阅读说明：本技术 一种可提供深加工性能的三价铬钝化液及其制备方法 (Trivalent chromium passivation solution capable of providing deep processing performance and preparation method thereof ) 是由 陆海涛 朱丹青 俞威 陈星� 倪俊刚 于 2021-06-23 设计创作，主要内容包括：本发明公开了一种可提供深加工性能的三价铬钝化液及其制备方法,该钝化液由水和以下主要成分组成：(A)至少含一种二足硅烷的硅烷水解溶液,(B)有机树脂的水性分散体或乳液,(C)水溶性三价铬盐,(D)磷酸或磷酸盐,(E)有机酸和(F)复合润滑剂。经过该钝化液处理的镀锌板可直接进行各类加工成型而无需涂敷机加工油。省略涂油工序不仅为板材加工用户提供了绿色环保的生产环境,同时也帮助用户节省了生产成本并提高了生产效率。本发明还公开了上述钝化液的制备方法。(The invention discloses a trivalent chromium passivation solution capable of providing deep processing performance and a preparation method thereof, wherein the passivation solution comprises water and the following main components: (A) a silane hydrolysis solution containing at least one bipod silane, (B) an aqueous dispersion or emulsion of an organic resin, (C) a water-soluble trivalent chromium salt, (D) phosphoric acid or a phosphoric acid salt, (E) an organic acid, and (F) a composite lubricant. The galvanized sheet treated by the passivating solution can be directly processed and formed without coating machining oil. Omitting the oiling process not only provides a green and environment-friendly production environment for the plate processing users, but also helps the users to save the production cost and improve the production efficiency. The invention also discloses a preparation method of the passivation solution.)

1. A trivalent chromium passivation solution capable of providing deep processing performance is characterized in that: the paint consists of the following components in percentage by weight:

(A) 1 to 10 percent of biped silane hydrolysis solution or mixed hydrolysis solution of biped silane and traditional silane

(B) 1-5% of aqueous dispersion or emulsion of organic resin

(C) 10 to 25 percent of water-soluble trivalent chromium salt

(D) 0.5 to 5 percent of phosphoric acid or phosphate

(E) 1 to 10 percent of organic acid

(F) 1 to 5 percent of composite lubricant

The balance being deionized water.

2. The trivalent chromium passivation solution capable of providing further processing performance as claimed in claim 1, wherein: the dipodal silane in the component (A) is one or more of 1, 2-bis (triethoxysilyl) ethane, 1, 2-bis (trimethoxysilyl) ethane, bis 3- (trimethoxysilyl) propylamine and bis 3- (triethoxysilyl) propylamine 4,4 '-bis (triethoxysilyl) -1,1' -biphenyl.

3. The trivalent chromium passivation solution capable of providing further processing performance as claimed in claim 1, wherein: the traditional silane in the component (A), namely the silane coupling agent, can be one or more of gamma-aminopropyl triethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-mercaptopropyl trimethoxysilane, ethyl orthosilicate and methyl orthosilicate.

4. The trivalent chromium passivation solution capable of providing further processing performance as claimed in claim 1, wherein: the component (B) is one or more of acidic water-based acrylic resin, water-based polyurethane resin, water-based epoxy resin and water-based phenolic resin.

5. The trivalent chromium passivation solution capable of providing further processing performance as claimed in claim 1, wherein: the component (C) is one or more of chromium phosphate, chromium nitrate and chromium sulfate.

6. The trivalent chromium passivation solution capable of providing further processing performance as claimed in claim 1, wherein: the component (D) is selected from phosphoric acid or water-soluble phosphate.

7. The trivalent chromium passivation solution capable of providing further processing performance as claimed in claim 1, wherein: the component (E) is one or more of citric acid, oxalic acid, tannic acid, glycolic acid and pear alcohol.

8. The trivalent chromium passivation solution capable of providing further processing performance as claimed in claim 1, wherein: the component (F) selects paraffin type lubricant as main lubricant, and is compounded with other types of lubricant.

