Surface conditioner containing manganese phosphate
Technical Field
The invention relates to the technical field of surface conditioning agents, in particular to a surface conditioning agent containing manganese phosphate.
Background
The main moving parts such as crankshaft, piston and external support in the refrigerator compressor are required to work in a reciprocating way under the condition of countless high-temperature motion, besides the processing precision is ensured, the surfaces of the parts are required to be degreased, surface adjusted, chemically converted by manganese phosphate and brushed, the abrasion resistance of the outer surfaces of the parts is enhanced, and the oil absorption of the refrigerator oil is enhanced.
The surface conditioning treatment is performed to form a film on the steel surface rapidly, uniformly, and at a high density from manganese phosphate crystals in a manganese phosphate-based chemical conversion treatment as a next step. In general, a steel material is immersed in a surface conditioning bath to form manganese phosphate nuclei on the steel surface. In the surface conditioning step, manganese phosphate crystal nuclei are generally formed on the surface of steel, and a good chemical conversion coating is formed on the surface of steel by using the manganese phosphate crystal nuclei in the manganese phosphate-based chemical conversion treatment.
The surface conditioner for surface conditioning is an aqueous solution comprising manganese phosphate and pyrophosphate, wherein the value of (weight of manganese phosphate)/(weight of pyrophosphate) is 0.5 to 2, and the pH is 7 to 9.5.
However, these various manganese phosphate crystal nuclei as surface conditioners have disadvantages in that the particle size of manganese phosphate is too large, agglomeration is easily generated with the passage of time, and the shape thereof is powder and is not convenient to use. And the chemical conversion coating formed after the manganese phosphate chemical conversion treatment can ensure the size precision and the abrasion resistance only by polishing.
The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a surface conditioner which is liquid, has excellent stability, and has excellent handling properties after wear-resistant manganese phosphate-based chemical conversion treatment of steel without brushing.
Disclosure of Invention
In order to solve the above problems, the present invention provides a chemical conversion coating steel material having excellent surface morphology, which comprises a surface conditioner comprising manganese phosphate dispersed in a specific state, wherein the surface conditioner comprises, in parts by weight, 0.4 to 5 parts of manganese phosphate, 80 to 100 parts of a solvent, 2 to 10 parts of a dispersant, 0.5 to 3 parts of a neutralizer, and 0.5 to 2 parts of a thickener, wherein the average particle size of manganese phosphate in the surface conditioner is 2 μm or less, D90 is 1.5 μm or less, and the pH is 3 to 9.
In one embodiment, the manganese phosphate-containing surface conditioner comprises, by weight, 0.4-4 parts of manganese phosphate, 80-100 parts of a solvent, 2-8 parts of a dispersant, 0.5-2 parts of a neutralizer, and 0.5-1 part of a thickener.
In one embodiment, the solvent comprises one or more of water, methanol, ethanol, isopropanol, ethylene glycol monobutyl ether, toluene, xylene, carbon ten oil, acetone, butanone, isophorone, N-methylpyrrolidone, ethyl acetate, butyl acetate.
In one embodiment, the dispersant includes one or more of animal glue, gelatin, gum arabic, sodium alginate, propylene glycol alginate, methylcellulose, carboxymethylcellulose, modified carboxymethylcellulose, hydroxyethylcellulose, polyacrylic acid-based resins, polycarboxylic acid-based resins, polyurethane-based resins, polyvinyl alcohols, polyacrylic acid-maleic acid copolymers, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene ethers, polyethylene glycol, polyoxyethylene fatty acid esters, and polyoxyethylene derivatives.
In one embodiment, the dispersant is carboxymethyl cellulose, modified carboxymethyl cellulose, polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: (0.1-0.5): (0.1-1).
In one embodiment, the neutralizing agent comprises one or more of diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, isopropylethanolamine, diisopropanolamine, 2-amino-2-methylpropanol, 2- (dimethylamino) -2-methylpropanol, morpholine, N-methylmorpholine, N-ethylmorpholine.
In one embodiment, the thickener comprises one or more of clay, diatomaceous earth, silica, carboxymethyl cellulose, carboxyethyl cellulose, polyethylene, polyacrylic acid, polyvinyl alcohol, xanthan gum.
