight:
the two-component structural adhesive comprises the following raw material components in percentage by mass:
the component A comprises the following components in percentage by mass of 100 percent:
50% of epoxy resin, 25% of toughening agent, 20% of diluent, 2% of crosslinking agent and 3% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
50% of aliphatic amine polyamine, 20% of epoxy resin-aliphatic amine copolymer, 20% of toughening agent, 5% of tertiary amine accelerator and 5% of reinforcing filler; wherein the mass ratio of the component A to the component B is 4: 1. wherein the epoxy resin adopts an epoxy resin with the epoxy equivalent of 182-192g/eq, the viscosity at 25 ℃ of 11000-15000cps, the epoxy equivalent of 220-240g/eq, the viscosity at 25 ℃ of 2000-4000cps, a mixture of an elastomer modified epoxy resin with the epoxy equivalent of 275-305g/eq and the viscosity at 25 ℃ of 4000-8000cps, the aliphatic amine polyamine adopts a mixture of triethylene tetramine with the active hydrogen equivalent of 24.3g/eq, the viscosity at 25 ℃ of 40-50mPa.s and 2,2, 4-trimethylhexamethylene diamine with the active hydrogen equivalent of 39.6g/eq, the viscosity at 25 ℃ of 6mPa.s, the toughening agent adopts carboxyl-terminated nitrile rubber with the average molecular weight of 4500 and the viscosity at 40 ℃ of 30,000mPa.s, the ternary amine accelerator adopts a ternary amine accelerator with the viscosity at 25 ℃ of 190 mPa.s of 250.s, the reinforcing filler is modified fumed silica.
The preparation method of the two-component structural adhesive comprises the following steps:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and stirring and mixing uniformly to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight parts, heating to 80 ℃, gradually adding epoxy resin for copolymerization under the protection of nitrogen and stirring, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the toughening agent, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of 4:1 to obtain the double-component structural adhesive.
Example 3
The two-component structural adhesive comprises the following raw material components in percentage by mass:
the component A comprises the following components in percentage by mass of 100 percent:
90% of epoxy resin, 5% of toughening agent, 3% of diluent, 1% of crosslinking agent and 1% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
60% of aliphatic amine polyamine, 10% of epoxy resin-aliphatic amine copolymer, 10% of toughening agent, 10% of tertiary amine accelerator and 10% of reinforcing filler; wherein the mass ratio of the component A to the component B is 10: 1.
wherein the epoxy resin adopts a mixture of the nuclear shell rubber modified epoxy resin with the epoxy equivalent of 232-254g/eq, the viscosity at 25 ℃ of 6000-8000cps and the nuclear shell rubber modified epoxy resin with the epoxy equivalent of 285-310g/eq, the viscosity at 50 ℃ of 16000-20000cps, the aliphatic amine polyamine adopts a mixture of the polyether amine with the active hydrogen equivalent of 60g/eq, the viscosity at 25 ℃ of 9.5mPa.s, the active hydrogen equivalent of 26g/eq, the ether diamine with the viscosity at 25 ℃ of 3.2mPa.s and the cyclic alkylamine with the active hydrogen equivalent of 43g/eq and the viscosity at 25 ℃ of 19-20mPa.s, the toughening agent adopts a core-shell structure methyl methacrylate-butadiene-styrene terpolymer particle, the tertiary amine accelerator adopts a tertiary amine accelerator with the viscosity at 25 ℃ of 190-250mPa.s, the reinforcing filler is fumed silica.
The preparation method of the two-component structural adhesive comprises the following steps:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and stirring and mixing uniformly to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight parts, heating to 80 ℃, gradually adding epoxy resin for copolymerization under the protection of nitrogen and stirring, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the toughening agent, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of 10:1 to obtain the double-component structural adhesive.
