CN110982405B - Anti-doodling surface treatment liquid and preparation method thereof - Google Patents
Anti-doodling surface treatment liquid and preparation method thereof Download PDFInfo
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- CN110982405B CN110982405B CN201911082028.3A CN201911082028A CN110982405B CN 110982405 B CN110982405 B CN 110982405B CN 201911082028 A CN201911082028 A CN 201911082028A CN 110982405 B CN110982405 B CN 110982405B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses an anti-doodling surface treatment liquid, which can effectively form a treatment coating with small surface tension and easy removal of stains by adopting a mode that aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion are jointly coated with polytetrafluoroethylene, and meanwhile, the treatment coating has good wear resistance and durability and can effectively improve the dirt resistance and durability of base materials including automobile decoration materials and the like.
Description
Technical Field
The invention relates to the technical field of surface treating agents, in particular to an anti-doodling surface treating fluid and a preparation method thereof.
Background
The anti-doodling coating is a coating with a special surface function, the surface has lower surface tension, the lotus leaf-shaped surface has a self-cleaning function, dirt naturally rolls off, and the self-adhesive paper can easily fall off after being pasted.
For occasions such as automobile interior decorations and the like, the materials such as clothes, bags and the like are contacted for a long time, so that the dyeing is easy, and particularly, after the light-color interior decorations are dyed, the appearance of the interior decoration products is seriously reduced, and the quality experience of automobiles is influenced; after the painting or dyeing, the decoration material is difficult to clean, and the decoration material is easy to damage by adopting a common cleaning means.
At present, the surface of the existing anti-doodling is coated by adopting a solvent type surface coating agent, a large amount of solvent is easily discharged, the surface has single hand feeling and higher glossiness, and the existing anti-doodling is mainly treated on a PU (polyurethane) base material and has smaller application range.
The solvent-based surface finishing agent generates a large amount of solvent during production, does not meet the current environmental protection requirement, and is easy to generate fire because the solvent volatilizes at high temperature during production. Meanwhile, the solvent-based surface finishing agent also needs high-temperature crosslinking in the production process, and the production efficiency is lower.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the objects of the present invention is to provide an anti-graffiti surface treatment solution which can be directly coated on a material layer including PVC and the like to form an anti-graffiti coating layer, which is free of volatile organic solvents, safer to the environment and human body, and can be directly coated to form a protective layer, thereby reducing the coating process; the formed coating has lower surface tension, and can resist pollution and graffiti continuously and strongly.
The invention also aims to provide a preparation method of the anti-doodling surface treatment liquid.
One of the purposes of the invention is realized by adopting the following technical scheme:
an anti-doodling surface treatment liquid is prepared from the following components in parts by weight: 1-20 parts of polytetrafluoroethylene, 80-120 parts of waterborne aliphatic polyurethane, 10-30 parts of waterborne styrene-acrylic emulsion, 10-30 parts of waterborne vinyl chloride-vinyl acetate emulsion, 0.5-2 parts of silane coupling agent, 3-8 parts of crosslinking curing agent and 2-6 parts of auxiliary agent; the particle size of the polytetrafluoroethylene is 0.5-5 mu m and is treated by vacuum plasma.
The anti-doodling surface treatment liquid is prepared by coating polytetrafluoroethylene particles treated by a silane coupling agent with aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion to form a film-forming coating with low surface tension, so that the adhesion of sewage, dirt and the like is effectively prevented; the working procedure that a bonding layer needs to be coated on the surface of a base material such as PVC in the prior art can be effectively reduced by using the aqueous chlorine vinegar and the aqueous polyurethane together, namely the anti-doodling surface treatment liquid can directly form an anti-doodling coating with good adhesive force with the base material on the surface of the base material.
Further, the polytetrafluoroethylene is cleaned by vacuum plasma until the wetting angle is 15.5-25 degrees. After the vacuum plasma treatment, the contact angle and the surface energy of the polytetrafluoroethylene particles are changed, and the polytetrafluoroethylene particles can be well dispersed in an aqueous resin system.