9. A method for preparing trivalent chromium passivation solution capable of providing deep processing property as claimed in claim 1, which is characterized by comprising the following steps: the method comprises the following steps:

(1) preparation of biped silane hydrolysis solution: weighing metered dipotassium silane, stirring and adding the weighed dipotassium silane into deionized water and/or alcohol solvent mixture for hydrolysis, adjusting the pH value of the mixed solution to 4-5 by using acid, and stirring until the solution is clear;

(2) preparation of a conventional silane hydrolysis solution: weighing a metered silane coupling agent, stirring and adding the silane coupling agent into deionized water and/or an alcohol solvent mixture for hydrolysis, adjusting the pH value of a mixed solution to 4-5 by using acid, and stirring until the solution is clear;

(3) mixing the biped silane hydrolysis solution and the traditional silane hydrolysis solution;

(4) preparing trivalent chromium passivation solution:

weighing measured trivalent chromium salt, dissolving the trivalent chromium salt with deionized water at 50-70 ℃, and uniformly stirring to form a trivalent chromium salt solution;

adding phosphoric acid or phosphate and organic acid into a trivalent chromium salt solution, and stirring until the solution is completely dissolved;

adding deionized water to make up for water volatilized in the solution preparation process;

adding the biped silane hydrolysis solution prepared in the step (1) or (3) or the mixed hydrolysis solution of the biped silane and the traditional silane into the trivalent chromium passivation solution while stirring, and uniformly stirring;

while stirring, adding the aqueous dispersion or emulsion of the organic resin and the lubricant, and stirring uniformly.

10. The use of the trivalent chromium passivation solution for providing deep processing property of claim 1 in coating galvanized steel sheets, characterized in that: the method comprises the following steps:

(a) the degreased and cleaned metal surface is contacted with the passivation composition for 1-10 seconds, and the coating mode can be roll coating, dipping or spraying, so that an uncured passivation coating is formed on the metal surface;

(b) heating the uncured passivation layer to a plate temperature of at least 80 ℃ and not greater than 120 ℃ to form a cured passivation layer.

Technical Field

The invention relates to trivalent chromium passivation solution capable of providing deep processing performance and a preparation method thereof.

Background

As a substitute product of the traditional hexavalent chromium passivation solution, the environment-friendly trivalent chromium passivation solution with high cost performance is widely used in the galvanized coil steel industry. On a continuous galvanizing line, trivalent chromium passivation solution is coated on a fresh galvanized plate surface in a roller coating mode, and active ingredients in the passivation solution form a compact passivation layer which is difficult to dissolve in water on the surface of a zinc layer through the reaction principle of dissolution and precipitation (conversion film). The passivation layer provides excellent protective performance for the galvanized sheet.

Recently, in order to further respond to environmental demands, galvanized sheet processing users desire trivalent chromium passivation sheets that provide more convenient performance without compromising production efficiency, such as passivation sheets that can be processed directly without being oiled. On one hand, the omission of the oiling process can solve the problems related to environmental pollution, such as cleaning of the oiling plate after processing and waste oil treatment, and create a healthy green environment-friendly production environment for workers. On the other hand, the simplification of the process also contributes to saving the production cost and improving the production efficiency.

Disclosure of Invention

The invention aims to meet the requirement of a galvanized plate processing user on the multi-functionalization of a trivalent chromium passivation plate, and provides a trivalent chromium passivation solution with excellent corrosion resistance and deep processing property, and a preparation method and application thereof.

The technical solution of the invention is as follows:

the trivalent chromium passivation solution capable of providing deep processing performance is characterized by comprising the following components in percentage by weight:

the dipodal silane in component (A) used in the present invention may be selected from one or more of 1, 2-bis (triethoxysilyl) ethane, 1, 2-bis (trimethoxysilyl) ethane, bis 3- (trimethoxysilyl) propylamine, bis 3- (triethoxysilyl) propylamine 4,4 '-bis (triethoxysilyl) -1,1' -biphenyl.

