KR20120100600A - Waterborne fluoride paint composition - Google Patents

Abstract

PURPOSE: A one-component type water-soluble paint composition is provided to improve staining resistance and weatherability. CONSTITUTION: A one-component type water-soluble paint composition comprises 10-60 weight% of acryl-modified fluorine emulsion resin, 5-30 weight% of self-crosslinked acrylic copolymer resin, 15-30 weight% of pigment, 1-15 weight% of water-soluble solvent and 5-15 weight% of water. The acryl-modified fluorine emulsion resin is formed by polymerizing and water bearing methyl methacrylate, and ethylacrylate at the end of the copolymer of vinylidene fluoride and hexafluoropropylene. The pigment is one or more selected from titanium dioxide, calcium carbonate, magnesium silicate, aluminum silicate, cobalt aluminate and cobalt chromite.

Description

Water-soluble fluoride paint composition

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble fluorine coating composition, and to a one-component heavy anticorrosive and architectural coating composition capable of drying at room temperature by containing an acrylic modified fluorine emulsion resin and an acrylic copolymer resin of self-crosslinking emulsion type.

Painting is done on the outer walls of steel structures or buildings to prevent corrosion and discoloration and to create a beautiful appearance. Currently, acrylic coatings, alkyd resins, acrylic urethane resins, fluorine resins, and the like are used as paints for medium corrosion protection, and acrylic resins are mainly used as paints for construction.

Heavy anticorrosive paints and architectural paints are treated as important physical properties because they form a coating film on exposed parts. However, acrylic paints and alkyd paints are more easily deformed by ultraviolet rays than acrylic urethane paints or fluorine paints, resulting in the need for repair painting after three to five years as the coating site is aging. In addition, acrylic urethane paints and fluorine paints are mainly oil-based paints have a disadvantage in that the use of the paint is restricted as the volatile organic compound (VOC) regulations are tightened.

In the case of the fluororesin, the bonding energy of the fluoro atom with the carbon atom of the fluoroolefin is 105.4 kcal / mol, which is very tightly bonded, and thus has a very strong characteristic against ultraviolet rays or air pollutants. Currently, most fluorine paints are two-part oil paints requiring an isocyanate curing agent. Therefore, it is expected that if a one-component fluorine paint which does not need to be mixed with a main agent and a curing agent can be obtained as an aqueous type, it can be used as a highly durable paint that can cope with the regulation of volatile organic compounds.

Korean Patent Laid-Open Publication No. 10-2000-0047281 proposes a one-component fluorine paint containing a fluoroolefin copolymer and melamine resin, but it has been difficult to be applied for heavy-duty or construction applications in that it requires a curing temperature of 170 ° C or higher. . Korean Patent No. 10-0710507 proposes a one-component fluorine paint in which a polyvinylidene fluoride (PVdF) resin, a thermoplastic acrylic resin, and a thermosetting acrylic resin are mixed, but requires high temperature baking at 200 ° C or higher. The disadvantage of requiring the condition was not overcome. In addition, Korean Patent No. 10-0879360 proposed a water-soluble fluorine paint that can be dried at room temperature by containing a water-soluble polyfluoropolymer in an emulsion state and a water-soluble polycarbonate polyurethane dispersion having a hydroxyl group, which is a PVC window paint Insufficient coating adhesion is required for heavy-duty or construction paints.

Accordingly, the present inventors have made efforts to solve the above problems, and developed a fluorine paint that can be dried at room temperature, containing water as a diluent while containing an acrylic modified fluorine emulsion resin and an acrylic copolymer resin of self-crosslinking type. By this, the present invention was completed. That is, the present invention has a very strong characteristics against ultraviolet rays, air pollutants and the like, and an object thereof is to provide a one-component water-soluble heavy anticorrosive and building paints that can be dried at room temperature.

The present invention

10 to 60% by weight of acrylic modified fluorine emulsion resin;

5 to 30% by weight of a self-crosslinkable acrylic copolymer resin;

Pigments 15-30 wt%;

Water soluble solvent 1 to 15% by weight; And

Water 5-15 wt%;

It is characterized by a water-soluble fluorine coating composition comprising a.