In a second aspect of the present invention, there is provided a method for producing a manganese phosphate-based chemical conversion treated steel sheet, comprising immersing a steel material in the manganese phosphate-containing surface conditioner and then performing a manganese phosphate-based chemical conversion treatment.
The third aspect of the invention provides a method for manufacturing a steel anti-wear phosphating film, which comprises the steps of dipping a steel material into the surface conditioner containing manganese phosphate, and then carrying out manganese phosphate chemical conversion treatment to obtain the steel anti-wear phosphating film.
The present invention provides, in a fourth aspect, a manganese phosphate dispersion for use in the preparation of a surface conditioner containing manganese phosphate, which is used for the surface conditioning of a steel material to be subjected to a pretreatment for a manganese phosphate chemical conversion film-forming treatment, contains 0.5 to 50% manganese phosphate, and has an average particle diameter of 2 μm or less, D90Below 2 μm, the pH is 3-9.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.
The invention adopts a substance obtained by dispersing manganese phosphate in a specific state as a surface conditioner, and can obtain a chemical conversion coating steel material with excellent surface morphology, wherein the manganese phosphate-containing surface conditioner comprises, by weight, 0.4-5 parts of manganese phosphate, 80-100 parts of a solvent, 2-10 parts of a dispersant, 0.5-3 parts of a neutralizer and 0.5-2 parts of a thickening agent, wherein the average particle size of the manganese phosphate in the manganese phosphate-containing surface conditioner is less than 2 mu m, and D is less than 2 mu m90Below 1.5 μm, and pH 3-9.
Manganese phosphate
The surface conditioner of the present invention contains manganese phosphate. The manganese phosphate is Mn3(PO4)2This means that the solid is generally colorless crystalline solid, and is commercially available as white or light pink powder.
The manganese phosphate of the invention can be prepared by mixing the following components in a molar ratio of 3: 2 mixing and heating the diluent of manganese sulfate and disodium hydrogen phosphate to generate a heptahydrate of manganese phosphate as a crystalline precipitate, or reacting an aqueous solution of phosphoric acid with manganese oxide or manganese carbonate to obtain a heptahydrate of manganese phosphate, wherein the heptahydrate is amorphous and heated to obtain a trihydrate at 100 ℃ and a monohydrate at 300 ℃. The manganese phosphate in the invention can adopt any one of heptahydrate, trihydrate and monohydrate, and the readily available trihydrate is generally directly adopted.
The shape of manganese phosphate is not particularly limited, and commercially available products are generally white or light pink powders, and the shape of the powder may be any shape such as a micro-sphere or a flake. The particle size is not particularly limited, and is usually a powder having an average particle size of the order of micrometers. The present invention can prepare a stable dispersion of a fine dispersion of manganese phosphate, and therefore can obtain a stable surface treatment effect without being affected by the primary particle size and shape of the powder.
The preparation method of the dispersion liquid comprises the following steps: the method for preparing an aqueous dispersion by dispersing manganese phosphate in an aqueous medium is not particularly limited, but it is preferably prepared by blending manganese phosphate in a dispersion medium such as water or an organic solvent and wet-pulverizing the mixture in the presence of a dispersant.
In the preparation of the aqueous dispersion of manganese phosphate, it is preferable in terms of process steps to blend manganese phosphate in an aqueous medium and wet-grind it, or to prepare a solution by wet-grinding it in a dispersion medium other than the aqueous medium and then replacing the solvent.
The amount of manganese phosphate added to the dispersion is usually 0.5 to 50%, and if the amount is less than 0.5%, the manganese phosphate content is too low, and the surface conditioner effect obtained from the dispersion is insufficient. If it exceeds 50%, it is difficult to obtain a uniform and fine particle size distribution by wet pulverization and to form a finely dispersed state. The blending amount is preferably 1 to 50%.
The amount of the dispersant added to the dispersion is preferably 0.1 to 10%, more preferably 0.2 to 5%. If the content of the dispersant is 0.1% or less, the dispersibility is insufficient, and if the content is 10% or more, the dispersibility is rather deteriorated due to interaction between the excessive dispersants, and the cost is too high even if the dispersibility is sufficient.
The manganese phosphate is finely dispersed in a dispersion medium, and the dispersion degree is that the average dispersed particle diameter is less than 1.5 mu m.
