CN103242792A - Primer for metal substrate structural bonding and preparation method thereof - Google Patents
Primer for metal substrate structural bonding and preparation method thereof Download PDFInfo
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- CN103242792A CN103242792A CN2013101986507A CN201310198650A CN103242792A CN 103242792 A CN103242792 A CN 103242792A CN 2013101986507 A CN2013101986507 A CN 2013101986507A CN 201310198650 A CN201310198650 A CN 201310198650A CN 103242792 A CN103242792 A CN 103242792A
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Abstract
The invention relates to a primer for metal substrate structural bonding and a preparation method thereof. The invention aims to solve the problems of narrow technical applicability and short storage period in the existing primer for metal substrate structural bonding. The primer for metal substrate structural bonding is prepared from the following components in parts by mass: 5.6-24.7 parts of epoxy resin system, 1.5-4.1 parts of curing system and 68.4-92.3 parts of solvent system. The preparation method comprises the following steps: 1. preparing the epoxy resin system; 2. preparing the curing system; and 3. weighing 5.6-24.7 parts of epoxy resin system, 1.5-4.1 parts of curing system and 68.4-92.3 parts of solvent system, putting in a stirring unit, and sufficiently stirring until no precipitate exists to obtain the primer for metal substrate structural bonding. The invention is applicable to the field of preparation of primers for metal substrate structural bonding.
Description
Technical field
The present invention relates to a kind of metal base structural adhesive bonding primer and preparation method thereof.
Background technology
The surface treatment of metal base is the prerequisite that the metal base structural adhesive bonding obtains best Joint strength.Metallic substrate surface after the processing no longer includes grease, dust dirt and zone of oxidation.Secondary pollution for fear of the metal to be treated substrate surface influences adhesiveproperties, in general requirement 8 hours after processing metal base is carried out bondingly, has so just limited ease of use.In this case, the metal base structural adhesive bonding has just been brought into play positive effect with primer, at the metallic substrate surface spraying of having handled well or brushing primer, can prolong the shelf-time of the metallic surface of handling well, and in the hardware use, play the rot-resistant effect.Primer should be complementary with glued membrane with structural adhesive bonding in addition, does not influence bonding strength and the performance of glued membrane self.
It is short with the primer shelf lives to be used at present the metal base structural adhesive bonding, only can preserve at ambient temperature about a week, as the storage period of BR127 primer under 23 ℃ of envrionment temperatures of Cytec company be 10 days.In addition, in the primer use, the primer that exists each company to produce is good with the glued membrane matching of producing with company, but the problem not good with other company similar glued membrane matching causes primer technology suitability narrow.
Summary of the invention
The present invention will solve the problem that existing metal base structural adhesive bonding is narrow with primer technology suitability and the shelf lives is short, and a kind of metal base structural adhesive bonding primer and preparation method thereof is provided.
A kind of metal base structural adhesive bonding of the present invention primer is characterized in that the metal base structural adhesive bonding is to be made by 5.6～24.7 parts of epoxy systems, 1.5～4.1 parts of curing systems and 68.4～92.3 parts of solvent systems with primer by mass fraction; Wherein the epoxy system is (8～12.5) by Resins, epoxy, toughner and thinner by mass ratio: (2～5): 1 forms; Curing system by amine curing agent and curing catalyst in mass ratio (6～12): 1 ratio is formed.
A kind of metal base structural adhesive bonding of the present invention preparation method of primer, carry out according to the following steps:
One, preparation epoxy system: (8～12.5) part Resins, epoxy is heated to 120 ℃～160 ℃, add (2～5) part toughner then, continue reaction after 1 hour～3 hours at 140～180 ℃, temperature of reaction system is controlled below 120 ℃, add 1 part of thinner, obtain the epoxy system; Wherein said Resins, epoxy is one or both mixtures formed by any ratio in bisphenol A type epoxy resin, bisphenol f type epoxy resin and the novolac epoxy; Toughner is one or more mixtures formed by any ratio in carboxyl end of the liquid acrylonitrile-butadiene rubber, thiorubber, liquid silastic, polyethers, polysulfones, polyethersulfone and the polyimide; Thinner is one or more mixtures formed by any ratio in single epoxy group(ing) reactive thinner propenyl glycidyl ether, butylglycidyl ether and the phenyl glycidyl ether;
Two, preparation curing system: be (6～12) in mass ratio: 1 ratio takes by weighing amine curing agent and curing catalyst, obtains curing system after the mixing; Wherein said amine curing agent is aromatic amine curing agent, be by diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3 '-diethyl-4,4 ' diaminodiphenylmethane, 3, in 3 ' two chloro-, 4,4 ' diaminodiphenylmethane, diethyl toluene diamine and the mphenylenediamine one or more are pressed arbitrarily than forming; Solidifying agent promotor is one or more mixtures formed by any ratio in tertiary amine and derivative, organic urea, imidazoles and the P contained compound;
Three, take by weighing 5.6～24.7 parts of epoxy systems, 1.5～4.1 parts of curing systems and 68.4～92.3 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is one or more mixtures formed by any ratio in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and the tetrahydrofuran (THF).