Example 4
The two-component structural adhesive comprises the following raw material components in percentage by mass:
the component A comprises the following components in percentage by mass of 100 percent:
45% of epoxy resin, 25% of toughening agent, 25% of diluent, 3% of crosslinking agent and 2% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
35% of aliphatic amine polyamine, 35% of epoxy resin-aliphatic amine copolymer, 15% of toughening agent, 10% of tertiary amine accelerator and 5% of reinforcing filler; wherein the mass ratio of the component A to the component B is 6: 1.
wherein the epoxy resin adopts a mixture of an epoxy resin with an epoxy equivalent of 165-185g/eq, a viscosity at 25 ℃ of 2500-4500cps, an epoxy equivalent of 210-220g/eq, an epoxy resin with a viscosity at 25 ℃ of 1800-2500cps, an elastomer modified epoxy resin with an epoxy equivalent of 325-375g/eq and a viscosity at 25 ℃ of 3000-8000cps, the aliphatic amine polyamine adopts a mixture of isophoronediamine with an active hydrogen equivalent of 42.6g/eq, a viscosity at 25 ℃ of 16mPa.s, an active hydrogen equivalent of 34g/eq, m-xylylenediamine with a viscosity at 25 ℃ of 6.8mPa.s and an active hydrogen equivalent of 56g/eq, a mixture of 4,7, 10-trioxo-1, 13-tridecanediamine with a viscosity at 25 ℃ of 13-14.4mPa.s, and the toughening agent adopts a mixture of a methyl methacrylate-butadiene-styrene terpolymer particle with a core-shell structure The triamine accelerator has viscosity of 190-250mPa.s at 25 ℃, and the reinforcing filler is fumed silica.
The preparation method of the two-component structural adhesive comprises the following steps:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and stirring and mixing uniformly to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight parts, heating to 80 ℃, gradually adding epoxy resin for copolymerization under the protection of nitrogen and stirring, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the toughening agent, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of 6:1 to obtain the double-component structural adhesive.
Example 5
The component A comprises the following components in percentage by mass of 100 percent:
55% of epoxy resin, 25% of toughening agent, 10% of diluent, 3% of crosslinking agent and 7% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
45% of aliphatic amine polyamine, 35% of epoxy resin-aliphatic amine copolymer, 15% of toughening agent, 5% of tertiary amine accelerator and 5% of reinforcing filler; wherein the mass ratio of the component A to the component B is 7: 1.
wherein the epoxy resin adopts a mixture of an epoxy resin with an epoxy equivalent of 165-185g/eq, a viscosity at 25 ℃ of 2500-4500cps, an epoxy equivalent of 210-220g/eq, an epoxy resin with a viscosity at 25 ℃ of 1800-2500cps, an elastomer modified epoxy resin with an epoxy equivalent of 325-375g/eq and a viscosity at 25 ℃ of 3000-8000cps, the aliphatic amine polyamine adopts a mixture of isophoronediamine with an active hydrogen equivalent of 42.6g/eq, a viscosity at 25 ℃ of 16mPa.s, an active hydrogen equivalent of 34g/eq, m-xylylenediamine with a viscosity at 25 ℃ of 6.8mPa.s and an active hydrogen equivalent of 56g/eq, a mixture of 4,7, 10-trioxo-1, 13-tridecanediamine with a viscosity at 25 ℃ of 13-14.4mPa.s, and the toughening agent adopts a mixture of a methyl methacrylate-butadiene-styrene terpolymer particle with a core-shell structure The triamine accelerator has viscosity of 190-250mPa.s at 25 ℃, and the reinforcing filler is fumed silica.
The preparation method of the two-component structural adhesive comprises the following steps:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and stirring and mixing uniformly to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight parts, heating to 80 ℃, gradually adding epoxy resin for copolymerization under the protection of nitrogen and stirring, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the toughening agent, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of 7:1 to obtain the double-component structural adhesive.