The water-soluble fluorine coating composition of the present invention is a room temperature dried one-component coating which does not require mixing of a main agent and a curing agent, and has excellent stain resistance and weather resistance, and can cope with the regulation of volatile organic compounds by using water as a diluent. Such a water-soluble fluorine coating composition can be usefully applied as a heavy anticorrosive paint or a building paint.

Hereinafter, the present invention will be described in more detail.

The present invention is an acrylic modified fluorine emulsion resin 10 to 60% by weight; 5 to 30% by weight of a self-crosslinkable acrylic copolymer resin; Pigments 15-30 wt%; Water soluble solvent 1 to 15% by weight; And water 5 to 15% by weight; relates to a water-soluble fluorine coating composition comprising.

Polyvinylidene fluoride (PVdF) resin having excellent weather resistance is melted at a high temperature of 230 캜 to form a coating film. However, the acrylic modified fluorine emulsion resin used in the present invention polymerizes methyl methacrylate and ethyl acrylate at the end of the fluorine-based resin in order to be able to dry the existing fluorine-based resin such as PVdF used only at high temperature at room temperature, By having such a form, a stable emulsion state is maintained even in an aqueous solution. The acrylic modified fluorine emulsion resin has a high number average molecular weight of 100,000 or more, the fluorine-based resin is vinylidene fluoride, vinyl fluoride, trifluoroethylene, cyclotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) And homopolymers or copolymers composed of one or more monomers selected from hexafluoropropylene (HFP), but are not limited thereto. Preferably, the copolymer is made of 85.8% by weight of vinylidene fluoride and 14.2% by weight of hexafluoroflopylene, and 50 to 70% by weight of the copolymer is mixed with methyl methacrylate and ethylacrylate, which are acrylic monomers. It is preferable to use an acrylic modified fluorine emulsion resin obtained by polymerizing 30 to 50% by weight of the resin. The commercialized product is Alkenma KYNAR AQUATEC ARC (RC-10206). RC-10206 has a solid content of 45 to 55% and can form a coating film at a temperature of -5 to 40 ° C.

The acrylic modified fluorine emulsion resin is contained in 10 to 60% by weight of the coating composition, if the content is less than 10% by weight may have a problem of poor weatherability of the coating film, on the contrary, when the content exceeds 60% by weight, the coating film There may be a problem of poor adhesion.

The self-crosslinkable acrylic copolymer resin is not a two-dimensional structure in which the particles and particles combine with the old particles to form a weak coating film, while the water is volatilized in the drying process, the particles and particles are combined, and the reactor (-NCO) chemically reacts with the water. The thing of the polymer emulsion state which forms the coating film of the three-dimensional crosslinked structure which combines and forms a strong coating film is used. In the self-crosslinkable acrylic copolymer resin, hexamethylene diisocyanate and isophorone diisocyanate are added, stirred, and reacted to synthesize an NCO prepolymer, and 2-hydroxy ethyl methacrylate and methyl methacrylate to block the reaction with water. Two or more selected from acrylate, ethyl acrylate, and styrene monomers are added, polymerized, and reacted, followed by neutralization with triethylamine, ammonia, and the like, followed by emulsification by high-speed stirring. As a commercialized product, LUBRIZOL's CA-600 can be used.

The content of the self-crosslinkable acrylic copolymer resin in the coating composition is preferably 5 to 30% by weight. If the content is less than 5% by weight, the coating film adhesion may be deteriorated. Since it is difficult to show excellent physical properties compared to the general acrylic paint, it is difficult to apply as a heavy coating or construction paint that requires high weather resistance and pollution resistance, which are advantages of water-soluble fluorine paint.

The pigment is used to impart color and hiding power to the coating film, and the pigment usable in the present invention is not particularly limited, and specifically, selected from titanium dioxide, calcium carbonate, magnesium silicate, aluminum silicate, cobalt aluminate and cobalt chromite. 1 or more types can be used. The content of the pigment in the coating composition of the present invention is preferably 15 to 30% by weight. If the content of the pigment is less than 15% by weight, it may be insufficient to impart hiding power by color and coating, and may have problems of poor chemical resistance and weather resistance. In addition, even if it exceeds 30% by weight, it is difficult to expect the benefit of the effect of the increase, rather it is good to select the above range because the physical properties such as impact resistance, adhesion, etc. may be reduced by decreasing the content of other components.