Metal base structural adhesive bonding of the present invention can be used for the epoxy resin-matrix system glued membrane of 110 ℃～180 ℃ of curing with primer, do not influence the adhesiveproperties of glued membrane, 20 days room temperature storage phases, store 12 months performance no changes down for-18 ℃, metal base structural adhesive bonding of the present invention is brushed or is sprayed in the test piece of aluminum base material with primer, room temperature was placed 20 minutes～60 minutes behind the test piece gluing, and primer dry film weight is 4.5g/m
2～9.9g/m
2, thickness 3.0 μ m～10.0 μ m solidified 1 hour～2 hours at 100 ℃～130 ℃ then, and the wiping that the primer layer after the curing can anti-butanone solvent illustrates that metal base structural adhesive bonding of the present invention is good to the wetting property of aluminum base material with primer, and bonding force is strong.Metal base structural adhesive bonding of the present invention is prepared easily with primer, can strengthen the sticking power of structural film adhesive and metal base effectively, is easier to realize industrialization.In addition, metal base structural adhesive bonding of the present invention has that viscosity is low, stable performance, is easy to advantages such as coating with primer, can form the good metallic substrate surface coating of performance.
Description of drawings
Fig. 1 uses the salt spray resistance test pattern of primer for the metal base structural adhesive bonding of test 6 preparations.
Embodiment
Embodiment one: a kind of metal base structural adhesive bonding of present embodiment primer is characterized in that the metal base structural adhesive bonding is to be made by 5.6～24.7 parts of epoxy systems, 1.5～4.1 parts of curing systems and 68.4～92.3 parts of solvent systems with primer by mass fraction; Wherein the epoxy system is (8～12.5) by Resins, epoxy, toughner and thinner by mass ratio: (2～5): 1 forms; Curing system by amine curing agent and curing catalyst in mass ratio (6～12): 1 ratio is formed.
The metal base structural adhesive bonding of present embodiment can be used for the epoxy resin-matrix system glued membrane of 110 ℃～180 ℃ of curing with primer, do not influence the adhesiveproperties of glued membrane, 20 days room temperature storage phases, store 12 months performance no changes down for-18 ℃, the metal base structural adhesive bonding of present embodiment is brushed or is sprayed in the test piece of aluminum base material with primer, room temperature was placed 20 minutes～60 minutes behind the test piece gluing, and primer dry film weight is 4.5g/m
2～9.9g/m
2Thickness 3.0 μ m～10.0 μ m solidified 1 hour～2 hours at 100 ℃～130 ℃ then, the wiping that the primer layer after the curing can anti-butanone solvent, the metal base structural adhesive bonding that present embodiment is described is good to the wetting property of aluminum base material with primer, and bonding force is strong.
Embodiment two: what present embodiment and embodiment one were different is: Resins, epoxy be in bisphenol A type epoxy resin, bisphenol f type epoxy resin and the novolac epoxy one or both by any than mixtures of forming.Other are identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is: toughner is one or more mixtures formed by any ratio in carboxyl end of the liquid acrylonitrile-butadiene rubber, thiorubber, liquid silastic, polyethers, polysulfones, polyethersulfone and the polyimide.Other are identical with embodiment one or two.
Embodiment four: what present embodiment was different with one of embodiment one to three is: thinner is one or more mixtures formed by any ratio in single epoxy group(ing) reactive thinner propenyl glycidyl ether, butylglycidyl ether and the phenyl glycidyl ether.Other steps are identical with one of embodiment one to three with parameter.