Example 6
The component A comprises the following components in percentage by mass of 100 percent:
38% of epoxy resin, 32% of toughening agent, 20% of diluent, 2% of crosslinking agent and 8% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
46% of aliphatic amine polyamine, 22% of epoxy resin-aliphatic amine copolymer, 12% of toughening agent, 7% of tertiary amine accelerator and 13% of reinforcing filler; wherein the mass ratio of the component A to the component B is 3: 1.
Wherein the epoxy resin adopts a mixture of an epoxy resin with an epoxy equivalent of 165-185g/eq, a viscosity of 3000-7000cps at 25 ℃, an elastomer modified epoxy resin with an epoxy equivalent of 275-305g/eq and a viscosity of 4000-8000cps at 25 ℃, the aliphatic amine polyamine adopts isophorone diamine with an active hydrogen equivalent of 42.6g/eq, an isophorone diamine with a viscosity of 16mPa.s at 25 ℃, the active hydrogen equivalent of 34g/eq, m-xylylenediamine with a viscosity of 6.8mPa.s at 25 ℃, and a mixture of 4,7, 10-trioxa-1, 13-tridecane diamine with an active hydrogen equivalent of 56g/eq, a viscosity of 13-14.4mPa.s at 25 ℃, the toughening agent adopts a core-shell structure methyl methacrylate-butadiene-styrene terpolymer microparticle, the ternary amine accelerator adopts a ternary amine accelerator with a viscosity of 190-250mPa.s at 25 ℃, the reinforcing filler is fumed silica. The preparation method of the two-component structural adhesive comprises the following steps:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and stirring and mixing uniformly to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight parts, heating to 80 ℃, gradually adding epoxy resin for copolymerization under the protection of nitrogen and stirring, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the toughening agent, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of 3:1 to obtain the double-component structural adhesive. Compared with the existing single-component structural adhesive on the market, the result is as follows:
the raw materials of comparative example 1 comprise, in parts by weight:
the raw materials of comparative example 2 comprise, in parts by weight:
the raw materials of comparative example 3 comprise, in parts by weight:
the components according to comparative examples 1 to 3 were weighed out by mass, placed in a plastic tank, stirred on a high-speed stirrer debubbling machine until a homogeneous mixture was obtained, and then examples 1 to 6 and comparative examples 1 to 3 were tested, with the following results:
| storing | Curing temperature | Degree of curing in the slit | |
| Example 1 | RT | RT | OK |
| Example 2 | RT | RT | OK |
| Example 3 | RT | RT | OK |
| Example 4 | RT | RT | OK |
| Example 5 | RT | RT | OK |
| Example 6 | RT | RT | OK |
| Comparative example 1 | -20℃ | 165℃ | NG |
| Comparative example 2 | -20℃ | 130℃ | NG |
| Comparative example 3 | -20℃ | 100℃ | NG |
Note: RT is room temperature. OK, complete curing. NG, no solidification.
As can be seen from the above table, examples 1 to 6 of the present invention can be cured at normal temperature while exhibiting good adhesion to the micro-scale slit part. The curing of comparative examples 1 to 3 was carried out at high temperature and the micron-sized slit parts were poorly bonded, because the particle size of the solid aliphatic amine polyamine was larger than the slit width and could not penetrate into the slit, so that the epoxy resin-aliphatic amine polyamine ratio was out of balance, resulting in poor curing.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may be readily effected by those skilled in the art, and the invention is thus not limited to the specific details and proportioning examples shown and described herein, without departing from the general concept defined by the claims and their equivalents.
Claims (8)
1. The two-component structural adhesive is characterized by comprising the following raw material components in percentage by mass:
the component A comprises the following components in percentage by mass of 100 percent:
40-90% of epoxy resin, 5-35% of toughening agent, 3-25% of diluent, 0.1-3% of cross-linking agent and 1-10% of reinforcing filler;
the component B comprises the following components in percentage by mass of 100 percent:
20-60% of aliphatic amine polyamine, 10-40% of epoxy resin-aliphatic amine copolymer, 5-20% of toughening agent, 1-10% of ternary amine accelerator and 3-15% of reinforcing filler;
wherein the mass ratio of the component A to the component B is 1-10: 1.