Further, the crosslinking curing agent is carbodiimide or aziridine. Compared with aziridine, the toxicity of the carbodiimide is relatively lower, the working life of the carbodiimide can be prolonged to several weeks to several months, and the application convenience of the anti-graffiti surface treatment liquid is greatly improved. The anti-doodling surface treatment liquid is preferably added into a system 30min before coating and uniformly stirred, or can be understood as a two-component form, and the cross-linking curing agent is packaged separately and mixed before use.
Further, the auxiliary agent comprises a leveling agent, a defoaming agent and a thickening agent. Wherein the thickener is used to adjust the viscosity to 800-1500 cps.
Further, the auxiliary agent also comprises polymethyl methacrylate urea resin. The polymethyl methacrylate urea resin, which can provide a good haze feeling to the simulated dermis, has a particle size of 4 to 10 μm, more preferably 2 to 5 μm. The polymethyl methacrylate urea resin belongs to reactive organic extinction powder, and can react with a base resin film-forming material so as to be uniformly dispersed in a system.
Further, the solid contents of the aqueous aliphatic polyurethane, the aqueous styrene-acrylic emulsion and the aqueous vinyl chloride-acetate emulsion are all 30-60%.
Further, the feed additive is prepared from the following components in parts by weight: 5-15 parts of polytetrafluoroethylene, 80-120 parts of water-based aliphatic polyurethane, 15-25 parts of water-based styrene-acrylic emulsion, 15-25 parts of water-based chlorine-vinegar emulsion, 1-1.5 parts of silane coupling agent, 5-6 parts of crosslinking curing agent, 1-1.5 parts of flatting agent, 1-1.5 parts of defoaming agent and 1-1.5 parts of thickening agent.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the anti-doodling surface treatment liquid comprises the following steps:
1) cleaning polytetrafluoroethylene powder by using vacuum plasma;
2) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 60-100 ℃, and reacting for 0.3-4 h;
3) adding the polytetrafluoroethylene powder treated in the step 2) into aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion, uniformly stirring, and adding an auxiliary agent;
4) adjusting pH to 8-9 with ammonia water;
5) adding a crosslinking curing agent, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
Further, in the step 2), the polytetrafluoroethylene powder and the silane coupling agent are subjected to cyclone mixing.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an anti-doodling surface treatment liquid, which uses polytetrafluoroethylene capable of effectively reducing the surface tension of a coating to carry out treatment by a silane coupling agent, and can effectively improve the dispersibility of polytetrafluoroethylene powder in aqueous resin, thereby obtaining a treatment coating with uniform texture and small surface tension;
after the anti-doodling surface treatment liquid is coated and molded, the water-based aliphatic polyurethane, the water-based styrene-acrylic emulsion and the water-based vinyl chloride-vinyl acetate emulsion form cross-linking coating on polytetrafluoroethylene under the action of a cross-linking curing agent, so that a protective coating with better hydrophobic and oleophobic properties is formed.
According to the preparation method, the styrene-acrylic emulsion and the vinyl chloride-vinyl acetate emulsion are added simultaneously, and the treatment coating with strong adhesive force with the matrix can be directly formed on the surface of the base materials such as PVC and the like, so that the process of coating the intermediate coating in advance in the traditional process is effectively reduced, the operation time is shortened, and the production efficiency is improved.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
The invention provides an anti-doodling surface treatment liquid which is prepared from the following components in parts by weight: 1-20 parts of polytetrafluoroethylene, 80-120 parts of waterborne aliphatic polyurethane, 10-30 parts of waterborne styrene-acrylic emulsion, 10-30 parts of waterborne vinyl chloride-vinyl acetate emulsion, 0.5-2 parts of silane coupling agent, 3-8 parts of crosslinking curing agent and 2-6 parts of auxiliary agent; the particle size of the polytetrafluoroethylene is 0.5-5 μm.