Embodiment five: what present embodiment was different with one of embodiment one to four is: amine curing agent is aromatic amine curing agent, be by diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3 '-diethyl-4,4 ' diaminodiphenylmethane, 3, in 3 ' two chloro-, 4,4 ' diaminodiphenylmethane, diethyl toluene diamine and the mphenylenediamine one or more are pressed arbitrarily than forming.Other steps are identical with one of embodiment one to four with parameter.
Embodiment six: what present embodiment was different with one of embodiment one to five is: solidifying agent promotor is one or more mixtures formed by any ratio in tertiary amine and derivative, organic urea, imidazoles and the P contained compound.Other steps are identical with one of embodiment one to five with parameter.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: solvent system is one or more mixtures formed by any ratio in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and the tetrahydrofuran (THF).Other steps are identical with one of embodiment one to six with parameter.
Embodiment eight: a kind of metal base structural adhesive bonding of present embodiment preparation method of primer is characterized in that the metal base structural adhesive bonding carries out according to the following steps with the preparation method of primer:
One, preparation epoxy system: take by weighing 8～12.5 parts of Resins, epoxy, 2～5 parts of toughner and 1 part of thinner by massfraction; 8～12.5 parts of Resins, epoxy that will take by weighing then are heated to 120 ℃～160 ℃, add 2～5 parts of toughner then, behind 140～180 ℃ of continuation reaction 1～3h, temperature of reaction system is controlled at 100 ℃～120 ℃, add 1 part of thinner, obtain the epoxy system; Wherein said Resins, epoxy is one or both mixtures formed by any ratio in bisphenol A type epoxy resin, bisphenol f type epoxy resin and the novolac epoxy; Toughner is one or more mixtures formed by any ratio in carboxyl end of the liquid acrylonitrile-butadiene rubber, thiorubber, liquid silastic, polyethers, polysulfones, polyethersulfone and the polyimide; Thinner is one or more mixtures formed by any ratio in single epoxy group(ing) reactive thinner propenyl glycidyl ether, butylglycidyl ether and the phenyl glycidyl ether;
Two, preparation curing system: be (6～12) in mass ratio: 1 ratio takes by weighing amine curing agent and curing catalyst, obtains curing system after the mixing; Wherein said amine curing agent is aromatic amine curing agent, be by diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3 '-diethyl-4,4 ' diaminodiphenylmethane, 3, in 3 ' two chloro-, 4,4 ' diaminodiphenylmethane, diethyl toluene diamine and the mphenylenediamine one or more are pressed arbitrarily than forming; Solidifying agent promotor is one or more mixtures formed by any ratio in tertiary amine and derivative, organic urea, imidazoles and the P contained compound;
Three, take by weighing 5.6～24.7 parts of epoxy systems, 1.5～4.1 parts of curing systems and 68.4～92.3 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is one or more mixtures formed by any ratio in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and the tetrahydrofuran (THF).
The metal base structural adhesive bonding of present embodiment is prepared easily with primer, can strengthen the sticking power of structural film adhesive and metal base effectively, is easier to realize industrialization.In addition, the metal base structural adhesive bonding of present embodiment has that viscosity is low, stable performance, is easy to advantages such as coating with primer, can form the good metallic substrate surface coating of performance.
Embodiment nine: what present embodiment and embodiment eight were different is: in the step 1 with temperature of reaction system control at 100～110 ℃.Other are identical with embodiment eight.
Embodiment ten: what present embodiment was different with embodiment eight or nine is: the whipping device in the step 3 is tightness system, and the rotating speed of stirring is 100～500 commentaries on classics/min.Other are identical with embodiment eight or nine.
By following verification experimental verification beneficial effect of the present invention:
Test 1, this tests a kind of metal base structural adhesive bonding primer, is to be made by epoxy system, curing system and solvent system; The preparation method carries out according to the following steps:
One, preparation epoxy system: take by weighing 500g Resins, epoxy, 150g toughner and 32g thinner; Then the 500g Resins, epoxy that takes by weighing is heated to 150 ℃, adds 150g toughner then, behind 150 ℃ of continuation reaction 1.5h, temperature of reaction system control at 100 ℃, is added the 32g thinner, obtain the epoxy system; Wherein said Resins, epoxy is bisphenol A type epoxy resin E-51; Toughner is polysulfones; Thinner is butylglycidyl ether;
Two, preparation curing system: be that 11.4: 1 ratio takes by weighing amine curing agent and curing catalyst in mass ratio, obtain curing system after the mixing; Wherein said amine curing agent is diaminodiphenylsulfone(DDS); Solidifying agent promotor is organic urea;
Three, take by weighing 7.9 parts of epoxy systems, 2.1 parts of curing systems and 90 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is the mixture of butanone, ethyl acetate and tetrahydrofuran (THF), and mass ratio is 4: 2: 1.