2. the two-component structural adhesive of claim 1, wherein the epoxy resin is any one or more of the following epoxy resins:
an epoxy resin having an epoxy equivalent of 182-192g/eq and a viscosity of 11000-15000cps at 25 ℃;
an epoxy resin having an epoxy equivalent of 165-185g/eq and a viscosity of 3000-7000cps at 25 ℃;
an epoxy resin with an epoxy equivalent of 200-210g/eq and a viscosity of 1600-2000cps at 25 ℃;
epoxy resin with the epoxy equivalent of 280-300g/eq and the viscosity of 8000-10000cps at 25 ℃;
an epoxy resin with an epoxy equivalent of 165-185g/eq and a viscosity of 2500-4500cps at 25 ℃;
epoxy resin with the epoxy equivalent of 210-220g/eq and the viscosity of 1800-2500cps at 25 ℃;
an elastomer modified epoxy resin having an epoxy equivalent of 325-375g/eq and a viscosity of 3000-8000cps at 25 ℃;
an elastomer modified epoxy resin with the epoxy equivalent of 275-305g/eq and the viscosity of 4000-8000cps at 25 ℃;
the epoxy equivalent is 220-240g/eq, and the viscosity at 25 ℃ is 2000-4000 cps;
the epoxy equivalent is 232-254g/eq, and the viscosity at 25 ℃ is 6000-8000 cps;
the epoxy equivalent is 285-310g/eq, and the viscosity at 50 ℃ is 16000-20000 cps.
3. The two-component structural adhesive of claim 1, wherein the diluent is one or more of:
dodecyl glycidyl ether with the epoxy equivalent of 280-295g/eq and the viscosity of 6-9cps at 25 ℃;
an aromatic glycidyl ether having an epoxy equivalent of 175-195g/eq and a viscosity of 5-10cps at 25 ℃;
t-butyl glycidyl ether with an epoxy equivalent of 225-240g/eq and a viscosity of 20-30cps at 25 ℃.
4. The two-component structural adhesive of claim 1, wherein the toughening agent is any one or more of the following toughening agents:
carboxyl-terminated liquid nitrile rubber with the average molecular weight of 2500-4500 and the viscosity of 30,000mPa.s at 40 ℃;
amino-terminated liquid nitrile rubber with the average molecular weight of 2500-4500 and the viscosity of 200,000mPa.s at 27 ℃;
the core-shell structure of methyl methacrylate-butadiene-styrene terpolymer particles.
5. The two-component structural adhesive of claim 1, wherein the aliphatic amine-based polyamine is any one or more of the following:
triethylene tetramine with active hydrogen equivalent of 24.3g/eq and viscosity of 40-50mPa.s at 25 ℃;
tetraethylenepentamine with 27g/eq of active hydrogen equivalent and 50-60mPa.s of viscosity at 25 ℃;
2,2, 4-trimethylhexamethylenediamine having an active hydrogen equivalent of 39.6g/eq and a viscosity of 6mPa.s at 25 ℃;
isophoronediamine having an active hydrogen equivalent of 42.6g/eq and a viscosity of 16mPa.s at 25 ℃;
m-xylylenediamine having an active hydrogen equivalent of 34g/eq and a viscosity of 6.8mPa.s at 25 ℃;
4,7, 10-trioxa-1, 13-tridecanediamine having an active hydrogen equivalent of 56g/eq and a viscosity of 13-14.4mPa.s at 25 ℃;
a polyether diamine having an active hydrogen equivalent of 57g/eq and a viscosity of 13.1mPa.s at 25 ℃;
a polyamine having an active hydrogen equivalent of 120g/eq and a viscosity of 40000mPa.s at 25 ℃;
a polyamine having an active hydrogen equivalent of 100g/eq and a viscosity of 11000mPa.s at 25 ℃;
a polyamine having an active hydrogen equivalent of 230g/eq and a viscosity of 6000mPa.s at 25 ℃;
polyetheramine having an active hydrogen equivalent of 60g/eq and a viscosity of 9.5mPa.s at 25 ℃;
an etherdiamine having an active hydrogen equivalent of 26g/eq and a viscosity of 3.2mPa.s at 25 ℃;
a cycloalkylamine having an active hydrogen equivalent of 43g/eq and a viscosity of 19 to 20mPa.s at 25 ℃.
