CN109136898B - Washing-free silane pretreatment liquid - Google Patents
Washing-free silane pretreatment liquid Download PDFInfo
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- CN109136898B CN109136898B CN201811081241.8A CN201811081241A CN109136898B CN 109136898 B CN109136898 B CN 109136898B CN 201811081241 A CN201811081241 A CN 201811081241A CN 109136898 B CN109136898 B CN 109136898B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention relates to a washing-free silane pretreatment liquid, which comprises the following components in parts by weight: 1-5 parts of silane, 1-5 parts of inorganic salt, 1-10 parts of aqueous resin, 1-5 parts of organic acid and 80-97 parts of water, wherein the aqueous resin contains carboxyl, the pH value of the silane pretreatment liquid is 5.5-6.5, the inorganic salt is metal salt capable of performing replacement reaction with a metal substrate under the condition that the pH value is 5.5-6.5, the silane is more than one of aminosilane, epoxysilane and double-bond silane, the organic acid is more than one of lactic acid, citric acid, tannic acid, tartaric acid, pyridine-3-carboxylic acid, phytic acid and oxalic acid, and the aqueous resin is aqueous acrylic resin and/or aqueous polyurethane resin. The washing-free silane pretreatment liquid disclosed by the invention has high compactness of a film formed after metal parts are treated, can be washed without water, can replace the traditional phosphating process, and is economic and environment-friendly.
Description
Technical Field
The invention belongs to the field of metal surface treatment, and relates to a washing-free silane pretreatment solution.
Background
At present, metal parts are often subjected to pre-coating treatment, and the purpose of the pre-coating treatment is to improve the binding force of a paint film such as electrophoretic paint, primer or powder coating and the like with a base material. At present, the coating pretreatment mainly uses the traditional phosphating process, and the traditional phosphating process generally comprises the procedures of oil removal, water washing, phosphating pretreatment, water washing and coating for the coating pretreatment of common metal parts. The purpose of water washing after phosphating pretreatment is to remove incompletely reacted phosphating solution, mainly because the phosphating solution is a strong acid system, if the phosphating solution remains on the surface, the strong acid continues to react with the metal substrate in a humid environment and has gas (such as H) in the presence of gas (such as H)2) Generation of bubbles in the paint film. In addition, the phosphating solution used for the phosphating pretreatment may contain heavy metal salts such as zinc, nickel or manganese. Therefore, the phosphating pretreatment can generate a large amount of phosphorus-containing wastewater, the treatment of the phosphorus-containing wastewater is difficult, and the use of the phosphating pretreatment process is forbidden in certain lake surrounding areas.
In recent years, researchers have developed some silane-containing phosphorus-free treatment liquids, the main components of which are silane hydrolysate, acrylic resin, inorganic acids such as nitric acid and the like, and the phosphorus-free treatment liquids can be used for replacing phosphating liquids in the traditional phosphating process. The general process flow of the non-phosphorus treatment solution containing silane for carrying out the pre-coating treatment on the metal parts comprises oil removal, water washing, non-phosphorus treatment, water washing and coating, the water washing after the non-phosphorus treatment wastes a large amount of manpower and material resources, the economic cost is high, and in addition, due to the existence of the water washing process, the content of acrylic resin is required to be higher, if the content is smaller, the residue is less after the water washing, and the effect is limited. However, the common silane-containing phosphorus-free treatment solution is required to be washed after phosphorus-free treatment of the metal substrate because: 1) the pH value of the conventional silane-containing phosphorus-free treatment solution is generally about 4.0-5.0, and the content of free acid in the treatment solution is high, so that if water washing is not carried out, when a paint film formed after drying is placed in a humid environment, residual acid can free hydrogen ions and can react with a metal base material to generate hydrogen, and meanwhile, the surface of the metal base material is sealed by the paint film, so that the generated hydrogen is difficult to quickly disperse, and the surface of the paint film can generate bubbles after long-time placement, and the paint film is easy to damage; 2) the silane-containing phosphorus-free treatment liquid has high content of inorganic acid, the inorganic acid mainly comprises nitric acid, fluorozirconic acid, fluorotitanic acid and the like, the content of the inorganic acid is too high, the reaction speed is too high, a paint film is too thick, and the coating performance is reduced.
