CN114672207A - Organic-inorganic composite normal-temperature autophoresis blackening agent - Google Patents

Organic-inorganic composite normal-temperature autophoresis blackening agent Download PDF

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Publication number
CN114672207A
CN114672207A CN202210317383.XA CN202210317383A CN114672207A CN 114672207 A CN114672207 A CN 114672207A CN 202210317383 A CN202210317383 A CN 202210317383A CN 114672207 A CN114672207 A CN 114672207A
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blackening
temperature
blackening agent
organic
inorganic composite
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CN202210317383.XA
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CN114672207B (en
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徐旭
魏大力
余瀚森
聂晓霖
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Nanjing Kerun Industrial Media Co ltd
Nanjing Kerun Industrial Technology Co ltd
Nanjing Kerun New Material Technology Co ltd
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Nanjing Kerun Industrial Media Co ltd
Nanjing Kerun Industrial Technology Co ltd
Nanjing Kerun New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses an organic-inorganic composite normal-temperature autophoresis blackening agent which is prepared by mixing the following components in percentage by mass: 30-40% of water-soluble acrylic resin, 0.5-1.5% of emulsifier, 3-6% of pigment, 1-2% of oxidant, 0.5-0.8% of activator, 0.1-0.5% of inhibitor and the balance of water. Compared with the existing normal-temperature blackening agent, the blackening agent can form an organic film layer on a metal workpiece, and the organic film layer is thicker than an inorganic film layer and has stronger covering power and stronger salt mist performance; compared with the waste heat blackening agent, the blackening agent disclosed by the invention can form a film without heat of a workpiece, so that on one hand, energy is greatly saved, and on the other hand, the problem that the waste heat blackening liquid is easy to break emulsion and precipitate when the workpiece works in a high-temperature environment for a long time can be prevented, so that the stability of the tank liquor is improved, and the service life of the tank liquor is prolonged.

