CN112143276A - Antifouling auxiliary agent for automobile varnish and preparation method and application thereof - Google Patents
Antifouling auxiliary agent for automobile varnish and preparation method and application thereof Download PDFInfo
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- CN112143276A CN112143276A CN202010881899.8A CN202010881899A CN112143276A CN 112143276 A CN112143276 A CN 112143276A CN 202010881899 A CN202010881899 A CN 202010881899A CN 112143276 A CN112143276 A CN 112143276A
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- varnish
- antifouling auxiliary
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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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
- 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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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Abstract
The invention relates to the technical field of automobile paint auxiliary agents, and particularly discloses an antifouling auxiliary agent for automobile varnish, a preparation method and application thereof, wherein the antifouling auxiliary agent comprises methyl hydrogen-containing silicone oil, aminosiloxane, an amine curing agent, organic silicon resin and an organic solvent; the antifouling auxiliary agent is added by 1-2% to endow the automobile varnish with excellent hydrophobic and oleophobic effects, so that the smoothness and wear resistance of a paint film can be improved, and the automobile varnish is enhanced in stain resistance and easy to clean; the antifouling auxiliary agent has the advantages of simple preparation process, low raw material cost and simple method for adding the antifouling auxiliary agent into the automobile varnish.
Description
Technical Field
The invention relates to the technical field of automobile paint auxiliaries, in particular to an antifouling auxiliary for automobile varnish and a preparation method and application thereof.
Background
Automotive clearcoats generally have two functions: firstly, the brightness and the light reflection degree of the paint surface are increased, and secondly, the paint is used for protecting the colored paint layer. The paint is mainly used in combination with base paint and colored paint, is a transparent finishing varnish, is inseparable from the base paint in a spraying process, and is generally sprayed with the base paint firstly and then with the varnish, wherein the varnish provides gloss and a protective layer for the base paint. The varnish coated in the original factory is high-temperature baking varnish generally, the baking temperature is 120-150 ℃, and the baking time is about half an hour. The self-drying varnish is generally used for paint layer repairing operation in the automobile maintenance industry, can be naturally dried at room temperature and can also be baked at low temperature, and the baking temperature can be set to be 50-80 ℃. At present, the varnish materials adopted by original factories are mainly single-component paints cured at high temperature, namely acrylic resin added with amino resin or polyester resin and the like, the varnish materials commonly used for refinishing paints are mainly two-component acrylic resins cured naturally (the two-component acrylic resins generally comprise main paint, curing agent and diluent), and the main components of the two are acrylic resins.
Varnishes are susceptible to slow attack by environmental contaminants, including: automobile exhaust, acid rain, bird droppings, animal urine, leaf putrefaction, and the like; in addition, road asphalt, tape, paint, etc., adhere tightly to the clear paint and are difficult to remove, or damage the clear paint during cleaning.
In order to prevent or alleviate the corrosion phenomenon, the prior vehicle paint technology adopts the following solutions: 1) the acrylic resin is subjected to simple organic silicon modification, but the modification method only can enable the automobile paint to obtain a certain hydrophobic effect and limited self-cleaning performance; 2) the acrylic resin is modified by fluorine-containing monomers or polymers, the modification method can achieve good hydrophobic and oleophobic effects of the car paint, but needs enough addition amount to have obvious effect, and in addition, the organic fluorine monomers or polymers are expensive, the production process is complex and can generate highly toxic byproducts, and the use of the organic fluorine monomers or polymers is limited in view of the factors; 3) the post-care technologies of the vehicle paint, such as waxing, crystal plating and the like, can enable the paint film to achieve certain smooth and hydrophobic effects, but the vehicle paint is expensive, time-consuming, labor-consuming and short in effective period.
The self-cleaning technology of the car body has wide prospect and is very beneficial to consumers. The problems of mechanical stability, service life, preparation cost, industrial production and the like of the super-hydrophobic and oleophobic surfaces are always important factors for restricting the self-cleaning technology of the automobile body to be used by a large number of users.
Disclosure of Invention
One of the purposes of the invention is to provide an antifouling auxiliary agent for automobile varnish aiming at the existing technical current situation, the antifouling auxiliary agent provided by the invention is organic silicon resin modified by a unique formula design, the cost is low, and the automobile varnish can achieve excellent hydrophobic and oleophobic effects by only adding 1-2% of the antifouling auxiliary agent, so that the smoothness and wear resistance of the varnish film can be improved, the automobile varnish is strong in stain resistance and easy to clean, the acid and alkali resistance and corrosion resistance of the varnish film are improved, and the cost for washing automobiles and a large amount of water resources are saved.
Another object of the present invention is to provide a method for preparing the above antifouling auxiliary, wherein the method for preparing the antifouling auxiliary is simple in process.