Where D is50(volume 50% diameter) as the average dispersed particle diameter and the average particle diameter.
The method for preparing a dispersion in which manganese phosphate is finely dispersed at a particle size of 2 μm or less is not particularly limited, but a method in which manganese phosphate and a dispersant are added to a dispersion medium to make the contents of each of them 0.5% to 50% and 0.1% to 10%, respectively, and then wet pulverization is carried out is preferred, and a conventionally known method may be used, and for example, a disk mill, a pin mill, a media disperser represented by a high-pressure homogenizer, an ultrasonic disperser, or the like may be used.
If excessive pulverization occurs during pulverization, the dispersant becomes insufficient as the specific surface area increases, and the particles excessively dispersed aggregate to form coarse particles, resulting in an excessive dispersion phenomenon in which dispersion stability is affected, and dispersion occurs depending on blending and dispersion conditions, resulting in aggregation and thickening due to the ultrafine particles and/or aggregation between fine particles. To prevent this, D should be monitored90(volume 90% diameter), the blending and dispersing conditions are selected so as not to produce an overdispersion, D in the present invention90The particle size is 2 μm or less.
Here, D50(volume 50% diameter) and D90(volume 90% diameter) is a particle diameter of 50% and 90% on the cumulative curve when the cumulative curve is obtained based on the particle size distribution in the dispersion with the total volume of the particles being 100%, and D is measured automatically by a laser particle analyzer50And D90。
By the above method, the average value of the dispersion particle size of manganese phosphate in the aqueous medium can be adjusted to 1.5 μm or less, and a stable and excellent aqueous dispersion having excellent performance as a surface conditioner can be obtained, and the average value of the dispersion particle size is generally 0.01 to 1.5 μm and can be adjusted to a desired level.
When the aqueous dispersion is prepared by the above method of the present invention, even manganese phosphate having a particle size of more than 1.5 μm can be dispersed in the dispersion at a dispersion particle size of 1.5 μm or less. The same is true for manganese phosphate particles having a primary particle size of several tens of microns. This means that the primary particle size of manganese phosphate can be reduced by wet grinding in the above-described manner, even if manganese phosphate having an originally small primary particle size is not used. By the above method, the average particle diameter of the dispersed particle diameter in the aqueous dispersion can be controlled to 1.5 μm or less, and also 1 μm or less, and even 0.5 μm or less.
The dispersion of the present invention thus obtained can be an aqueous dispersion which has an average value of the particle size of the manganese phosphate dispersed in the dispersion of 1.5 μm or less according to the application, and which has excellent dispersion stability and excellent performance as a surface conditioner.
By the wet pulverization method, coarse particles, i.e., particles having a diameter exceeding D, can be reduced90The proportion of particles, and therefore the distribution D of the dispersed particle diameters90A dispersion having a narrow distribution of dispersed particle diameters which can suppress large dispersed particle diameters and is 1.5 μm or less, 1 μm or less, and even 0.5 μm or less. It is inferred that the manganese phosphate is dispersed in a fine dispersion particle size and the dispersion state is extremely stable. Further, since the dispersed particle size distribution is narrow and the particle size is uniform, it is presumed that more uniform crystal nuclei can be formed in the surface conditioning treatment step, more uniform manganese phosphate crystal nuclei can be formed in the subsequent chemical conversion treatment, the surface properties of the obtained chemical conversion treated steel are uniform and excellent, and the treatment properties of steel which is difficult to be subjected to chemical conversion treatment, such as a deep groove portion having a complicated structure and cast steel, can be improved.
The particle size of the manganese phosphate dispersed in the dispersion was determined by measuring the particle size distribution using a laser doppler particle size analyzer.
The amount of manganese phosphate incorporated in the aqueous dispersion of the present invention is 10% or more, and may be 20% or more, or even 30% or more, and a high-concentration aqueous dispersion can be obtained, and therefore a surface conditioner having high performance can be easily prepared.
As described above, the surface conditioner can be obtained by finely dispersing the manganese phosphate prepared in advance in the aqueous medium to obtain an aqueous dispersion, and then appropriately adding the aqueous medium to obtain a surface conditioner.