Therefore, it is very important to research a water-washing-free silane pretreatment solution capable of forming a dense film.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a washing-free silane pretreatment solution capable of forming a compact film.
In order to achieve the purpose, the invention adopts the technical scheme that:
the washing-free silane pretreatment liquid comprises the following components in parts by weight:
the water-based resin contains carboxyl, the carboxyl is well combined with epoxy, polyurethane or polyester paint, the carboxyl can react with an epoxy group, can also react with-NH in the polyurethane, and can also react with hydroxyl in the polyester paint, the binding force between a metal substrate and the paint during subsequent coating can be improved, the pH value of the silane pretreatment liquid is 5.5-6.5, the inorganic salt is metal salt which can perform replacement reaction with a metal substrate under the condition that the pH value is 5.5-6.5, and the inorganic salt can play a promoting role, so that the silane treatment liquid can achieve the effect of (4.0-5.0) when the pH value is lower under the condition that the pH value is higher (5.5-6.5).
The silane pretreatment liquid mainly comprises silane hydrolysis liquid, inorganic acid such as nitric acid and the like, the silane pretreatment liquid free of washing by water mainly comprises silane, organic acid, inorganic salt, water-based resin and water, the inorganic salt is used for accelerating the etching of the surface by the organic acid, the inorganic acid can achieve the effect of the inorganic acid by containing a small amount of the organic acid, the use amount of the acid is reduced, the addition of the inorganic acid is avoided, and in addition, the organic acid in the pretreatment liquid has smaller influence on products due to residue compared with the inorganic acid adopted in the prior art.
The pH value of the conventional silane-containing treatment liquid is generally about 4.0-5.0, and when a metal substrate is treated (taking an iron substrate as an example), Fe and acid react first, and Fe which needs to participate in film formation2+Ion-wise, this reaction is generally excessive, resulting in Fe being used2+Excessive, adding hydrogen peroxide in the follow-up process to lead Fe2+Is oxidized into Fe3+And a precipitate formed and was filtered off. For the system of the invention, the pH value is 5.5-6.5, the system is neutral, Fe is firstly mixed with metal ions such as Cu in inorganic salt2+Has replacement and is not easy to cause Fe in the using process2+And meanwhile, after subsequent electrophoresis, the copper is attached to the surface of the material, so that the material has better conductivity compared with iron, and the formed electrophoresis film is more compact and uniform. In addition, the pH value of the invention is relatively high, which is not beneficial to forming free acid, and the corrosion to the metal substrate can be reduced due to the low content of the free acid.
The water-based resin in the silane pretreatment liquid can be bonded with a silane product, so that the density of the film layer is improved, and the anti-corrosion effect of the metal substrate is improved.
The content of each component in the silane pretreatment liquid is required to be within a specific range, otherwise, the washing-free effect is difficult to achieve, if the content of the silane is too high, other components are reduced, and the complexing force of the pure silane and the metal substrate is insufficient; if the content of the inorganic salt is too high, the reaction is too fast, the corrosion to the metal substrate is too strong, and the content of ferrous ions in the solution is high; if the content of the aqueous resin is too high, other components are reduced, and the complexing force of the pure resin and the metal substrate is insufficient; if the content of the organic acid is too high, the reaction is too fast, the corrosion of the metal substrate is too strong, and the content of ferrous ions in the solution is too high.
As a preferred technical scheme:
the silane pretreatment solution free of washing with water is characterized in that the silane is more than one of aminosilane, epoxy silane and double-bond silane. The functional group such as amino, epoxy or double bond is contained in the silane mainly for improving the binding force in the subsequent coating, the scope of the invention is not limited thereto, and common silanes are all suitable for the invention, and only some preferred silanes are listed here.
The aminosilane is more than one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltriethoxysilane.
The silane pretreatment solution free of washing with water is characterized in that the epoxy silane is at least one of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3- [ (2,3) -epoxypropoxy ] propylmethyldimethoxysilane and 3- [ (2,3) -epoxypropoxy ] propylmethyldiethoxysilane.
The silane pretreatment solution without washing with water is characterized in that the double-bond silane is more than one of vinyltrimethoxysilane, vinyltrichlorosilane and vinyltriethoxysilane.