Description

Organic-inorganic composite normal-temperature autophoresis blackening agent
Technical Field
The invention relates to an organic-inorganic composite normal-temperature autophoresis blackening agent.
Background
The blackening process is to form a compact and smooth black protective film on the surface of a metal workpiece by a physical or chemical method, so that the antirust capacity of the metal workpiece is enhanced, and the appearance is beautified. The waste heat blackening technology is commonly used in the industry at present, the thermosetting acrylic resin, the inorganic film forming additive and the color paste are mainly adopted to compound to form the blackening liquid, and a workpiece to be treated is tempered at high temperature and then enters the blackening liquid with heat, so that the resin-coated color paste is quickly cured and attached to the surface of the workpiece to form a bright and smooth resin film layer. Although the residual heat blackening agent is taken as the mainstream blackening technology at present, a sufficient amount of heat is required in the blackening process to form a film, and the residual heat blackening agent is not suitable for some secondary processing or processes without a high-temperature tempering process.
In recent years, in order to overcome the high energy consumption condition required by waste heat blackening, a normal temperature blackening process is developed in the hot working industry. The process mainly comprises the steps of enabling a workpiece with a well-cleaned surface to pass through an acid blackening liquid containing copper and selenium compounds at normal temperature, and generating black copper selenide or cuprous selenide on the surface of the workpiece through an oxidation-reduction reaction to realize black dyeing. The blackening film generated by the process is an inorganic film layer, has poor antirust performance compared with an organic film layer, has high requirement on the surface smoothness of a previous workpiece, is easy to generate uneven color on the surface of the workpiece after reaction, and cannot be popularized and used in the industry in a large area.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide an organic-inorganic composite normal-temperature autophoretic blackening agent which does not need to form a film by utilizing high-temperature waste heat of a workpiece in a blackening process, can be suitable for blackening a steel metal workpiece subjected to secondary processing or a high-temperature tempering procedure, and has a formed blackening film which is an organic film layer and has good antirust performance.
The technical scheme is as follows: the organic-inorganic composite normal-temperature autophoretic blackening agent is prepared by mixing the following components in percentage by mass: 30-40% of water-soluble acrylic resin, 0.5-1.5% of emulsifier, 3-6% of pigment, 1-2% of oxidant, 0.5-0.8% of activator, 0.1-0.5% of inhibitor and the balance of water.
Wherein the pH value of the blackening agent is 2-5.
Wherein the emulsifier is one or a mixture of more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block copolymer or alkylphenol polyoxyethylene phosphate. The added emulsifier can better emulsify the color paste and the resin, so that the latex particles and the pigment particles are more stable, and the color is uniform and is not easy to bloom after film forming.
Wherein the pigment is one of carbon black, iron oxide black or aniline black.
Wherein the oxidant is hydrogen peroxide or iodic acid.
Wherein the activating agent is acetic acid or citric acid.
Wherein the inhibitor is fluozirconic acid or ferric trifluoride. The inhibitor is added into the bath solution to react with excessive Fe in the bath solution after a period of time3+Complexing and maintaining the stability of the whole solution. No inhibitor is contained in the system, the bath solution is easy to destabilize, and the resin is separated out; the inhibitor provides initial metal cations, when the initial metal cation content in the blackening agent system is too small and the blackening is carried out after the metal workpiece is added, the reaction speed of the system is very slow, the blackening time is very long and can reach several hours; therefore, it is necessary to make the initial metal cation concentration in the blackening agent system not higher than 1000ppm, to stably exist the emulsified liquid system of the blackening agent, to quickly blacken the metal workpiece after adding the metal workpiece, and to control the precipitation rate of the resin without making the film layer too thick.
The blackening mechanism of the normal-temperature blackening liquid is as follows: the micro-area electrochemical reaction of the steel metal workpiece in the acid solution is formed, so that the concentration of iron ions in the local solution is increasedThe emulsion charge layer in the local solution is unstable, the high molecular emulsion particles are demulsified and separated out to be attached on the workpiece, and then the high molecular emulsion particles are crosslinked into a resin film through heat curing; the method specifically comprises the following steps: iron reacts with acid in solution to produce Fe2+Ion, Fe2+Oxidized by an oxidizing agent to Fe3+In the local solution of Fe3+When the concentration reaches a certain value, the double electric layers of the interface of the iron and the resin emulsion are damaged and destabilized to cause emulsion breaking, and the resin emulsion at the interface wraps pigment particles to quickly aggregate and precipitate on the metal surface; the thickening of the coating is the result of continuous reaction deposition, the reaction of the steel surface and acid becomes slow along with the increase of the coating thickness, and the thickness increase becomes slow until the autophoretic film forming is terminated. And (3) performing self-electrophoresis to form a resin film, and performing thermosetting film forming at 170-200 ℃ to form a paint film.
The paint film thickness will gradually increase with increasing autophoretic time, but the reaction will gradually slow down until substantial termination. The termination of blackening was judged by observing the presence or absence of bubbling, and the reaction was usually terminated completely within 3 min.
The concentration of metal cations in the bath solution determines the reaction rate and the film-forming density, the film is rough and uneven when the concentration is low, the film is too thick when the concentration is too high, and the stability of the bath solution is poor. The metal cations in the system provide the cation concentration required to initiate the reaction, with the Fe in the system proceeding as the bath solution is used3+The concentration will slowly increase, so regular monitoring of Fe is required3+Concentration, addition of inhibitor to complex iron, and even addition of strong oxidant to remove precipitate.
Has the advantages that: compared with the existing normal-temperature blackening agent, the blackening agent can form an organic film layer on a metal workpiece, and the organic film layer is thicker than an inorganic film layer and has stronger covering power and stronger salt mist performance; compared with the waste heat blackening agent, the blackening agent disclosed by the invention can form a film without heat of a workpiece, so that on one hand, energy is greatly saved, and on the other hand, the problem that the waste heat blackening liquid is easy to break emulsion and precipitate when the workpiece works in a high-temperature environment for a long time can be prevented, so that the stability of the tank liquor is improved, and the service life of the tank liquor is prolonged. The blackening agent forms a blackening film on the surface of a workpiece through self-deposition, and can be applied to blackening treatment of fasteners and automobile parts.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
Example 1
The invention relates to an organic-inorganic composite normal-temperature autophoretic blackening agent, which is prepared by mixing the following components in percentage by mass: 40% of water-soluble acrylic resin, 0.6% of fatty alcohol-polyoxyethylene ether, 4% of carbon black color paste, 2% of hydrogen peroxide, 0.5% of acetic acid, 0.2% of ferric trifluoride and 52.7% of deionized water.
Adding the water-soluble acrylic resin, the fatty alcohol-polyoxyethylene ether, the carbon black color paste, hydrogen peroxide, acetic acid and ferric trifluoride into deionized water according to the formula ratio, and uniformly mixing to obtain the blackening emulsion.
Example 2
The invention relates to an organic-inorganic composite normal-temperature autophoretic blackening agent, which is prepared by mixing the following components in percentage by mass: 30% of water-soluble acrylic resin, 0.5% of fatty alcohol-polyoxyethylene ether, 3% of carbon black color paste, 1.5% of hydrogen peroxide, 0.5% of acetic acid, 0.1% of ferric trifluoride and 64.4% of deionized water.
Adding the water-soluble acrylic resin, the fatty alcohol-polyoxyethylene ether, the carbon black color paste, hydrogen peroxide, acetic acid and ferric trifluoride into deionized water according to the formula ratio, and uniformly mixing to obtain the blackening emulsion.
Example 3
The invention relates to an organic-inorganic composite normal-temperature autophoretic blackening agent, which is prepared by mixing the following components in percentage by mass: 40% of water-soluble acrylic resin, 1.5% of fatty alcohol-polyoxyethylene ether, 6% of aniline black, 1.5% of iodic acid, 0.8% of citric acid, 0.5% of fluozirconic acid and 49.7% of deionized water.
Adding the water-soluble acrylic resin, the fatty alcohol-polyoxyethylene ether, the aniline black, the iodic acid, the citric acid and the fluorozirconic acid into deionized water according to the formula ratio, and uniformly mixing to obtain the blackening emulsion.
Example 4
The invention relates to an organic-inorganic composite normal-temperature autophoretic blackening agent, which is prepared by mixing the following components in percentage by mass: 30% of water-soluble acrylic resin, 1.0% of fatty alcohol-polyoxyethylene ether, 4% of aniline black, 1% of iodic acid, 0.8% of citric acid, 0.3% of fluozirconic acid and 62.9% of deionized water.
Adding the water-soluble acrylic resin, the fatty alcohol-polyoxyethylene ether, the aniline black, the iodic acid, the citric acid and the fluorozirconic acid into deionized water according to the formula ratio, and uniformly mixing to obtain the blackening emulsion.
Diluting the blackening emulsion prepared in the embodiment 1-4 into working solution with the mass fraction of 10% by using deionized water when in use; the workpiece to be blackened is an M20 multiplied by 100 fastener, specifically, four M20 multiplied by 100 fasteners with the same specification are degreased and cleaned by alcohol, and then are respectively put into the working solution obtained by the blackening liquid in the embodiment 1-4, the blackening time is 3min at normal temperature (20 ℃), and the workpiece is baked and solidified for 20min at 180 ℃.
Comparative example 1: and (3) preparing a blackening working solution according to the recommended mass concentration by using a commercially available waste heat blackening agent, and putting an M20 multiplied by 100 fastener with the temperature of 450 ℃ into the blackening working solution for waste heat blackening, wherein the blackening time is 1.5 min.
Comparative example 2: preparing a blackening working solution according to the suggested mass concentration by using a commercially available normal-temperature blackening solution (acidic blackening solution containing copper and selenium compounds), degreasing surface oil stains on an M20X 100 fastener by using alcohol, and then putting the fastener into the blackening working solution for normal-temperature blackening, wherein the blackening time is 3 min.
Table 1 shows a comparison of the properties of the black films on the respective workpieces:
Figure BDA0003570256730000041
as can be seen from Table 1, the higher the solid content of the water-soluble acrylic resin is, the higher the thickness of the finally formed paint film is, the longer the salt spray resistance time is, but when the acidity of the oxidizing agent in the blackening agent system is too strong, the reaction speed of the iron metal workpiece and the acid is too fast, so that the local iron ion concentration is too high, the resin is rapidly separated out, and the formed resin film is thick but has poor compactness, and the salt spray resistance time is affected.