The conventional silane, i.e., the silane coupling agent, in the component (A) used in the present invention may be one or more selected from gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, tetraethoxysilane, and methylmethacrylate.

The formula of the bivalent silane is (RO)3Si (CH2) nR' (CH2) nSi (OR)3, (wherein OR is hydrolysable silane ester (ester), and n is 0,1,2,3 …). One bipod silane molecule has 2 silicon atoms and 6 hydrolysable silane esters. The silane ester hydrolyzes to yield a siloxy group (Si-OH). In the fully hydrolyzed state, 6 siloxy groups are available for one hydrolyzed podosilane molecule. In contrast, one silane coupling agent molecule (R' (CH2) nsi (or)3) can only obtain 3 siloxy groups by hydrolysis.

These siloxy groups combine with the hydrated oxide layer on the metal surface to form covalent bonds Si-O-Me, Me referring to the metal), which provide excellent adhesion. It must be noted that the Si-O-Me covalent bond can also be hydrolyzed in aqueous corrosive environments (e.g., hot and humid, salt spray, etc.). If a large number of covalent bonds on the metal surface are hydrolyzed, this can result in loss of adhesion. Because the higher-density Si-O-Me covalent bonds can be formed on the metal surface by the podosilane, the hydrolysis resistance of the podosilane is far better than that of the traditional silane. Theoretical calculations have shown that the hydrolysis resistance of the bipedal silane is 10,000 times that of the conventional silane [1 ]. This unique advantage of the dipodal silanes helps to maintain the adhesion of the polymeric coating or adhesive primer to the metal surface in an aqueous corrosive environment, thereby improving the "wet" durability of the overall system.

The traditional inorganic trivalent chromium film passive film is brittle, and the passive film on a galvanized sheet is easy to crack in the machining process, so that the corrosion resistance of the galvanized sheet is poor. The purpose of adding the sufficient silane into the trivalent chromium passivation solution is to further compact the passivation film and improve the breakage resistance of the passivation film in the processing process.

In the present invention, the dipodal silane or silane coupling agent is hydrolyzed in the presence of deionized water and/or an organic solvent such as methanol or ethanol to produce reactive siloxy groups. The hydrolysis is generally promoted by mechanically stirring the solution and adjusting the pH of the solution to 4-5 with an acid. The pH adjustment is generally carried out using a volatile weak acid such as acetic acid or a strong acid such as sulfuric acid. The concentration of the silane hydrolysis solution used is generally between 1 and 10%, preferably between 2 and 7%.

The component (B) used in the invention can be one or more of acidic aqueous acrylic resin, aqueous polyurethane resin, aqueous epoxy resin and aqueous phenolic resin. The organic resin after drying and crosslinking can improve the compactness and the ductility of the trivalent chromium passivation film. In the invention, the selected acidic resin can be directly added into the prepared trivalent chromium passivation solution. The addition amount of one or a mixture of several aqueous resins is generally between 1 and 10%, preferably between 2 and 5%.

The component (C) in the composition used in the present invention may be one or more selected from chromium phosphate, chromium nitrate and chromium sulfate. The addition amount of one or more water-soluble phosphates is generally 10-25%, preferably 15-20%

The component (D) in the composition used in the present invention may be one or more selected from phosphoric acid or water-soluble phosphates such as monohydrogen phosphate and dihydrogen phosphate. The amount of water or a mixture of several phosphoric acids or phosphates is generally between 0.5 and 5%, preferably between 1 and 3%

The component (E) of the composition used in the present invention may be one or more selected from citric acid, oxalic acid, tannic acid, glycolic acid and mandelic acid. These organic acids have reducing properties, which prevent trivalent chromium ions from being oxidized into harmful hexavalent chromium ions, and participate in film formation. The amount of water or a mixture of several organic acids is generally between 1 and 10%. The preferable addition amount is 2-5%

The component (F) in the composition used in the invention can be selected from paraffin type lubricants, and is compounded with one or more of other types of lubricants such as tetrafluoroethylene fluoropolymer (PTFE), polyethylene and the like. Paraffin-type lubricants are preferred because of their excellent lubricity.