In one embodiment, the manganese phosphate-containing surface conditioner comprises, by weight, 0.4-4 parts of manganese phosphate, 80-100 parts of a solvent, 2-8 parts of a dispersant, 0.5-2 parts of a neutralizer, and 0.5-1 part of a thickener.
In one embodiment, the solvent comprises one or more of water, methanol, ethanol, isopropanol, ethylene glycol monobutyl ether, toluene, xylene, carbon ten oil, acetone, butanone, isophorone, N-methylpyrrolidone, ethyl acetate, butyl acetate; preferably, the solvent is water.
In the present invention, the water is purified water.
In one embodiment, the dispersant includes one or more of animal glue, gelatin, gum arabic, sodium alginate, propylene glycol alginate, methylcellulose, carboxymethylcellulose, modified carboxymethylcellulose, hydroxyethylcellulose, polyacrylic acid-based resins, polycarboxylic acid-based resins, polyurethane-based resins, polyvinyl alcohols, polyacrylic acid-maleic acid copolymers, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene ethers, polyethylene glycol, polyoxyethylene fatty acid esters, and polyoxyethylene derivatives.
In one embodiment, the dispersant is carboxymethyl cellulose, modified carboxymethyl cellulose, polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: (0.1-0.5): (0.1-1); preferably, the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: 0.3: 0.7.
the preparation method of the modified carboxymethyl cellulose comprises the following steps:
(1) adding concentrated sulfuric acid and sodium nitrate into a reactor, cooling in an ice-water bath, stirring and adding graphene at 0-5 ℃, uniformly mixing, slowly adding potassium permanganate, controlling the reaction temperature to be 10-15 ℃, reacting for 2 hours, continuously stirring and reacting for 2 hours at 35 ℃, adding deionized water, controlling the temperature of the reaction solution to be 98 ℃, continuously stirring for 0.5 hour, adding hydrogen peroxide with the mass concentration of 30%, filtering while hot, washing the product to be neutral by using dilute hydrochloric acid (1mol/L), and drying under reduced pressure for 24 hours at 60 ℃ to obtain graphene oxide; the weight ratio of the graphene to the sodium nitrate to the potassium permanganate is 1: 0.6: 5; the mass volume ratio of the graphene to the concentrated sulfuric acid with the mass concentration of 98%, the hydrogen peroxide with the mass concentration of 30% and the deionized water is 1: 20: 3: 22;
(2) adding graphene oxide and deionized water into a reactor, stirring for 5h, then adding carboxymethyl cellulose, stirring for 1h, adding a cross-linking agent glutaraldehyde with the mass fraction of 2%, reacting and stirring for 48h at 35 ℃, filtering with a cellulose acetate filter membrane with the pore diameter of 0.45 mu m, drying a filter cake under reduced pressure for 24h at 80 ℃, and grinding into powder to obtain the modified carboxymethyl cellulose; the weight ratio of the graphene oxide to the deionized water, the carboxymethyl cellulose and the cross-linking agent glutaraldehyde with the mass fraction of 2% is 1: 50: 20: 2.
in one embodiment, the neutralizing agent comprises one or more of diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, isopropylethanolamine, diisopropanolamine, 2-amino-2-methylpropanol (CAS number: 124-68-5), 2- (dimethylamino) -2-methylpropanol, morpholine, N-methylmorpholine, N-ethylmorpholine; preferably, the neutralizing agent is 2-amino-2-methyl-1-propanol.
In one embodiment, the thickener comprises one or more of clay, diatomaceous earth, silica, carboxymethyl cellulose, carboxyethyl cellulose, polyethylene, polyacrylic acid, polyvinyl alcohol, xanthan gum; preferably, the thickening agent is diatomite and xanthan gum.
In one embodiment, the weight ratio of the diatomaceous earth to the xanthan gum in the thickener is 1: (2-5); preferably, the weight ratio of the diatomaceous earth to the xanthan gum is 1: 3.6.
the invention can also be added with preservative, mildew preventive and the like for preventing and killing bacteria and mildew of the dispersion. When used, the proper type and addition amount can be selected.
In a second aspect of the present invention, there is provided a method for producing a manganese phosphate-based chemical conversion treated steel sheet, comprising immersing a steel material in the manganese phosphate-containing surface conditioner and then performing a manganese phosphate-based chemical conversion treatment.