The silane pretreatment solution without washing with water can be applied to the present invention as long as the metal salt can perform a displacement reaction with the metal substrate at a pH of 5.5-6.5, and only some common metal salts are listed here.
The washing-free silane pretreatment solution comprises copper salt, manganese salt, zirconium salt, cerium salt and strontium salt, wherein the copper salt is more than one of copper nitrate, copper sulfate and copper chloride, the manganese salt is manganese nitrate, the zirconium salt is zirconium nitrate, the cerium salt is cerium nitrate, and the strontium salt is strontium nitrate.
The washing-free silane pretreatment solution is characterized in that the organic acid is more than one of lactic acid, citric acid, tannic acid, tartaric acid, pyridine-3-carboxylic acid, phytic acid and oxalic acid. The organic acid of the present invention includes, but is not limited to, organic acids which are commonly used, to name only.
The washing-free silane pretreatment solution is characterized in that the aqueous resin is an aqueous acrylic resin and/or an aqueous polyurethane resin, and the aqueous resin can also be other common carboxyl-containing aqueous resins, so that the aqueous resin can be applied to the invention and is within the protection scope of the invention.
The invention mechanism is as follows:
the washing-free silane pretreatment liquid mainly comprises silane, water-based resin, inorganic salt, organic acid and water, and the washing-free silane pretreatment liquid has the following functions:
the organic acid and the inorganic salt can react with the metal substrate to generate metal ions, and the reaction equation is as follows (taking the iron metal substrate as an example):
2H++Fe→H2+Fe2+；
Fe+Cu2+→Fe2++Cu；
the silane can be hydrolyzed in an aqueous system to form oligomers, the oligomers can be condensed to form silane polymers, the silane polymers can react with metal ions and/or metals to form a film on the surface of a metal substrate, and the reaction equation is as follows:
silane hydrolysis: -Si-OR' + H2O→-Si-OH+R′OH；
The silanol is condensed to form a silane polymer: -Si-OH + HO-Si- → -Si-O-Si- + H2O；
Silane polymers react with metal ions to form a film (taking an iron metal substrate as an example):
-Si-O-Si-OH+Fe2+→Fe-O-Si-O-Si+H+；
silane polymers react with metals to form films: -Si-OH + Me-OH- → -Si-O-Me- + H2O, Me represents a metal element;
the-COOH in the water-based resin can react with the condensed silane polymer (-Si-O-Si-) to form a space network structure, so that gaps formed by silane film formation are filled, and the density of the film layer is improved.
The silane pretreatment solution can be free from washing mainly due to the following reasons:
(1) according to the invention, no strong corrosive inorganic acid is added, only organic acid and inorganic salt are added, and the corrosion effect of residues on the metal substrate is small when the metal substrate is not washed by water;
(2) the invention has less content of added organic acid and inorganic salt, and more content of added inorganic acid in the prior art, and the invention can reduce the adding amount of the organic acid and the inorganic salt, because the capability of reacting with a metal substrate to generate metal ions after the organic acid and the inorganic salt are matched is stronger, and better effect can be achieved without excessive adding amount;
(3) the silane pretreatment liquid has a high overall pH value of 5.5-6.5, the silane pretreatment liquid in the prior art has a pH value of 4.0-5.0 generally, and the quantity of free acid is in inverse proportion to the pH value, so that the generation of free acid can be inhibited, and further, the corrosion to a metal substrate is reduced;
(4) according to the silane pretreatment liquid disclosed by the invention, the silane and the water-based resin are matched with each other to form a compact film layer, the organic acid and the inorganic salt can be isolated from the metal substrate due to the high density of the film layer, and the metal substrate is prevented from being contacted with the organic acid and the inorganic salt, so that the residual organic acid and the inorganic salt are not easy to corrode the metal substrate, and the metal substrate does not need to be washed with water.
Has the advantages that:
(1) the washing-free silane pretreatment solution disclosed by the invention contains water-based resin, and a film formed after a metal part is treated is high in compactness, washing-free and simplified in process;
(2) the washing-free silane pretreatment liquid disclosed by the invention is phosphorus-free, can replace the traditional phosphating process, and is economic and environment-friendly;
(3) the washing-free silane pretreatment solution disclosed by the invention is low in free acid content, and a formed film is not easy to damage when the silane pretreatment solution is stored in a humid environment;
(4) according to the washing-free silane pretreatment liquid, a silane polymer formed by silane hydrolysis and polycondensation can form a space network structure with-COOH in water-based resin, so that gaps formed by silane film forming are filled, and the density of a film layer is improved.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 5.5.