Test 2, this tests a kind of metal base structural adhesive bonding primer, is to be made by epoxy system, curing system and solvent system; The preparation method carries out according to the following steps:
One, preparation epoxy system: take by weighing 500g Resins, epoxy, 150g toughner and 28g thinner; Then the 500g Resins, epoxy that takes by weighing is heated to 150 ℃, adds 150g toughner then, behind 150 ℃ of continuation reaction 1.5h, temperature of reaction system control at 105 ℃, is added the 28g thinner, obtain the epoxy system; Wherein said Resins, epoxy is bisphenol A type epoxy resin E-51; Toughner is polysulfones; Thinner is butylglycidyl ether;
Two, preparation curing system: be that 9.2: 1 ratio takes by weighing amine curing agent and curing catalyst in mass ratio, obtain curing system after the mixing; Wherein said amine curing agent is diaminodiphenylsulfone(DDS); Solidifying agent promotor is organic urea;
Three, take by weighing 7.9 parts of epoxy systems, 1.7 parts of curing systems and 87 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is the mixture of butanone, ethyl acetate and tetrahydrofuran (THF), and mass ratio is 5: 1: 1.
Test 3, this tests a kind of metal base structural adhesive bonding primer, is to be made by epoxy system, curing system and solvent system; The preparation method carries out according to the following steps:
One, preparation epoxy system: take by weighing 500g Resins, epoxy, 110g toughner and 40g thinner; Then the 500g Resins, epoxy that takes by weighing is heated to 150 ℃, adds 110g toughner then, behind 150 ℃ of continuation reaction 1.5h, temperature of reaction system control at 120 ℃, is added the 40g thinner, obtain the epoxy system; Wherein said Resins, epoxy is bisphenol A type epoxy resin E-51; Toughner is polyethersulfone; Thinner is butylglycidyl ether;
Two, preparation curing system: be that 8: 1 ratio takes by weighing amine curing agent and curing catalyst in mass ratio, obtain curing system after the mixing; Wherein said amine curing agent is 3,3 '-diethyl-4,4 ' diaminodiphenylmethane; Solidifying agent promotor is organic urea;
Three, take by weighing 7 parts of epoxy systems, 1.3 parts of curing systems and 82 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is tetrahydrofuran (THF), butanone and diacetone alcohol mixture, and mass ratio is 1: 5.5: 1.5.
Test 4, this tests a kind of metal base structural adhesive bonding primer, is to be made by epoxy system, curing system and solvent system; The preparation method carries out according to the following steps:
One, preparation epoxy system: take by weighing 400g bisphenol A type epoxy resin, 100g novolac epoxy DEN438,110g toughner and 25g thinner; Then with the 500g bisphenol A type epoxy resin that takes by weighing and 100g Resins, epoxy DEN438 Hybrid Heating to 150 ℃, add 110g toughner then, behind 150 ℃ of continuation reaction 1.5h, temperature of reaction system is controlled at 100 ℃, add the 25g thinner, obtain the epoxy system; Wherein said toughner is polyethersulfone; Thinner is the propenyl glycidyl ether;
Two, preparation curing system: be that 8: 1 ratio takes by weighing amine curing agent and curing catalyst in mass ratio, obtain curing system after the mixing; Wherein said amine curing agent is 3,3 '-diethyl-4,4 ' diaminodiphenylmethane; Solidifying agent promotor is organic urea;
Three, take by weighing 6.9 parts of epoxy systems, 1.5 parts of curing systems and 88 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is tetrahydrofuran (THF), butanone and diacetone alcohol mixture, and mass ratio is 1.5: 5: 1.