The third aspect of the invention provides a method for manufacturing a steel anti-wear phosphating film, which comprises the steps of dipping a steel material into the surface conditioner containing manganese phosphate, and then carrying out manganese phosphate chemical conversion treatment to obtain the steel anti-wear phosphating film.
The present invention provides, in a fourth aspect, a manganese phosphate dispersion for use in the preparation of a surface conditioner containing manganese phosphate, which is used for surface conditioning of a steel material to be subjected to a pretreatment for manganese phosphate chemical conversion film-forming treatment, and which contains 0.5 to 50% manganese phosphate, wherein the manganese phosphate has an average particle diameter of 2 μm or less, D90 of 2 μm or less, and a pH of 3 to 9.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.
Example 1
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, the dispersing agent is carboxymethyl cellulose, modified carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: 0.3: 0.7; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is1:3.6;
The preparation method of the surface conditioner containing manganese phosphate comprises the following steps:
adding 2 parts of manganese phosphate, 100 parts of solvent, 6 parts of dispersant, 1 part of neutralizer and 0.4 part of thickener into a reactor according to the parts by weight, uniformly stirring, carrying out wet grinding by using a high-efficiency grinder (alkali glass hollow particles with the diameter of 1 mm), adding 0.4 part of thickener, and continuously stirring to obtain the manganese phosphate-containing surface conditioner.
The preparation method of the modified carboxymethyl cellulose comprises the following steps:
(1) adding concentrated sulfuric acid and sodium nitrate into a reactor, cooling in an ice-water bath, stirring and adding graphene at 0-5 ℃, uniformly mixing, slowly adding potassium permanganate, controlling the reaction temperature to be 10-15 ℃, reacting for 2 hours, continuously stirring and reacting for 2 hours at 35 ℃, adding deionized water, controlling the temperature of the reaction solution to be 98 ℃, continuously stirring for 0.5 hour, adding hydrogen peroxide with the mass concentration of 30%, filtering while hot, washing the product to be neutral by using dilute hydrochloric acid (1mol/L), and drying under reduced pressure for 24 hours at 60 ℃ to obtain graphene oxide; the weight ratio of the graphene to the sodium nitrate to the potassium permanganate is 1: 0.6: 5; the mass volume ratio of the graphene to the concentrated sulfuric acid with the mass concentration of 98%, the hydrogen peroxide with the mass concentration of 30% and the deionized water is 1: 20: 3: 22;
(2) adding graphene oxide and deionized water into a reactor, stirring for 5h, then adding carboxymethyl cellulose, stirring for 1h, adding a cross-linking agent glutaraldehyde with the mass fraction of 2%, reacting and stirring for 48h at 35 ℃, filtering with a cellulose acetate filter membrane with the pore diameter of 0.45 mu m, drying a filter cake under reduced pressure for 24h at 80 ℃, and grinding into powder to obtain the modified carboxymethyl cellulose; the weight ratio of the graphene oxide to the deionized water, the carboxymethyl cellulose and the cross-linking agent glutaraldehyde with the mass fraction of 2% is 1: 50: 20: 2.
example 2
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the manganese phosphateParticle diameter D of manganese phosphate in the surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, the dispersing agent is carboxymethyl cellulose, modified carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: 0.1: 0.7; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 3.6;
the preparation method of the surface conditioner containing manganese phosphate and the preparation method of the modified carboxymethyl cellulose are the same as those in example 1.
Example 3
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, the dispersing agent is carboxymethyl cellulose, modified carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: 0.5: 0.1; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 3.6;
the preparation method of the surface conditioner containing manganese phosphate and the preparation method of the modified carboxymethyl cellulose are the same as those in example 1.
Example 4
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, the dispersing agent is carboxymethyl cellulose, modified carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: 0.3: 0.7; the neutralizer is 2-amino-2-methyl-1-propanol; the above-mentionedThe thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 2;
the preparation method of the surface conditioner containing manganese phosphate and the preparation method of the modified carboxymethyl cellulose are the same as those in example 1.
Example 5
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, the dispersing agent is carboxymethyl cellulose, modified carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: 0.3: 0.7; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 5;
the preparation method of the surface conditioner containing manganese phosphate and the preparation method of the modified carboxymethyl cellulose are the same as those in example 1.