It is another object of the present invention to provide a use of the above-mentioned anti-fouling assistant, wherein the anti-fouling assistant of the present invention can be added to a one-component varnish for automotive refinish coating or a two-component refinish paint for automotive refinish coating, to provide excellent hydrophobic and oleophobic effects to an automotive varnish, and to provide a simple method for adding the anti-fouling assistant to the automotive varnish.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an antifouling auxiliary agent for automobile varnish, which comprises the following components in parts by weight:
in the antifouling auxiliary agent of the invention, the methyl hydrogen-containing silicone oil has Si-H reactive groups and contains a large amount of Si-CH3The groups provide a hydrophobic, oleophobic effect.
The amino siloxane provides strong reactive amino groups, has bridging effect, reacts with hydrogen-containing groups of methyl hydrogen-containing silicone oil, is dehydrogenated and crosslinked to form a polycondensate with a three-dimensional crosslinking structure, and greatly improves hydrophobicity.
The organic silicon resin contains a large number of active hydroxyl groups, and continuously reacts with primary polycondensate generated by the reaction of methyl hydrogen-containing silicone oil and aminosiloxane under the catalysis and crosslinking action of an amine curing agent and aminosiloxane to form a reticular crosslinking prepolymer, hydrophobic and oleophobic groups play an antifouling effect outwards, and a crosslinking system plays a role in structural support; in addition, some active hydroxyl groups are reserved and can be grafted, polymerized or copolymerized with an acrylic resin system in subsequent automobile varnish, so that a paint film is denser.
The reaction principle of the invention is as follows:
the methyl hydrogen-containing silicone oil is condensed under the bridging of the amino siloxane to form a primary condensation polymer;
the primary polycondensate and the organic silicon resin are subjected to complex crosslinking reaction under the promotion of an amine curing agent and aminosiloxane to form a reticular crosslinking prepolymer-modified organic silicon resin, namely the antifouling auxiliary agent, the hydrophobic and oleophobic groups of the antifouling auxiliary agent outwards play an antifouling effect, a crosslinking system plays a role in structural support, and a certain amount of active hydroxyl groups are reserved in the antifouling auxiliary agent;
when the antifouling auxiliary agent is added into the automobile varnish of an acrylic resin system, under the crosslinking and curing action of isocyanate or amino resin and the like at a certain temperature, the modified organic silicon resin in the antifouling auxiliary agent is embedded into the acrylic resin, so that the hydrophobic and oleophobic effects of an organic silicon product are exerted, a paint film is more smooth and wear-resistant, an automobile is not easy to stain and clean, and the acid-base resistance and corrosion resistance of the automobile varnish are improved.
The methyl hydrogen-containing silicone oil condensate has excellent hydrophobic and oleophobic effects, the condensation compound of the methyl hydrogen-containing silicone oil and the aminosiloxane reacts with the organic silicon resin under the promotion of the amine curing agent and the aminosiloxane, the proportion of hydrophobic and oleophobic groups in the organic silicon resin is improved, the organic fusion of the methyl hydrogen-containing silicone oil, the aminosiloxane condensation compound, the organic silicon resin and the acrylic resin is ensured, and the antifouling effect can be maintained for a long time.
Preferably, the hydrogen content of the methyl hydrogen-containing silicone oil is 1.0-1.6%.
Preferably, the aminosiloxane comprises one or more of beta-aminoethyl-gamma-aminopropyltrimethoxysilane, gamma-anilinopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta-aminoethyl-gamma-aminopropyltriethoxysilane and amino-terminated polydimethylsiloxane.
Preferably, the amine curing agent is one or a combination of more of a modified aliphatic amine curing agent, an aromatic amine curing agent, a polyether amine curing agent and a dicyandiamide curing agent.
Preferably, the silicone resin is one or a combination of more of methyl silicone resin, vinyl silicone resin, methyl phenyl silicone resin, epoxy modified silicone resin and acrylic modified silicone resin.
Preferably, the organic solvent is one or more of an aromatic solvent, an ester solvent and an alcohol ether solvent.
Preferably, the aromatic solvent is one or more of toluene, xylene, styrene and mixed aromatic hydrocarbon; the ester solvent is one or a combination of more of ethyl acetate, n-butyl acetate, sec-butyl acetate, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; the alcohol ether solvent is one or a combination of more of ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether and propylene glycol butyl ether.
The invention also provides a preparation method of the antifouling auxiliary agent for the automobile varnish, which comprises the following steps:
s, under the condition that the temperature is 1.20-40 ℃ and the air humidity is less than or equal to 40%, sequentially adding methyl hydrogen-containing silicone oil and amino siloxane into an organic solvent, and stirring for 4-24 hours to obtain a primary condensation compound;
and S2, after the reaction in the previous step is finished, sequentially adding the amine curing agent and the organic silicon resin, and continuously stirring for 4-24 hours to obtain a finished product.
