KR20090055437A - Fluorine-containing waterborne polyurethane paint - Google Patents
Fluorine-containing waterborne polyurethane paint Download PDFInfo
- Publication number
- KR20090055437A KR20090055437A KR1020070122361A KR20070122361A KR20090055437A KR 20090055437 A KR20090055437 A KR 20090055437A KR 1020070122361 A KR1020070122361 A KR 1020070122361A KR 20070122361 A KR20070122361 A KR 20070122361A KR 20090055437 A KR20090055437 A KR 20090055437A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- fluorine
- polyurethane paint
- pigment
- aqueous polyurethane
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- 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
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
- C09D7/43—Thickening agents
-
- 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
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- 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
Abstract
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous polyurethane coating containing a fluorine group having anti-fingerprint, and in detail, the coating properties of the conventional water-based polyurethane paint, for example, heat resistance, light resistance, etc., are maintained as they are. It relates to an aqueous polyurethane coating containing a fluorine group having anti-fingerprint properties that can be improved.
In the current automobile market, a variety of products that meet the consumer's preferences are being released, and they are increasingly developing and applying advanced and advanced products. In this regard, the upholstery of automobiles is becoming an issue, and the world's leading automakers are also actively investing in the luxury of interiors. Currently, technologies related to interior materials enhancement include real wood coating technology, metallizing technology, water-based soft texture paints, and these items are being developed with environmentally friendly materials and methods while improving interior materials.
Anti-fingerprint water-based polyurethane paint is a functional paint that is one step further from the existing paint concept for simply protecting the appearance of parts or painted parts, embodying various colors and decorating them. Commonly used coating materials mainly use polar materials with high surface energy to improve adhesion and physical properties. When these coatings are used as automobile interior materials with high frequency of contact between driver and passenger, The appearance is easily contaminated. Therefore, when using urethane paints containing fluorine groups having a low surface energy of 5 to 6 dyne / cm 2 , the fluorine groups move toward the surface of the coating film due to the low surface energy. At the same time, it is possible to realize high quality interior materials that reduce the contamination of the coating and improve the appearance.
Such a water-based polyurethane paint containing a fluorine group is an oligomer having a molecular weight of 5,000 or less obtained by reacting a polyurethane resin having a molecular weight of 50,000 or more synthesized by a reaction between an isocyanate and a polyol and a monomer containing a fluorine group at the end of the chain based on the urethane structure. It is made by blending, it is possible to implement a variety of properties according to the content and molecular weight changes of the urethane oligomer containing a fluorine group.
Fluorine groups are hydrophobic and have low surface free energy, and thus can improve surface contamination and wear characteristics. However, since the affinity with the organic material is inferior due to the nature of the material, a simple blend of the organic compound and fluorine has a problem of phase separation. Therefore, the prior art attempts to solve this problem by using a solvent, but after separation of the solvent, phase separation still occurs, which does not become a fundamental solution and causes odor and environmental problems of the interior materials.
In addition, when the fluorine group is added to the urethane main chain that influences the physical properties, the phase separation problem is solved, but the fluorine group not only affects urethane physical properties much, but also difficult to control the fluorine content.
Accordingly, the present inventors synthesized an oligomer having a molecular weight of 50,000 or more and a molecular weight of 5000 or less and an oligomer having a molecular weight of 5000 or less, which are the main resins that influence the physical properties of the coating film, and a fluorine group in the chain. However, in order to maximize the affinity between the two chains, the polyol used in the urethane oligomer containing fluorine groups was similar to the polyol structure constituting the main resin.
In addition, since the polymer chain has a small molecular weight as shown in Equation 1 below, and the end of the chain has the most active diffusion rate, that is, the chain movement is the most active, a small amount of fluorine is added and thus the surface modification is not affected. In order to obtain the maximum effect, the molecular weight of an oligomer was made into 5000 or less, and the method of synthesize | combining a fluorine group at the chain terminal was selected.
D: diffusion rate, Mw: molecular weight
Therefore, a synthetic polyurethane coating based on the above contents is to provide a polyurethane coating with improved coating properties, such as heat resistance, light resistance, etc., while maintaining the rubbing resistance as well as wear resistance while maintaining the coating properties of the resin. will be.
As a means for achieving the object of the present invention, the anti-fingerprint aqueous polyurethane paint of the present invention is
Resin blended 20 to 35% by weight of polyurethane and 5 to 15% by weight of urethane oligomer including a fluorine group; and 35 to 55% by weight of deionized water; And
2 to 5% by weight of pigment, 0.5 to 2% by weight of light stabilizer, 0.3 to 2% by weight of thickener, 3 to 7% by weight of photosensitive agent (quencher) and 2 to 5% by weight of organic organic solvent; It is characterized by.