Surfactants such as defoamers, wetting agents, leveling agents, film forming aids, and the like are also used in the present invention to help achieve optimal use of the passivation solution on the production line.

The invention also provides a preparation method of the trivalent chromium passivation solution capable of providing deep processing performance, which comprises the following steps:

(1) preparation of biped silane hydrolysis solution: weighing metered dipotassium silane, stirring and adding the weighed dipotassium silane into deionized water and/or alcohol solvent mixture for hydrolysis, adjusting the pH value of the mixed solution to 4-5 by using acid, and stirring until the solution is clear; if necessary, heating can be carried out to promote hydrolysis;

(2) preparation of a conventional silane hydrolysis solution: weighing a metered silane coupling agent, stirring and adding the silane coupling agent into deionized water and/or an alcohol solvent mixture for hydrolysis, adjusting the pH value of a mixed solution to 4-5 by using acid, and stirring until the solution is clear;

(3) mixing the biped silane hydrolysis solution and the traditional silane hydrolysis solution;

(4) preparing trivalent chromium passivation solution:

weighing measured trivalent chromium salt, dissolving the trivalent chromium salt with deionized water at 50-70 ℃, and uniformly stirring to form a trivalent chromium salt solution;

adding phosphoric acid or phosphate and organic acid into a trivalent chromium salt solution, and stirring until the solution is completely dissolved;

adding deionized water to make up for water volatilized in the solution preparation process;

adding the biped silane hydrolysis solution prepared in the step (1) or (3) or the mixed hydrolysis solution of the biped silane and the traditional silane into the trivalent chromium passivation solution while stirring, and uniformly stirring;

while stirring, adding the aqueous dispersion or emulsion of the organic resin and the lubricant, and stirring uniformly.

The application of trivalent chromium passivating solution capable of providing deep processing performance in coating galvanized steel sheets is characterized in that: the method comprises the following steps:

(a) the degreased and cleaned metal surface is contacted with the passivation composition for 1-10 seconds, and the coating mode can be roll coating, dipping or spraying, so that an uncured passivation coating is formed on the metal surface;

(b) the uncured passivation layer is heated to a plate Temperature (PMT) of at least 80 ℃ and not higher than 120 ℃ to form a cured passivation layer.

The trivalent chromium passivation solution prepared by the invention not only can provide excellent corrosion resistance, but also can endow galvanized steel sheets with unique deep processing performance.

The invention has the following beneficial effects:

does not contain hexavalent chromium compounds, and is an environment-friendly passivation technology; the formed film is compact, the stable performance of the passive film is ensured, and the zinc-plated plate has excellent corrosion resistance and endows the passive zinc-plated plate with deep processing performance. Under the condition of not using processing machine oil, various types of processing and forming can be directly carried out, a green and environment-friendly production environment is provided for downstream customers, and meanwhile, the production cost is saved and the production efficiency is improved for the customers.

Drawings

The invention is further illustrated by the following figures and examples.

FIG. 1 is a schematic diagram comparing the bonding process of hydrolyzed conventional and gemini silanes on hydrated metal substrates.

(a) Hydrolysis of a conventional silane to generate 3 siloxy groups; (b) one bipedal silane can be hydrolyzed to yield 6 siloxy groups.

FIG. 2 is a schematic diagram showing the molecular structure of 1, 2-bis (triethoxysilyl) ethane (abbreviated as BTSE).

Detailed Description

The using method of the passivation solution comprises spraying and roll coating, and the passivation solution is uniformly coated on the surface of the galvanized material. And drying the coated galvanized sheet to form a compact film with the film thickness of 40-80mg/cm 2. The drying plate temperature (PMT) is between 80 and 120 ℃.