Test 5, this tests a kind of metal base structural adhesive bonding primer, is to be made by epoxy system, curing system and solvent system; The preparation method carries out according to the following steps:
One, preparation epoxy system: take by weighing 400g bisphenol A type epoxy resin E-51,100g Resins, epoxy DER354,150g toughner and 37g thinner; Then with the 500g bisphenol A type epoxy resin E-51 that takes by weighing, 100g Resins, epoxy DER354 Hybrid Heating to 150 ℃, add 150g toughner then, behind 150 ℃ of continuation reaction 1.5h, temperature of reaction system is controlled at 100 ℃, add the 37g thinner, obtain the epoxy system; Wherein said toughner is polyethersulfone; Thinner is butylglycidyl ether;
Two, preparation curing system: be that 8.4: 1 ratio takes by weighing amine curing agent and curing catalyst in mass ratio, obtain curing system after the mixing; Wherein said amine curing agent is diethyl toluene diamine; Solidifying agent promotor is organic urea;
Three, take by weighing 7.9 parts of epoxy systems, 1.6 parts of curing systems and 88 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is tetrahydrofuran (THF), butanone and diacetone alcohol mixture, and mass ratio is 1.5: 5: 1.
Test 6, this tests a kind of metal base structural adhesive bonding primer, is to be made by epoxy system, curing system and solvent system; The preparation method carries out according to the following steps:
One, preparation epoxy system: take by weighing 400g bisphenol A type epoxy resin, 50g Resins, epoxy DER354,50g Resins, epoxy DEN438,140g toughner and 35g thinner; Then with the 500g bisphenol A type epoxy resin, 50g Resins, epoxy DER354 and the 50g Resins, epoxy DEN438 Hybrid Heating to 150 that take by weighing ℃, add 140g toughner then, behind 150 ℃ of continuation reaction 1.5h, temperature of reaction system is controlled at 100 ℃, add the 35g thinner, obtain the epoxy system; Wherein said toughner is polyethersulfone; Thinner is butylglycidyl ether;
Two, preparation curing system: be that 8: 1 ratio takes by weighing amine curing agent and curing catalyst in mass ratio, obtain curing system after the mixing; Wherein said amine curing agent is diethyl toluene diamine; Solidifying agent promotor is organic urea;
Three, take by weighing 6.9 parts of epoxy systems, 1.5 parts of curing systems and 85 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is tetrahydrofuran (THF), butanone and diacetone alcohol mixture, and mass ratio is 1.5: 5: 1.
More than test 1～test 6 all add account for whole primer system quality than 1% strontium yellow with account for the silane coupling agent KH560 of whole primer system quality than 0.05%.
With test 1～test 6 metal base structural adhesive bonding primers that prepare, brush or be sprayed at according to HB/Z197-91 " structural adhesive bonding aluminium alloy phosphoric acid technological specification " and carry out on the surface-treated aluminum alloy base material, after at room temperature placing 30 minutes, base material is placed in 60 ℃ of baking ovens baking 30 minutes, in 120 ℃ of baking ovens, solidified 60 minutes then.Primer dry film thickness range after requiring to solidify is between 3.0 μ m～10.0 μ m.The glued membrane sample situation that adopts is as shown in table 1.Adopt BR127, EC3960 primer to compare test with the primer of test 1～6 preparation simultaneously, primer sample situation sees Table 2.
Table 1 primer performance test structural film adhesive
The primer sample that the performance test of table 2 primer is used
BR127, EC3960 primer are carried out anti-butanone test, peel strength test and shearing resistance test with the primer of test 1～6 preparation, the result is shown in table 3～5, by table 3～5 as can be known, the equal ability butanone solvent of the primer wiping of test 1～6 preparation, primer and the structure of not using primer are bonding to compare discovery to using simultaneously, the primer of test 5 preparations is to conservation rate 〉=98% of glued membrane stripping strength, to conservation rate 〉=95% of glued membrane shearing resistance, the primer of preparation can use with different epoxy group(ing) structural film adhesive couplings.
Table 3 primer performance test---anti-butanone test
| ? | Test 1 | Test 2 | Test 3 | Test 4 | Test 5 | Test 6 |
| Anti-butanone whether | Be | Be | Be | Be | Be | Be |
Annotate: carry out this test behind the curing cycle of primer plate through 23 ℃ * 30min+120 ℃ * 60min, test primer film thickness scope is at 2.5 μ m～3.5 μ m, and test is according to ASTM D5402.