The water-based polyurethane paint of the present invention can produce an advanced paint product having significantly improved surface properties such as fingerprint resistance and abrasion resistance while maintaining the film properties, for example, heat resistance and light resistance, of the existing water-based polyurethane paint. It works.
The present invention is a blend of a urethane oligomer containing a fluorine group in the existing water-based polyurethane paint (blend) while maintaining the heat resistance, light resistance, etc. of the existing urethane paint, while improving the surface properties of the coating film, such as anti-fingerprint, wear resistance More detailed description is as follows.
Anti-fingerprint aqueous polyurethane paint of the present invention is a resin blended 20 to 35% by weight of polyurethane and 5 to 15% by weight of a urethane oligomer including a fluorine group; and 35 to 55% by weight of deionized water; And
It is characterized by comprising 2 to 5% by weight of pigment, 0.5 to 2% by weight of light stabilizer, 0.3 to 2% by weight of thickener, 3 to 7% by weight of photosensitive agent (quencher) and 2 to 5% by weight of organic organic solvent. It is done.
In the polyurethane paint of the present invention, the polyurethane is mainly 45 to 50% by weight of polyester polyol having a molecular weight of 10,000 or more, 15 to 20% by weight of polycarbonate polyol having a molecular weight of 10,000 or more, 20 to 30% by weight of a non-yellowing isocyanate resin as a curing agent and hydrophilicity. It contains 5 to 27% by weight of resin.
In addition, the urethane oligomer including the fluorine group is 45 to 50% by weight of polyester polyol, 15 to 20% by weight of polycarbonate polyol, 20 to 30% by weight of a non-yellowing isocyanate resin as a curing agent, 5 to 7% by weight of a hydrophilic resin and a fluorine group It consists of 5 weight% of monomers which contained.
The non-yellowing isocyanate resin used as a curing agent in the present invention may be used at least one selected from isopron diisocyanate and hydrophilic hexamethylene diisocyanate, and the hydrophilic resin may be used in dimethylolpropionic acid and dimethylolbutanoic acid. Preference is given to using at least one selected.
In the present invention, the urethane oligomer including the fluorine group is used in the same polyester polyol and polycarbonate polyol used in the main polyurethane, but the molecular weight is adjusted to not exceed 5000, dimethylol is a hydrophilic resin used in the main polyurethane Improving the hydrophilicity of the chain by introducing propionic acid and / or dimethylolbutanoic acid to improve the storage stability of the resin, and finally including one or more selected from monomers containing 9 to 15 fluorine groups at the ends of the chain. It is characterized by that.
The water-based polyurethane paint containing the fluorine group of the present invention is prepared by blending the above-described main polyurethane and fluorine-containing oligomer in bulk and dispersing the resin in water using deionized water, followed by blending an additive. can do.
As the deionized water used in the present invention, cations such as sodium and calcium, and anions such as chlorine ions and sulfate ions are removed from natural water, and if the amount of deionized water is less than 35% by weight, the amount of hydrophilic resin is used. There is a problem to improve the dispersibility by increasing the, and if the content exceeds 55% by weight there is a problem that the content of the solid content is reduced.
The pigment may be used by selecting and mixing inorganic pigments according to a desired color, preferably one selected from titanium dioxide (TiO 2 ), carbon black, yellow pigment, blue pigment, green pigment, and red pigment. It is preferable to mix and use the above suitably. If the content of the inorganic pigment is less than 2% by weight, there is a problem in that coloring and concealment is difficult, and when it exceeds 5% by weight, heat resistance, light resistance, etc., may cause a problem in coating film properties.
On the other hand, the above-mentioned light stabilizer is suitably used by mixing the UV up-sub system and UV Hals system, preferably, it is preferably used by mixing the ratio of the UV Halz system and UV up-sub system 2 to one. If the content of the light stabilizer is less than 0.5% by weight, there is a problem of yellowing and a decrease in gloss, and if it exceeds 2% by weight, the coating surface is unstable.
The thickener may be used including one or more selected from an acrylic thickener and a urethane thickener, and if the content of the thickener is less than 0.3 wt%, there is a problem in that the paint flows down during painting, resulting in poor workability, 2 wt% If it exceeds, there is a problem that the storage capacity is reduced and the pot life is shortened.
As the photosensitizer (quenching agent), one or more selected from silica-based, aliphatic hydrocarbon-based waxes and silica-based waxes can be used, and preferably silica- or silica-based waxes are used. If the content of the photosensitizer is less than 3% by weight or more than 7% by weight, a weak problem in scratching occurs.
The aliphatic organic solvent may be one containing ethyl acetate, butyl acetate, propyl acetate, and one or more selected from ethyl glycol, butyl glycol, and propyl glycol. Preferably, a glycol system having excellent hydrophilicity in terms of dispersion stability is used. It is appropriate. If the content thereof is less than 2% by weight, there is a problem that the surface leveling is lowered, and if it exceeds 5% by weight, there is a problem that whitening occurs during curing.