The performance test items of the galvanized sheet coated with the trivalent chromium passivating solution capable of being deeply processed are as follows:

corrosion resistance: according to the national standard (GB/T10125-. 1) The salt spray test time of the plate part (unprocessed) is 96 h; 2) after the passivation plate was subjected to 6mm cupping, a salt spray test was carried out for 48 hours, and the corrosion state of the cup protrusion part (deformed part) was observed.

Processability: (1) and (3) measuring the friction coefficient: ALTEK Instrument 9505B test friction coefficient; (2) according to the method for testing the cup punching of the non-ferrous metal of GB/T5125-.

Example (b):

(1) preparation of a 10% 1, 2-bis (triethoxysilyl) ethane (BTSE) hydrolysis solution ("BTSE") 10 parts BTSE silane were weighed, 85 parts deionized water and ethanol mixture (deionized water: ethanol 6: 4 by volume) were added and stirring was started. 5 parts of acetic acid are added with stirring. Stirring was continued for 3 hours and allowed to stand overnight.

(2) Procedure for preparation of 10% 1, 2-bis (triethoxysilyl) ethane + 5% gamma-aminopropyltriethoxysilane (gamma-APS) mixed hydrolysis solution ("BTSE-a"): the above silane hydrolysis solutions were prepared separately. The 10% BTSE hydrolysis solution was prepared as described in (1). The hydrolysis solution of 5% γ -APS was prepared as follows: 5 parts BTSE silane was weighed, a mixture of deionized water and acetic acid (90 parts deionized water +5 parts acetic acid) was added and stirring was started. Stirring is continued for 1 hour. The 10% BTSE and 5% gamma-APS hydrolyzed solutions were then mixed (mixed volume ratio 3: 1).

Trivalent chromium solution ("Cr 3") preparation process: selecting chromium phosphate as main film forming salt, sequentially adding 5 parts of sodium hydrogen phosphate, 5 parts of nitric acid, 20 parts of chromium phosphate solution and 4 parts of oxalic acid, maintaining the temperature at 50 ℃, stirring for 30min, then adding 5 parts of citric acid, stirring for dissolving, and standing to obtain the trivalent chromium passivation solution.

And (2) adding the dipodal silane hydrolysis solution into a trivalent chromium solution under the condition of room temperature while stirring, then adding the aqueous resin and the lubricant emulsion, and stirring uniformly. The components (weight ratio) of the prepared passivation solution are shown in Table 1.

A Galvanized (GI) sample plate (10cm x 15cm) is cleaned by spraying an alkaline degreasing agent for 15 seconds at 55 ℃, washed by tap water for 15 seconds and dried by hot air. On the clean plate surface, the formulated passivation solution was spread down with a #3 draw down bar. An automatic take-off type drying oven was used, and PMT was set to 90 ℃, and the obtained dry film weighed 55mg/m 2. The components of the passivation solution are shown in Table 1.

TABLE 1 (weight ratio)

Examples	BTSE	BTSE-A	Cr3	Acrylic emulsion	Paraffin lubricant	Polyethylene lubricant
							Example 1	7		100	1	5	-
Example 2	5		100	2	3	2
							Example 3	3		100	3	5	-
Example 4	7	5	100	2	3	2
							Example 5		3	100	5	5	-
Example 6		7	100	2	3	2
							Example 7	3	3	100	2	5	-

In the table, acrylic emulsion: 50% solids, pH 3.5; paraffin lubricant: 40% solids, pH 4.5; polyethylene lubricant: 45% solids, pH 3.5

Table 2 summarizes the test results. Two trivalent chromium passivation solution products are selected as comparison references in the test work. Respectively, trivalent chromium passivation solution of the company of comparative example 1-A; comparative example 2 trivalent chromium passivation solution from company B.

Table 2.

The test results show that the trivalent chromium passivation solutions (examples 1-7) prepared by the invention have good initial corrosion resistance and processed corrosion resistance. The processability is much better than that of the common trivalent chromium passivation solution.