Example 2
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 5.5.
Example 3
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of 3-aminopropyltriethoxysilane and 3- (2, 3-glycidoxy) propyltrimethoxysilane (the mass ratio is 6: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 5.8.
Example 4
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the inorganic salt is a mixture of copper nitrate and copper chloride (mass ratio is 1: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 5.7.
Example 5
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the inorganic salt is a mixture of copper sulfate and copper chloride (the mass ratio is 3: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 6.2.
Example 6
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the inorganic salt is a mixture of copper nitrate, copper sulfate and copper chloride (the mass ratio is 3:2: 2).
The pH value of the prepared silane pretreatment liquid free of washing is 6.5.
Example 7
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (the mass ratio is 7: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 6.0.
Example 8
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the aqueous resin is a mixture of aqueous acrylic resin and aqueous polyurethane resin (the mass ratio is 4: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 5.6.
Example 9
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 5.9.
Example 10
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 5.7.
Example 11
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 6.3.
Example 12
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the aqueous resin is a mixture of aqueous acrylic resin and aqueous polyurethane resin (the mass ratio is 5: 2).
The pH value of the prepared silane pretreatment liquid free of washing is 5.7.
Example 13
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 6.3.
Example 14
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of 3- (2, 3-glycidoxy) propyltrimethoxysilane and 3- (2, 3-glycidoxy) propyltriethoxysilane (the mass ratio is 3:1), and the water-based resin is a mixture of water-based acrylic resin and water-based polyurethane resin (the mass ratio is 4: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 6.5.
Example 15
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein, the silane is a mixture of 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and 3- [ (2,3) -glycidoxy ] propyl methyldiethoxysilane (the mass ratio is 3: 2); the inorganic salt is a mixture of copper nitrate and manganese nitrate (mass ratio is 5:3)
The pH value of the prepared silane pretreatment liquid free of washing is 5.5.
Example 16
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane and 3- [ (2,3) -epoxypropoxy ] propylmethyldiethoxysilane (the mass ratio is 3:1: 1); the inorganic salt is a mixture of copper sulfate and zirconium nitrate (mass ratio is 6: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 5.7.
Example 17
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 6.5.
Example 18
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the inorganic salt is a mixture of copper chloride, cerium nitrate and strontium nitrate (the mass ratio is 3:2: 2); the aqueous resin is a mixture of aqueous acrylic resin and aqueous polyurethane resin (mass ratio is 3: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 6.4.
Example 19
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
the pH value of the prepared silane pretreatment liquid free of washing is 5.5.
Example 20
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is vinyltrimethoxysilane, a mixture of vinyltrichlorosilane and vinyltriethoxysilane (the mass ratio is 5: 3).
The pH value of the prepared silane pretreatment liquid free of washing is 5.9.
Example 21
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of vinyltrichlorosilane and vinyltriethoxysilane (the mass ratio is 8: 3); the inorganic salt is a mixture of copper nitrate and cerium nitrate (mass ratio is 5: 3).
The pH value of the prepared silane pretreatment liquid free of washing is 6.3.
Example 22
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of 3-aminopropyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane and vinyltrimethoxysilane (mass ratio is 2:1: 2).
The pH value of the prepared silane pretreatment liquid free of washing is 6.5.
Example 23
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of 3-aminopropyltrimethoxysilane and vinyltriethoxysilane (the mass ratio is 1: 1); the aqueous resin is a mixture of aqueous acrylic resin and aqueous polyurethane resin (mass ratio is 2: 3).
The pH value of the prepared silane pretreatment liquid free of washing is 6.4.
Example 24
The washing-free silane pretreatment liquid comprises the following components in parts by weight:
wherein the silane is a mixture of 3-aminopropyltriethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and vinyltrimethoxysilane (the mass ratio is 1:1: 1).
The pH value of the prepared silane pretreatment liquid free of washing is 6.2.