In addition, the aqueous polyurethane paint containing a fluorine group according to the present invention may further contain various additives such as a wetting agent, an isotropy agent, etc., and the amount of these additives may be appropriately selected depending on various factors including the desired end use and properties. It can be adjusted and applied.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
Example 1 to 3 and Comparative example One
The main polyurethane was synthesized by adjusting the weight ratio of the polyester polyol having a molecular weight of 10,000, the polycarbonate polyol having a molecular weight of 10,000, and the non-yellowing isocyanate resin at the composition ratio shown in Table 1 below. In addition, a polyester polyol having a molecular weight of 1,000, a polycarbonate polyol having a molecular weight of 1,000, a non-yellowing isocyanate resin, and a monomer containing a fluorine group at a chain end were blended in the composition ratios shown in Table 1 to synthesize a fluorine-based polyurethane oligomer.
To the composition ratio shown in Table 2 below, the polyurethane coating sample was prepared by blending an additive to the urethane oligomer containing the main polyurethane and the fluorine group. The case where the urethane oligomer containing the said fluorine group was not mix | blended was set to the comparative example 1 according to the compounding ratio of the said main polyurethane and the urethane oligomer containing a fluorine group, respectively.
Inorganic pigments as additives in Examples 1 to 3 and Comparative Example 1 were prepared by mixing carbon black and titanium dioxide (TiO 2 ) in a 2.5 to 1 ratio. The mixture was used in a ratio of 1 to 1, and propylene glycol methyl ether and dipropylene glycol methyl ether were mixed in a ratio of 1 to 1 as a solvent.
After coating an aqueous primer about 7 to 10 microns (micron) for adhesion between the material and the paint on a test piece of polypropylene material [HT240, Hyundai EP (Engineering Plastic)], and dried at 80 ℃ for 10 minutes, Example 1 The paints prepared in ˜3 and Comparative Example 1 were coated with about 20 to 25 microns, left at room temperature for 10 minutes, and then dried at 80 ° C. for 20 minutes to complete a test sample, and then subjected to a coating film evaluation test as follows.
Experimental Example
Coating property evaluation
Room temperature Adhesion exam
The specimen in the horizontal and vertical directions by 11 cut into 2 mm gap cross-after after performing the cuts (Cross-cut) clean with a soft brush the surface and securely attached to the tape rule of a suitable width and length of one side of the tape 90 o angle By pulling strongly, the number of peeled coating scales was leaked. Also called the checkerboard adhesion test, the greater the number of peelings on a total of 100 checkerboard scales, the poorer the adhesion.
Heat resistant Adhesion exam
In the case of automotive interior parts were left for 300 hours at 80 ℃ and then taken out, and left for 1 hour at room temperature, the adhesion test was carried out immediately.
Light Adhesion exam
For automotive interior parts, the total cumulative amount of light under XENON ARC under the condition of black panel temperature 89 ± 3 ℃, ambient humidity 50 ± 5% RH, irradiation illuminance 0.55 ± 0.02 W / m 2 nm (at 340 nm) After irradiating until it became 1050 KJ / m <2> , it took out and wash | cleaned the test piece with the neutral detergent aqueous solution, it was made to dry with Air, it was left to stand at room temperature for 1 hour, and the said adhesion test was done.
Contact angle Measure
Measurement was performed using a Goniometer (Rame-Hart 100-series) equipped with an illuminator using two types of contact liquids, water and methylene iodine at 20 ± 1 ° C. The measurement was made at five different points with droplets of 2 mm in diameter, and the average was recorded.
Anti-fingerprint test: The thumb was pressed on the surface of the treated substrate for 30 seconds, and after 5 minutes, the fingerprint was rubbed 10 times with Kimwipes and the surface was observed. The remaining fingerprints were identified and classified as follows.
A: No fingerprints left, B: Some fingerprints remain,
C: Fingerprint is not erased at all.
Dry wear test: Using double-sided cloth friction agent under the condition of test load 1kg f , test speed 60 reciprocation / minute, friction stroke 100mm using reciprocating wear tester, and checking the number of times of exposure. It was.
The coating properties were averaged after evaluating five specimens for each test, and the results are shown in Table 3 below.
As shown in Table 3, when the urethane oligomer including the fluorine group in the main polyurethane is blended, the physical properties such as heat resistance and light resistance did not change, but surface properties such as rubbing and abrasion were significantly improved. In particular, when looking at Example 1 and Comparative Example 1, even if a small amount of the urethane oligomer containing a fluorine group it can be seen that the surface properties significantly improved. However, as can be seen in Example 3, the increase in the content of the fluorine-containing urethane oligomer showed the best properties at the surface contact angle or rubbing resistance, but the phase separation between the main polyurethane and the urethane oligomer containing the fluorine group occurred heat and light After the test, it was found that not only the adhesion but also the surface wearability was reduced.