6. The two-component structural adhesive of claim 1, wherein the viscosity of the tertiary amine accelerator at 25 ℃ is 190-250 mpa.s.
7. The two-component structural adhesive of claim 1, wherein the reinforcing filler is one or a mixture of two of fumed silica and modified fumed silica.
8. The method of claim 4, wherein the method comprises the steps of:
(a) weighing the epoxy resin, the toughening agent, the diluent and the crosslinking agent according to the weight components, putting the epoxy resin, the toughening agent, the diluent and the crosslinking agent into a plastic tank, and stirring the epoxy resin, the toughening agent, the diluent and the crosslinking agent on a high-speed stirring defoaming machine to obtain a homogeneous mixture;
(b) then adding a reinforcing filler into the mixture obtained in the step (a), and uniformly stirring and mixing to obtain a component A;
(c) weighing aliphatic amine polyamine according to the weight part, heating to 80 ℃, gradually adding epoxy resin and modified epoxy resin under the protection of nitrogen and stirring to form an epoxy resin-aliphatic amine copolymer, and carrying out polymerization reaction for 1 hour;
(d) after the polymerization reaction in the step (c) is finished, when the temperature is reduced to 40 ℃, adding a triamine accelerator and uniformly stirring; adding the reinforcing filler, stirring and mixing uniformly, adding the flexibilizer and the aliphatic amine polyamine, and continuously stirring uniformly to obtain a component B;
(e) and (d) uniformly mixing the component A prepared in the step (B) and the component B prepared in the step (d) according to the mass ratio of claim 1 to obtain the two-component structural adhesive.
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| EP3275913B1 (en) * | 2016-07-28 | 2021-11-10 | 3M Innovative Properties Company | High performance epoxy adhesive compositions |
| CN106753143A (en) * | 2016-12-21 | 2017-05-31 | 南京诺邦新材料有限公司 | A kind of low-temperature setting underfill with heat conduction function and preparation method thereof |
| CN107987771A (en) * | 2017-11-30 | 2018-05-04 | 安徽坤大化学锚固有限公司 | A kind of two-component anchor pole steel bonding glue and preparation method thereof |
| CN111234752A (en) * | 2020-03-31 | 2020-06-05 | 苏州巨峰电气绝缘系统股份有限公司 | High-thermal-conductivity electrical insulation packaging material and preparation method thereof |
| CN112480787B (en) * | 2020-12-16 | 2022-06-14 | 中国科学院兰州化学物理研究所 | Polymer mineral gap filler for engine containment ring and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103068946A (en) * | 2010-08-10 | 2013-04-24 | 3M创新有限公司 | Epoxy structural adhesive |
| CN103160234A (en) * | 2013-04-09 | 2013-06-19 | 南京大学 | High-performance thermosetting epoxy resin adhesive for roads and bridges and preparation method thereof |
| CN105062395A (en) * | 2015-08-21 | 2015-11-18 | 广州市白云化工实业有限公司 | Two-component epoxy glue and preparation method thereof |
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| CN103068946A (en) * | 2010-08-10 | 2013-04-24 | 3M创新有限公司 | Epoxy structural adhesive |
| CN103160234A (en) * | 2013-04-09 | 2013-06-19 | 南京大学 | High-performance thermosetting epoxy resin adhesive for roads and bridges and preparation method thereof |
| CN105062395A (en) * | 2015-08-21 | 2015-11-18 | 广州市白云化工实业有限公司 | Two-component epoxy glue and preparation method thereof |
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