Table 4 primer performance test---90 degree stripping strengths (N/mm)
| The glued membrane trade mark/title | No primer | BR127 | 3960 | Test 2 | Test 3 | Test 4 | Test 5 | Test 6 |
| FM73K | 10.780 | 10.190 | 9.521 | 9.541 | 10.550 | 8.030 | 10.670 | 10.173 |
| AF163 | 8.232 | 7.839 | 7.659 | 7.387 | 8.474 | 8.013 | 8.129 | 7.946 |
| J-95 | 11.920 | 9.366 | 10.66 | 10.800 | 10.982 | 8.794 | 11.680 | 9.890 |
| J-272 | 9.780 | 10.160 | 8.49 | 9.352 | 10.27 | 9.722 | 9.786 | 9.46 |
| J-159 | 8.451 | 7.239 | 7.376 | 7.564 | 8.728 | 7.378 | 8.542 | 7.923 |
| J-159 | 10.42 | 8.274 | 8.937 | 9.743 | 10.50 | 7.990 | 10.270 | 9.740 |
Annotate: the peel strength test covering is the thick 2024-T3 alclad of 0.3mm, and backboard is the thick 2024-T3 alclad of 1.6mm, and the test foundation is GJB446.Each test data is the mean value of 6 groups of data in the table.
Table 5 primer performance test---shearing resistance (MPa)
Annotate: the shearing resistance testing substrates is the naked aluminium of the thick 2024-T3 of 2mm, and the overlap joint area is 20mm * 15mm, and room temperature is tested according to GB/T7124, and high temperature test is according to GJB444.Each test data is the mean value of 6 groups of test datas in the table.
In addition, the primer of testing 5 preparations has been carried out further performance test, result such as table 6 and shown in Figure 1 as shown in Table 6, solidify back primer film and base material adhesivity, satisfactory mechanical property.Fig. 1 is the primer of test 5 preparations, and the salt spray resistance test pattern does not have catabiosis from cut apart from the primer coating or the base material that surpass 3.2mm as seen from Figure 1, and other test result in the associative list 6 illustrates that this primer environmental resistance is good.
Table 6
Annotate: test is of a size of 100mm * 150mm * 0.5mm with the naked aluminium sheet of 2024-T3 and 2024-T3 alclad sheet.
The primers of testing 5 preparations have been carried out the performance test of storage period, the results are shown in Table 7, illustrated under 23 ℃, storage period 〉=20 of primer day.
Test storage period of table 7 primer
Annotate: to peel off the data of shearing with room temperature be the mean value of 5 groups of data to 90 degree in the form.
Claims (10)
1. a metal base structural adhesive bonding primer is characterized in that the metal base structural adhesive bonding is to be made by 5.6～24.7 parts of epoxy systems, 1.5～4.1 parts of curing systems and 68.4～92.3 parts of solvent systems with primer by mass fraction; Wherein the epoxy system is (8～12.5) by Resins, epoxy, toughner and thinner by mass ratio: (2～5): 1 forms; Curing system by amine curing agent and curing catalyst in mass ratio (6～12): 1 ratio is formed.
2. a kind of metal base structural adhesive bonding primer according to claim 1 is characterized in that described Resins, epoxy is one or both mixtures formed by any ratio in bisphenol A type epoxy resin, bisphenol f type epoxy resin and the novolac epoxy.
3. a kind of metal base structural adhesive bonding primer according to claim 1 is characterized in that described toughner is one or more mixtures formed by any ratio in carboxyl end of the liquid acrylonitrile-butadiene rubber, thiorubber, liquid silastic, polyethers, polysulfones, polyethersulfone and the polyimide.
4. a kind of metal base structural adhesive bonding primer according to claim 1 is characterized in that described thinner is one or more mixtures formed by any ratio in single epoxy group(ing) reactive thinner propenyl glycidyl ether, butylglycidyl ether and the phenyl glycidyl ether.
5. a kind of metal base structural adhesive bonding primer according to claim 1, it is characterized in that described amine curing agent is aromatic amine curing agent, be by diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3 '-diethyl-4,4 ' diaminodiphenylmethane, 3, in 3 ' two chloro-, 4,4 ' diaminodiphenylmethane, diethyl toluene diamine and the mphenylenediamine one or more are pressed arbitrarily than forming.
6. metal base structural adhesive bonding primer according to claim 1 is characterized in that described solidifying agent promotor is one or more mixtures formed by any ratio in tertiary amine and derivative, organic urea, imidazoles and the P contained compound.
7. metal base structural adhesive bonding primer according to claim 1 is characterized in that described solvent system is one or more mixtures formed by any ratio in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and the tetrahydrofuran (THF).