As a result of the test, it was confirmed that the most satisfactory anti-fingerprint and surface properties in Examples 1 and 2.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070122361A KR20090055437A (en) | 2007-11-28 | 2007-11-28 | Fluorine-containing waterborne polyurethane paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070122361A KR20090055437A (en) | 2007-11-28 | 2007-11-28 | Fluorine-containing waterborne polyurethane paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20090055437A true KR20090055437A (en) | 2009-06-02 |
Family
ID=40987103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020070122361A KR20090055437A (en) | 2007-11-28 | 2007-11-28 | Fluorine-containing waterborne polyurethane paint |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20090055437A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101131888B1 (en) * | 2009-11-27 | 2012-04-03 | 주식회사 노루비케미칼 | Paint composition for plastics and method of preparing the same |
| KR20160009122A (en) * | 2014-07-15 | 2016-01-26 | (주)엘지하우시스 | Anti-pollution wall paper |
| US9920158B2 (en) | 2014-12-12 | 2018-03-20 | Hyundai Motor Company | Coating composition having smooth texture for one-coat-one bake coating |
| KR102176746B1 (en) | 2019-05-15 | 2020-11-09 | 한국신발피혁연구원 | Coating composition for weather strips |
| KR20200132037A (en) | 2019-05-15 | 2020-11-25 | 한국신발피혁연구원 | Urethane acrylate hybrid coating composition for weather strips |
-
2007
- 2007-11-28 KR KR1020070122361A patent/KR20090055437A/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101131888B1 (en) * | 2009-11-27 | 2012-04-03 | 주식회사 노루비케미칼 | Paint composition for plastics and method of preparing the same |
| KR20160009122A (en) * | 2014-07-15 | 2016-01-26 | (주)엘지하우시스 | Anti-pollution wall paper |
| US9920158B2 (en) | 2014-12-12 | 2018-03-20 | Hyundai Motor Company | Coating composition having smooth texture for one-coat-one bake coating |
| KR102176746B1 (en) | 2019-05-15 | 2020-11-09 | 한국신발피혁연구원 | Coating composition for weather strips |
| KR20200132037A (en) | 2019-05-15 | 2020-11-25 | 한국신발피혁연구원 | Urethane acrylate hybrid coating composition for weather strips |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100828789B1 (en) | Thinwall Waterborne Soft Feel Paint | |
| CN103732631B (en) | The coating composition of aqueous radiation curable | |
| KR100635996B1 (en) | Composition for aqueous coating for plastic interior in automobile | |
| RU2695222C2 (en) | Method of producing a multilayer paint system | |
| JP2680508B2 (en) | Water-based paint for constant drying | |
| RU2686904C1 (en) | Method of producing multilayer paint system on plastic bases | |
| ITVA20080046A1 (en) | AQUEOUS DISPERSIONS OF ANIONIC POLYURETHANE | |
| KR101766013B1 (en) | High elasticity aqueous adhesive composition and method for surface treatment of molded article using the same | |
| JP2010241963A (en) | Leather imparted with antifouling property | |
| KR20090055437A (en) | Fluorine-containing waterborne polyurethane paint | |
| JP2019506492A (en) | Water-soluble paint composition for automobile intermediate coating and automobile painting method using the same | |
| EP2821446B1 (en) | Very low gloss coatings with high resistance to burnishing | |
| CN106519950A (en) | Rubber paint for windshield and preparation method thereof | |
| KR100629766B1 (en) | Coating composition for interior panel of automobile | |
| KR101412758B1 (en) | 2-component type aqueous polyurethane coating composition | |
| CN115851099B (en) | Water-based two-component coating for plastic and preparation method and application thereof | |
| CN100381517C (en) | Coating composition and coating article | |
| KR101054372B1 (en) | Water Soluble Polyurethane Paint Composition | |
| KR20040073698A (en) | Composition for aqueous coating for plastic interior finish in automobile | |
| JP2009029856A (en) | Reactive diluent for modifying thermosetting paint composition and paint composition using it | |
| KR101365199B1 (en) | Water-soluble paint composition for plastics and method of manufacturing paint film using the same | |
| JP2000345109A (en) | Peelable coating material having excellent appearance and peeling properties | |
| KR20120021739A (en) | Method of painting plastic parts of automobile | |
| KR101365198B1 (en) | Water-soluble paint composition for plastics and method of manufacturing paint film using the same | |
| KR100643678B1 (en) | Crosslinked urethane-acrylic copolymer and paint composition comprising it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WITN | Withdrawal due to no request for examination |