Comparative example 1
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, the dispersing agent is carboxymethyl cellulose, carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the polyethylene glycol is 1: 0.3: 0.7; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 3.6;
the preparation method of the surface conditioner containing manganese phosphate is the same as that of the example 1.
Comparative example 2
The surface conditioning agent containing manganese phosphate comprises 2 parts of manganese phosphate and 100 parts of solvent by weight,6 parts of dispersing agent, 1 part of neutralizing agent and 0.8 part of thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, and the dispersant is carboxymethyl cellulose; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 3.6;
the preparation method of the surface conditioner containing manganese phosphate and the preparation method of the modified carboxymethyl cellulose are the same as those in example 1.
Comparative example 3
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, and the dispersant is modified carboxymethyl cellulose; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 3.6;
the preparation method of the surface conditioner containing manganese phosphate and the preparation method of the modified carboxymethyl cellulose are the same as those in example 1.
Comparative example 4
The manganese phosphate-containing surface conditioner comprises, by weight, 2 parts of manganese phosphate, 100 parts of a solvent, 6 parts of a dispersing agent, 1 part of a neutralizing agent and 0.8 part of a thickening agent; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 1.40 μm, D50At 0.45 μm; the solvent is water, the dispersant is carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the polyethylene glycol is 1: 0.7; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 3.6;
the preparation method of the surface conditioner containing manganese phosphate is the same as that of the example 1.
Comparative example 5
Calculated by weight portionThe surface conditioner containing manganese phosphate comprises 2 parts of manganese phosphate, 100 parts of solvent, 6 parts of dispersant, 1 part of neutralizer and 0.8 part of thickener; the particle size D of the manganese phosphate in the manganese phosphate-containing surface conditioner90At 5 μm, D50At 4 μm; the solvent is water, the dispersing agent is carboxymethyl cellulose, modified carboxymethyl cellulose and polyethylene glycol, and the weight ratio of the carboxymethyl cellulose to the modified carboxymethyl cellulose to the polyethylene glycol is 1: 0.3: 0.7; the neutralizer is 2-amino-2-methyl-1-propanol; the thickening agent is diatomite and xanthan gum, and the weight ratio of the diatomite to the xanthan gum is 1: 3.6;
the preparation method of the surface conditioner containing manganese phosphate and the preparation method of the modified carboxymethyl cellulose are the same as those in example 1.
And (3) performance testing:
1. stability of surface conditioner
The surface conditioning liquid in the examples was placed in a thermostatic bath at 50 ℃ to perform a stability-promoting test with time, and observed for 2 months. The surface conditioning fluid has good stability: the phenomena of sedimentation and thickening are not found at all, and the particle size distribution is not changed; the stability of the surface conditioning liquid is generally: no sedimentation and thickening phenomena are found, and the particle size distribution is unchanged; poor stability of the surface conditioning fluid: the phenomena of sedimentation and thickening are found, and the particle size distribution is changed;
2. chemical conversion treatability of film layer
Cold-rolled steel Sheets (SPC) (70 mm. times.150 mm. times.0.8 mm) which had been previously subjected to degreasing treatment were immersed in the surface conditioning liquid at room temperature for 30 seconds. Immediately after the rolling, the plate was chemically converted at 43 ℃ for 2 minutes by dipping in a manganese phosphate treatment solution, washed with water, then with pure water, and dried to obtain a test plate.
The manganese phosphate chemical conversion film of each of the obtained test panels was observed by SEM (JSM 5600 manufactured by japan electron corporation). The surface state was visually observed ∈ indicating uniform rust-free spots, ° indicating slight spots but no rust spots, and ×. indicating marked spots and rust spots.
Table 1 results of performance testing
From the above data, it can be seen that the manganese phosphate-containing surface conditioner provided by the present invention is a surface conditioner that has excellent stability and excellent treatability on steel after wear-resistant manganese phosphate-based chemical conversion treatment without brushing.
The above examples are merely illustrative and serve to explain some of the features of the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims not be limited by the choice of examples illustrating features of the invention, and that technological advances will form possible equivalents or sub-substitutes not presently contemplated for reasons of inaccuracy of the linguistic expressions, and that such variations are to be construed as being covered by the appended claims where possible.