According to the anti-doodling surface treatment liquid, the polytetrafluoroethylene with the specified particle size range is subjected to silane surface treatment and is dispersed in the aqueous aliphatic polyurethane, the aqueous styrene-acrylic emulsion and the aqueous vinyl chloride-acetate emulsion to form a compact and uniform coating system, the formed coating has small surface tension, is not beneficial to the adhesion of aqueous or oily substances, can effectively and durably remove dirt, and meanwhile, the film layer has good wear resistance and durability, is stable and is not yellowed.
In the following embodiments, the leveling agent may be an aqueous leveling agent produced by Picker; the defoaming agent and the thickening agent can be selected from the conventional defoaming agent and thickening agent on the market. The silane coupling agent may be a methyl acetyl type silane coupling agent having a high durability.
Example 1:
an anti-doodling surface treatment liquid is prepared from the following components in parts by weight: 5 parts of polytetrafluoroethylene, 80 parts of aqueous aliphatic polyurethane, 15 parts of aqueous styrene-acrylic emulsion, 15 parts of aqueous vinyl chloride-vinyl acetate emulsion, 1 part of silane coupling agent, 5 parts of carbodiimide, 1 part of flatting agent, 1 part of defoaming agent, 1 part of thickening agent and 5 parts of polymethyl methacrylate urea resin.
The method for preparing the anti-doodling surface treatment liquid comprises the following steps:
1) cleaning polytetrafluoroethylene powder by using vacuum plasma; the wetting angle after vacuum plasma treatment is 15.5-25 degrees;
2) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 60 ℃, and reacting for 4 hours;
3) adding the polytetrafluoroethylene powder treated in the step 2) into aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion, uniformly stirring, adding a flatting agent, a defoaming agent and a thickening agent, and uniformly stirring and mixing;
4) adjusting pH to 8-9 with ammonia water;
5) and adding carbodiimide into the mixture within 30min-1h before use, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
Example 2:
an anti-doodling surface treatment liquid is prepared from the following components in parts by weight: 10 parts of polytetrafluoroethylene, 100 parts of aqueous aliphatic polyurethane, 20 parts of aqueous styrene-acrylic emulsion, 20 parts of aqueous vinyl chloride-vinyl acetate emulsion, 1.2 parts of silane coupling agent, 6 parts of carbodiimide, 1.2 parts of flatting agent, 1.2 parts of defoaming agent, 1.2 parts of thickening agent and 5 parts of polymethyl methacrylate urea resin.
The method for preparing the anti-doodling surface treatment liquid comprises the following steps:
1) cleaning polytetrafluoroethylene powder by using vacuum plasma; the wetting angle after vacuum plasma treatment is 15.5-25 degrees;
2) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 80 ℃, and reacting for 2 hours;
3) adding the polytetrafluoroethylene powder treated in the step 2) into aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion, uniformly stirring, adding a flatting agent, a defoaming agent and a thickening agent, and uniformly stirring and mixing;
4) adjusting pH to 8-9 with ammonia water;
5) and adding carbodiimide into the mixture within 30min-1h before use, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
Example 3:
an anti-doodling surface treatment liquid is prepared from the following components in parts by weight: 15 parts of polytetrafluoroethylene, 120 parts of aqueous aliphatic polyurethane, 25 parts of aqueous styrene-acrylic emulsion, 25 parts of aqueous vinyl chloride-vinyl acetate emulsion, 1.5 parts of silane coupling agent, 6 parts of carbodiimide, 1.5 parts of flatting agent, 1.5 parts of defoaming agent, 1.5 parts of thickening agent and 5 parts of polymethyl methacrylate urea resin.
The method for preparing the anti-doodling surface treatment liquid comprises the following steps:
1) cleaning polytetrafluoroethylene powder by using vacuum plasma; the wetting angle after vacuum plasma treatment is 15.5-25 degrees;
2) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 100 ℃, and reacting for 0.5 h;
3) adding the polytetrafluoroethylene powder treated in the step 2) into aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion, uniformly stirring, adding a flatting agent, a defoaming agent and a thickening agent, and uniformly stirring and mixing;
4) adjusting pH to 8-9 with ammonia water;
5) and adding carbodiimide into the mixture within 30min-1h before use, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
Comparative example 1:
an anti-doodling surface treatment liquid is prepared from the following components in parts by weight: 10 parts of polytetrafluoroethylene, 100 parts of aqueous aliphatic polyurethane, 20 parts of aqueous vinyl chloride-vinyl acetate emulsion, 1.2 parts of silane coupling agent, 6 parts of carbodiimide, 1.2 parts of flatting agent, 1.2 parts of defoaming agent, 1.2 parts of thickening agent and 5 parts of polymethyl methacrylate urea resin.