Claims (7)

1. An organic-inorganic composite normal-temperature autophoresis blackening agent is characterized by being prepared by mixing the following components in percentage by mass: 30-40% of water-soluble acrylic resin, 0.5-1.5% of emulsifier, 3-6% of pigment, 1-2% of oxidant, 0.5-0.8% of activator, 0.1-0.5% of inhibitor and the balance of water.
2. The organic-inorganic composite room-temperature autophoretic blackening agent as claimed in claim 1, wherein: the pH value of the blackening agent is 2-5.
3. The organic-inorganic composite room-temperature autophoretic blackening agent as claimed in claim 1, wherein: the emulsifier is one or a mixture of several of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block copolymer or alkylphenol polyoxyethylene phosphate.
4. The organic-inorganic composite room-temperature autophoretic blackening agent according to claim 1, wherein: the pigment is one of carbon black, iron oxide black or aniline black.
5. The organic-inorganic composite room-temperature autophoretic blackening agent as claimed in claim 1, wherein: the oxidant is hydrogen peroxide or iodic acid.
6. The organic-inorganic composite room-temperature autophoretic blackening agent as claimed in claim 1, wherein: the activating agent is acetic acid or citric acid.
7. The organic-inorganic composite room-temperature autophoretic blackening agent as claimed in claim 1, wherein: the inhibitor is fluozirconic acid or ferric trifluoride.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785751A (en) * 2022-12-29 2023-03-14 南京科润新材料技术有限公司 Waste heat blackening agent with high salt spray performance

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN106011830A (en) * 2016-07-29 2016-10-12 南京科润新材料技术有限公司 Emulsified blackening liquid
CN109735181A (en) * 2018-12-26 2019-05-10 南京科润工业介质股份有限公司 A kind of emulsification hair blackening liquid used under the conditions of hardness
WO2021103361A1 (en) * 2019-11-27 2021-06-03 南京科润工业介质股份有限公司 Blackening liquid containing no bactericide

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Publication number Priority date Publication date Assignee Title
CN106011830A (en) * 2016-07-29 2016-10-12 南京科润新材料技术有限公司 Emulsified blackening liquid
CN109735181A (en) * 2018-12-26 2019-05-10 南京科润工业介质股份有限公司 A kind of emulsification hair blackening liquid used under the conditions of hardness
WO2021103361A1 (en) * 2019-11-27 2021-06-03 南京科润工业介质股份有限公司 Blackening liquid containing no bactericide

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785751A (en) * 2022-12-29 2023-03-14 南京科润新材料技术有限公司 Waste heat blackening agent with high salt spray performance
CN115785751B (en) * 2022-12-29 2024-03-22 南京科润新材料技术有限公司 Waste heat blackening agent with high salt fog performance

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