And S3, pouring the finished product into a light-tight HDPE bottle or barrel, storing the finished product in a dry and cool place, wherein the finished product cannot meet water, cannot be stored in a transparent PET bottle and cannot be exposed to sunlight in the storage process so as not to influence the stability and the quality guarantee period.
Preferably, the addition amount of the antifouling auxiliary agent is 1-2% of the total weight of the automobile varnish.
Preferably, the automotive varnish comprises a single-component varnish for automotive original factory painting or a two-component refinish paint for automotive refinish painting.
Preferably, the method for adding the antifouling auxiliary agent into the automobile varnish is as follows:
adding the antifouling auxiliary agent into the single-component varnish, slowly stirring for half an hour, and curing for 24 hours;
or slowly adding the antifouling auxiliary agent into the main paint of the two-component repair paint, slowly stirring for half an hour, curing for 24 hours, and adding the curing agent and the diluent of the two-component repair paint before use.
After the antifouling auxiliary agent and the automobile varnish are cured, conventional spraying, baking and other processes can be carried out.
The antifouling auxiliary agent is simple in adding method, the mixed liquid after mixing is stable in properties, and the mixed liquid is not layered after being placed for a long time.
The invention has the beneficial effects that:
1) according to the invention, the condensation compound of methyl hydrogen-containing silicone oil and aminosiloxane reacts with organic silicon resin under the promotion of the amine curing agent and aminosiloxane, so that the proportion of hydrophobic and oleophobic groups is greatly increased, and thus a better antifouling effect is achieved, and only 1-2% of antifouling auxiliary agent is needed to be added, so that excellent hydrophobic and oleophobic effects can be achieved, and an excellent antifouling effect is given to the automobile varnish.
2) The antifouling auxiliary agent provided by the invention is relatively low in use cost, and under the condition of the same antifouling effect, the use cost is only 5-10% of that of the existing organic fluorine antifouling auxiliary agent, and only the extremely low cost of the automobile varnish is increased.
3) The antifouling auxiliary agent provided by the invention is simple in addition process, good in intersolubility with the automobile varnish, and capable of maintaining the antifouling effect for a long time, and the addition of the antifouling auxiliary agent does not influence the transparency, glossiness and the like of the original paint.
Detailed Description
In order to make the technical problems solved, technical solutions adopted, and technical effects achieved by the present invention clearer, the technical solutions of the embodiments of the present invention will be described in further detail below.
An antifouling auxiliary agent for automobile varnish comprises the following components in parts by weight:
the preparation method of the antifouling auxiliary agent comprises the following steps:
s, under the condition that the temperature is 1.20-40 ℃ and the air humidity is less than or equal to 40%, sequentially adding methyl hydrogen-containing silicone oil and amino siloxane into an organic solvent, and stirring for 4-24 hours to obtain a primary condensation compound;
and S2, after the reaction in the previous step is finished, sequentially adding the amine curing agent and the organic silicon resin, and continuously stirring for 4-24 hours to obtain a finished product.
And S3, pouring the finished product into a light-tight HDPE bottle or barrel, and storing the product in a dry and cool place.
The antifouling auxiliary agent has stable performance, and the prepared antifouling auxiliary agent still has an antifouling modification effect after 6 months of testing.
The method for adding the antifouling auxiliary agent into the automobile varnish comprises the following steps:
1) when the single-component varnish for coating in an automobile original factory is modified, the antifouling auxiliary agent is added into the single-component varnish, slowly stirred for half an hour and then cured for 24 hours;
2) when the two-component refinishing paint for automobile refinishing and coating is modified, the antifouling auxiliary agent is slowly added into the main paint of the two-component refinishing paint, the main paint is slowly stirred for half an hour and then is cured for 24 hours, and the curing agent and the diluent of the two-component refinishing paint are added before use.
The stability of the antifouling auxiliary agent of the invention after being respectively mixed with single-component varnish and double-component refinishing paint is respectively observed, and the mixed solution has no turbidity and delamination.
Performance testing
And (3) carrying out performance test on the prepared antifouling auxiliary agent:
sample group: adding the antifouling auxiliary agent prepared in each embodiment into a conventional automobile varnish, wherein the addition amount of the antifouling auxiliary agent is 2% of the total weight of the automobile varnish, and then spraying the modified automobile varnish on a tinplate test board;
blank group: spraying conventional automobile varnish on a tinplate test plate;
control group: the commercially available organic fluorine-based antifouling auxiliary agent was added to a conventional automobile varnish in an amount of 2% by weight based on the total weight of the automobile varnish, and then the modified automobile varnish was sprayed on a tinplate test board.