The method for preparing the anti-doodling surface treatment liquid comprises the following steps:
1) cleaning polytetrafluoroethylene powder by using vacuum plasma; the wetting angle after vacuum plasma treatment is 15.5-25 degrees;
2) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 80 ℃, and reacting for 2 hours;
3) adding the polytetrafluoroethylene powder treated in the step 2) into aqueous aliphatic polyurethane and aqueous vinyl chloride-vinyl acetate emulsion, uniformly stirring, adding a flatting agent, a defoaming agent and a thickening agent, and uniformly stirring and mixing;
4) adjusting pH to 8-9 with ammonia water;
5) and adding carbodiimide into the mixture within 30min-1h before use, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
Comparative example 2:
an anti-doodling surface treatment liquid is prepared from the following components in parts by weight: 10 parts of polytetrafluoroethylene, 100 parts of water-based aliphatic polyurethane, 20 parts of water-based styrene-acrylic emulsion, 1.2 parts of silane coupling agent, 6 parts of carbodiimide, 1.2 parts of flatting agent, 1.2 parts of defoaming agent, 1.2 parts of thickening agent and 5 parts of polymethyl methacrylate urea resin.
The method for preparing the anti-doodling surface treatment liquid comprises the following steps:
1) cleaning polytetrafluoroethylene powder by using vacuum plasma; the wetting angle after vacuum plasma treatment is 15.5-25 degrees;
2) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 80 ℃, and reacting for 2 hours;
3) adding the polytetrafluoroethylene powder treated in the step 2) into the aqueous aliphatic polyurethane and the aqueous styrene-acrylic emulsion, uniformly stirring, adding the flatting agent, the defoaming agent and the thickening agent, and uniformly stirring and mixing;
4) adjusting pH to 8-9 with ammonia water;
5) and adding carbodiimide into the mixture within 30min-1h before use, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
Comparative example 3
An anti-doodling surface treatment liquid is prepared from the following components in parts by weight: 10 parts of polytetrafluoroethylene, 100 parts of aqueous aliphatic polyurethane, 20 parts of aqueous styrene-acrylic emulsion, 20 parts of aqueous vinyl chloride-vinyl acetate emulsion, 1.2 parts of silane coupling agent, 6 parts of carbodiimide, 1.2 parts of flatting agent, 1.2 parts of defoaming agent, 1.2 parts of thickening agent and 5 parts of polymethyl methacrylate urea resin.
The method for preparing the anti-doodling surface treatment liquid comprises the following steps:
1) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 80 ℃, and reacting for 2 hours;
2) adding the polytetrafluoroethylene powder treated in the step 1) into aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion, uniformly stirring, adding a flatting agent, a defoaming agent and a thickening agent, and uniformly stirring and mixing;
3) adjusting pH to 8-9 with ammonia water;
4) and adding carbodiimide into the mixture within 30min-1h before use, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
Performance detection
The anti-graffiti surface treatment liquids obtained in examples 1 to 3 and comparative examples 1 to 3 were respectively roll-coated on a PVC substrate of 10cm × 30cm using a reverse roll coater, and were dried at 120 ℃.
1. Adhesion detection
The adhesion of the coating was tested according to GB/T9286-1998 with the following results:
TABLE 1 adhesion of the coatings
| Example 1 | Example 2 | Example 3 | |
| Grade | 4B | 4B | 4B |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Grade | 3B | 2B | 3B |
As can be seen from the above table, the adhesion of the coating of the present application has a higher coating adhesion by the composite combination of the styrene-acrylic emulsion, the vinyl chloride emulsion and the aqueous aliphatic polyurethane, whereas comparative examples 1 and 2 do not contain the styrene-acrylic emulsion or the vinyl chloride emulsion, and are reduced in adhesion.