8. a metal base structural adhesive bonding is characterized in that the metal base structural adhesive bonding carries out according to the following steps with the preparation method of primer with the preparation method of primer:
One, preparation epoxy system: take by weighing 8～12.5 parts of Resins, epoxy, 2～5 parts of toughner and 1 part of thinner by massfraction; 8～12.5 parts of Resins, epoxy that will take by weighing then are heated to 120 ℃～160 ℃, add 2～5 parts of toughner then, behind 140～180 ℃ of continuation reaction 1～3h, temperature of reaction system is controlled at 100～120 ℃, add 1 part of thinner, obtain the epoxy system; Wherein said Resins, epoxy is one or both mixtures formed by any ratio in bisphenol A type epoxy resin, bisphenol f type epoxy resin and the novolac epoxy; Toughner is one or more mixtures formed by any ratio in carboxyl end of the liquid acrylonitrile-butadiene rubber, thiorubber, liquid silastic, polyethers, polysulfones, polyethersulfone and the polyimide; Thinner is one or more mixtures formed by any ratio in single epoxy group(ing) reactive thinner propenyl glycidyl ether, butylglycidyl ether and the phenyl glycidyl ether;
Two, preparation curing system: be (6～12) in mass ratio: 1 ratio takes by weighing amine curing agent and curing catalyst, obtains curing system after the mixing; Wherein said amine curing agent is aromatic amine curing agent, be by diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3 '-diethyl-4,4 ' diaminodiphenylmethane, 3, in 3 ' two chloro-, 4,4 ' diaminodiphenylmethane, diethyl toluene diamine and the mphenylenediamine one or more are pressed arbitrarily than forming; Solidifying agent promotor is one or more mixtures formed by any ratio in tertiary amine and derivative, organic urea, imidazoles and the P contained compound;
Three, take by weighing 5.6～24.7 parts of epoxy systems, 1.5～4.1 parts of curing systems and 68.4～92.3 parts of solvent systems by mass fraction, be placed in the whipping device, be stirred well to sediment-free, obtain metal base structural adhesive bonding primer, namely finish the preparation that the metal base structural adhesive bonding is used primer; Wherein solvent system is one or more mixtures formed by any ratio in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and the tetrahydrofuran (THF).
9. a kind of metal base structural adhesive bonding according to claim 8 is characterized in that in the step 1 temperature of reaction system being controlled at 100～110 ℃ with the preparation method of primer.
10. a kind of metal base structural adhesive bonding according to claim 8 is characterized in that with the preparation method of primer the whipping device in the step 3 is tightness system, and the rotating speed of stirring is 100～500 commentaries on classics/min.
Priority Applications (1)
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| CN104178072A (en) * | 2014-07-24 | 2014-12-03 | 山东华林防腐技术有限公司 | Concrete base wet-curing anticorrosive adhesive material and preparation method thereof |
| CN104449434A (en) * | 2014-12-12 | 2015-03-25 | 青岛驰科工业技术有限公司 | High-temperature-resistant heat curing adhesive film and preparation method |
| CN105255427A (en) * | 2015-11-30 | 2016-01-20 | 贵州航天风华精密设备有限公司 | High-strength adhesive and preparation method thereof |
| CN107083220A (en) * | 2017-04-24 | 2017-08-22 | 海鹰企业集团有限责任公司 | A kind of formula for pouring into a mould polyether-type PU rubber and metal adhesive primer |
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| CN104178072A (en) * | 2014-07-24 | 2014-12-03 | 山东华林防腐技术有限公司 | Concrete base wet-curing anticorrosive adhesive material and preparation method thereof |
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| CN108409152A (en) * | 2018-04-23 | 2018-08-17 | 合肥协耀玻璃制品有限公司 | A kind of sound control glass with air purification function |
| CN108587187A (en) * | 2018-05-16 | 2018-09-28 | 青岛格林沃德新材料科技有限公司 | A kind of abrasion resistant particles glue and preparation method thereof |
| CN109852308A (en) * | 2018-12-24 | 2019-06-07 | 惠州市杜科新材料有限公司 | A kind of fire resistant epoxy glue film and preparation method thereof |
| CN114507483A (en) * | 2022-03-22 | 2022-05-17 | 深圳市图特美高分子材料有限公司 | Flame-retardant insulating glue film for side plate of power battery cell module and preparation method thereof |
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