1) Performance test for preventing adhesive tape trace
After the adhesive tape is adhered, glue is usually remained on the surface of the substrate, so that adhesive tape traces appear on the surface of the substrate, the test adhesive tape is adhered to the sample group, the blank group and the control group respectively, after the test adhesive tape is placed for a certain time, the adhesive tape is manually peeled off, the condition of the adhesive part of the adhesive tape on each group of substrates is observed, so as to test the performance of the adhesive tape traces of each group, and the test result is as follows:
2) oil pen test
Marking the sample group, the blank group and the control group by using an oil pen, wiping the mark after placing for a certain time, observing the condition of each group of base materials after wiping so as to test the oleophobic performance of each group, wherein the test results are as follows:
an antifouling auxiliary agent for automobile varnish comprises the following components in parts by weight:
in addition, the antifouling auxiliary agent provided by the invention can also be applied to coating products such as polyurethane resin wood paint, epoxy resin paint, amino baking paint, coating agent, powder coating and the like.
The technical principles of the present invention have been described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without any inventive step, which shall fall within the scope of the present invention.
Claims (11)
1. The antifouling auxiliary agent for the automobile varnish is characterized by comprising the following components in parts by weight:
5-20 parts by weight of methyl hydrogen-containing silicone oil
1 to 10 parts by weight of aminosiloxane
0 to 5 parts by weight of amine curing agent
5-20 parts by weight of organic silicon resin
50-90 parts by weight of organic solvent
2. The antifouling auxiliary for automotive varnishes according to claim 1, wherein the hydrogen content of said methyl hydrogen silicone oil is 1.0 to 1.6%.
3. The antifouling auxiliary for automotive varnishes according to claim 1, wherein said aminosilicone comprises one or more combinations of β -aminoethyl- γ -aminopropyltrimethoxysilane, γ -anilinopropyltrimethoxysilane, γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- β -aminoethyl- γ -aminopropyltriethoxysilane, amino-terminated polydimethyl siloxane.
4. The antifouling auxiliary for automotive varnishes according to claim 1, wherein the amine curing agent is one or a combination of more of a modified aliphatic amine curing agent, an aromatic amine curing agent, a polyetheramine curing agent and a dicyandiamide curing agent.
5. The antifouling auxiliary agent for automotive varnish according to claim 1, wherein the silicone resin is one or more of methyl silicone resin, vinyl silicone resin, methyl phenyl silicone resin, epoxy-modified silicone resin and acrylic-modified silicone resin.
6. The antifouling auxiliary for automotive varnishes according to any one of claims 1 to 3, wherein the organic solvent is one or a combination of aromatic solvents, ester solvents and alcohol ether solvents.
7. The antifouling auxiliary for automotive varnishes according to claim 4, wherein the aromatic solvent is one or a combination of toluene, xylene, styrene and mixed aromatic hydrocarbon; the ester solvent is one or a combination of more of ethyl acetate, n-butyl acetate, sec-butyl acetate, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; the alcohol ether solvent is one or a combination of more of ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether and propylene glycol butyl ether.
8. The method for producing the antifouling auxiliary for automotive varnish according to any one of claims 1 to 3, characterized by comprising the steps of:
s, under the condition that the temperature is 1.20-40 ℃ and the air humidity is less than or equal to 40%, sequentially adding methyl hydrogen-containing silicone oil and amino siloxane into an organic solvent, and stirring for 4-24 hours to obtain a primary condensation compound;
and S2, after the reaction in the previous step is finished, sequentially adding the amine curing agent and the organic silicon resin, and continuously stirring for 4-24 hours to obtain a finished product.
9. The use of the antifouling auxiliary for automotive varnishes according to any one of claims 1 to 3, wherein the antifouling auxiliary is added in an amount of 1 to 2% by weight based on the total weight of the automotive varnish.
10. The use of an antifouling auxiliary for automotive varnishes according to claim 7, wherein the automotive varnish comprises a one-component varnish for automotive refinish coating or a two-component refinish paint for automotive refinish coating.
11. The use of an anti-soiling aid for use in automotive varnishes according to claim 8, characterised in that it is added to an automotive varnish by:
adding the antifouling auxiliary agent into the single-component varnish, slowly stirring for half an hour, and curing for 24 hours;
or slowly adding the antifouling auxiliary agent into the main paint of the two-component repair paint, slowly stirring for half an hour, curing for 24 hours, and adding the curing agent and the diluent of the two-component repair paint before use.
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| CN202010881899.8A CN112143276B (en) | 2020-08-28 | 2020-08-28 | Antifouling auxiliary agent for automobile varnish and preparation method and application thereof |
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