The performance test is carried out on the cold-rolled sheet (Bao steel) after being treated by the pretreatment liquid of the invention, and the method specifically comprises the following steps: the water-free silane pretreatment solution prepared in examples 1 to 24 was used, a mixed solution prepared from the water-free treatment solution of the present invention and water at a mass ratio of 2:98 was used for preparing a bath, then the cold-rolled sheet to be treated was subjected to alkali cleaning to remove oil and two water washes, and then the cold-rolled sheet was immersed in the bath solution for 2 minutes and then taken out, and then cured in an oven at 70 ℃ for 5 minutes, followed by electrostatic powder spraying (electrophoretic paint: BASF, Cathoguard 320 (product brand), paint film thickness 20 μm).
The results of the performance test of the treated cold-rolled sheet are shown in table 1, wherein the specific process of the hundred grid test in table 1 is as follows: marking with a hundred-grid cutter at a length of 1mm horizontally and vertically, marking for 100 grids, and testing by adopting a standard ASTM D3359 to test whether a paint film is subjected to paint dropping; the 5J impact test is carried out by adopting a standard ASTM D3359 to test whether a paint film is stripped; carrying out a salt spray test for 1000h common salt spray by adopting a standard DIN 50021, and testing whether the surface of a paint film is foamed after the salt spray test is carried out; salt spray 1000h after scribing, edge expanding corrosion and corrosion width testing, wherein the adopted scribing standard is ISO 17872-2007.
TABLE 1
Claims (7)
1. The washing-free silane pretreatment liquid is characterized by comprising the following components in parts by weight:
the aqueous resin contains carboxyl, the aqueous resin is aqueous acrylic resin and/or aqueous polyurethane resin, the pH value of the silane pretreatment liquid is 5.5-6.5, the inorganic salt is metal salt capable of performing a displacement reaction with the metal substrate under the condition that the pH value is 5.5-6.5, and the metal salt is more than one of copper salt, cerium salt and strontium salt.
2. The washing-free silane pretreatment solution of claim 1, wherein the silane is one or more of aminosilane, epoxy silane and double bond silane.
3. The water-washing-free silane pretreatment solution according to claim 2, wherein the aminosilane is at least one selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -3-aminopropyltriethoxysilane.
4. The water-washing-free silane pretreatment solution according to claim 2, wherein the epoxysilane is at least one selected from the group consisting of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 3- [ (2,3) -glycidoxy ] propylmethyldiethoxysilane.
5. The washing-free silane pretreatment solution of claim 2, wherein the double-bond silane is one or more of vinyltrimethoxysilane, vinyltrichlorosilane and vinyltriethoxysilane.
6. The washing-free silane pretreatment solution of claim 1, wherein the copper salt is one or more of copper nitrate, copper sulfate and copper chloride, the cerium salt is cerium nitrate, and the strontium salt is strontium nitrate.
7. The washing-free silane pretreatment solution of claim 1, wherein the organic acid is one or more of lactic acid, citric acid, tannic acid, tartaric acid, pyridine-3-carboxylic acid, phytic acid and oxalic acid.
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| CN112226752A (en) * | 2020-10-16 | 2021-01-15 | 台州青源精细化工有限公司 | Formula of silane coupling pre-film agent before metal coating and preparation method thereof |
| CN113845843A (en) * | 2021-11-04 | 2021-12-28 | 福建三钢闽光股份有限公司 | Silane composite water-based treating agent for pretreatment before metal surface coating |
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| JP3898302B2 (en) * | 1997-10-03 | 2007-03-28 | 日本パーカライジング株式会社 | Surface treatment agent composition for metal material and treatment method |
| JP2007321224A (en) * | 2006-06-04 | 2007-12-13 | Jfe Steel Kk | CHROMATE-FREE SURFACE-TREATED Al-Zn-BASED ALLOY-PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AND ITS PRODUCTION METHOD |
| CN106756967B (en) * | 2016-12-02 | 2019-01-25 | 兰州理工大学 | A kind of chrome-free tanning agent and the method that aluminum or aluminum alloy surface is passivated |
| CN107460465B (en) * | 2017-08-21 | 2020-03-17 | 佛山市顺德区美硕金属表面技术有限公司 | Silane treatment agent and method for producing silane treatment agent |
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