2. Graffiti and stain resistance test
Referring to the test method 5.24 in QJLY J7110614B-2015, the surface was directly soiled with different stain sources for film layers, cleaned with water after 24h, and the degree of staining of the surface was recorded at normal and after abrasion resistance, respectively, as shown in the following table:
TABLE 2 anti-smudge test of anti-graffiti coatings
As is clear from the above table, the surface treatment liquids obtained in examples 1 to 3 each formed a coating having a high stain resistance and maintained a stain resistance level of 4 or more after abrasion resistance, while the surface treatment liquids obtained in comparative examples 1 to 3 formed coatings having a relatively low stain resistance.
3. Abrasion resistance test of coatings
The abrasion resistance of the anti-graffiti coating was tested according to the method of 4.42 of GB/T17657-2013, with the results shown in the following table:
TABLE 3 abrasion resistance test for anti-graffiti coatings
| Example 1 | Example 2 | Example 3 | |
| Results | 15 | 14 | 16 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Results | 11 | 8 | 10 |
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (7)
1. The anti-doodling surface treatment liquid is characterized by being prepared from the following components in parts by weight: 1-20 parts of polytetrafluoroethylene, 80-120 parts of waterborne aliphatic polyurethane, 10-30 parts of waterborne styrene-acrylic emulsion, 10-30 parts of waterborne vinyl chloride-vinyl acetate emulsion, 0.5-2 parts of silane coupling agent, 3-8 parts of crosslinking curing agent and 2-6 parts of auxiliary agent; the particle size of the polytetrafluoroethylene is 0.5-5 mu m and the polytetrafluoroethylene is subjected to vacuum plasma treatment;
the wetting angle of the polytetrafluoroethylene is 15.5-25 degrees; the crosslinking curing agent is carbodiimide or aziridine;
the preparation method of the anti-doodling surface treatment liquid comprises the following steps:
1) cleaning polytetrafluoroethylene powder by using vacuum plasma;
2) mixing the polytetrafluoroethylene powder treated in the step 1) with a silane coupling agent, heating to 60-100 ℃, and reacting for 0.3-4 h;
3) adding the polytetrafluoroethylene powder treated in the step 2) into aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion and aqueous vinyl chloride-vinyl acetate emulsion, uniformly stirring, and adding an auxiliary agent;
4) adjusting pH to 8-9 with ammonia water;
5) adding a crosslinking curing agent, and uniformly stirring to obtain the anti-doodling surface treatment liquid.
2. The anti-graffiti surface treatment fluid of claim 1, wherein the adjuvants comprise leveling agents, antifoaming agents, and thickening agents.
3. The anti-graffiti surface treatment fluid of claim 2, wherein the adjuvant further comprises a polymethyl methacrylate urea resin.
4. The anti-graffiti surface treatment fluid according to claim 3, wherein the polymethylmethacrylate urea resin has a particle size of 4 to 10 μm.
5. The anti-graffiti surface treatment fluid of claim 1, wherein the aqueous aliphatic polyurethane, aqueous styrene-acrylic emulsion, and aqueous vinyl chloride-acetate emulsion each have a solids content of 30-60%.
6. The anti-graffiti surface treatment fluid of claim 1, which is prepared from the following components in parts by weight: 5-15 parts of polytetrafluoroethylene, 80-120 parts of water-based aliphatic polyurethane, 15-25 parts of water-based styrene-acrylic emulsion, 15-25 parts of water-based chlorine-vinegar emulsion, 1-1.5 parts of silane coupling agent, 5-6 parts of crosslinking curing agent, 1-1.5 parts of flatting agent, 1-1.5 parts of defoaming agent and 1-1.5 parts of thickening agent.
7. The anti-graffiti surface treatment fluid of claim 1, wherein in step 2), polytetrafluoroethylene powder is cyclonically mixed with a silane coupling agent.
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