The water-soluble solvent is a medicament that can be mixed with water, at least one selected from ethyl cellulsolve, butyl cellulsolve, methyl carbitol, ethyl carbitol, butyl carbitol, ethyl alcohol, methyl alcohol, butyl alcohol and isobutyl alcohol. Can be used. The amount of the water-soluble solvent is preferably 1 to 15% by weight in the coating composition. When the content of the water-soluble solvent is less than 1% by weight, the drying may be slow, and coating film formation may be difficult. If the content of the water-soluble solvent exceeds 15% by weight, the content of volatile organic compounds in the composition may increase, which is disadvantageous in response to environmental regulations.

Water contained in the water-soluble fluorine coating composition of the present invention is used as a diluent, the content of the composition is preferably 5 to 15% by weight. If the amount of water is too small, it is disadvantageous in terms of storage stability, and if it exceeds 15% by weight, there is a problem that the paint workability is lowered due to the low viscosity of the paint.

In addition to the above essential components, the water-soluble fluorine coating composition of the present invention may further contain conventional additives usable in paints such as antifoaming agents, surfactants, wetting agents, wetting dispersants, plasticizers, preservatives, pH adjusting agents, thickeners and the like as necessary. Can be.

The water-soluble fluorine coating composition of the present invention is a room temperature dry type one-component coating which does not require mixing of the main agent and the curing agent, and is excellent in fouling resistance and weather resistance, and thus can be usefully applied as a heavy anticorrosive paint or a building paint.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

[Example]

Example 1

Into the flask, 7 g of water, 1 g of a surfactant (Triton cf-10, DOW), and 1 g of a wet dispersant (BYK154, BYK) of an emulsion paint were added and stirred using a stirrer. In order to remove bubbles generated on the surface during stirring, 0.2 g of an antifoaming agent (TEGOFOMAX 810, TEGO Co., Ltd.) was added thereto and stirred for 5 minutes, and 20 g of titanium dioxide (R960, DuPont Co., Ltd.) was added thereto and stirred for 5 minutes. Thereafter, 0.5 g of antifreeze ethylene glycol and 0.5 g of polyether-modified siloxane (BYK349, BYK) as a wetting agent were added and stirred at 3000 rpm. After checking the particle size below 10 ㎛ 2g of urethane thickener (HIRESOL 200, HANKUCK LATICES Co., Ltd.) was added and stirred at high speed again at 3000 rpm.

Then 50 g of acrylic modified fluorine emulsion resin (RC-10206, Alkema, solid content 48% by weight) and 7 g of self-crosslinkable acrylic copolymer resin (CA-600, LUBRIZOL) were added and stirred at 1000 rpm. 3 g of ester alcohol (texanol, ESTMAN Co., Ltd.), 0.2 g of preservative (BETACIDE LX, Osan Chemical Co., Ltd.) and 0.1 g of pH adjuster (25% ammonia water) were added thereto, followed by stirring at 1000 rpm. In order to remove bubbles generated during stirring, 0.6 g of an antifoaming agent was added, and then 0.1 g of polyether-modified dimethylpolysiloxane (BYK333, BYK), an ionic surfactant, was added, and 0.5 g of ethyl celusolve, a water-soluble solvent, was stirred. And 1.5 g of water were added thereto. Thereafter, 3 g of butyl celusolve, a water-soluble solvent, 0.5 g of an acrylic thickener (HISOL D206, HANKUCK LATICES Co., Ltd.) and 1.3 g of water were added thereto, followed by stirring at 1000 rpm to prepare a coating composition.

Example 2

The coating composition was prepared in the same manner as in Example 1, but changing the content of acrylic modified fluorine emulsion resin, self-crosslinkable acrylic copolymer resin, water-soluble solvent and water as shown in Table 1 below.

Comparative Example 1

AK ChemTech's KSM 6010 class 1 class 1, an aqueous acrylic emulsion paint, was used as a control.

Comparative Example 2

AK ChemTech's AU 6203 B, an oilless yellowing type acrylic urethane paint, was used as a control.

Comparative Example 3

AK Prom of AK ChemTech, an oil-based natural dry fluorine paint, was used as a control.

division weight% Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Acrylic modified
Fluorine Emulsion Resin 50 40 30 Mercury
Acrylic
Emulsion
varnish
(KS M 6010 Class 1 Class 1) meteor
Yellowing
Type of
acryl
urethane
varnish
(AU 6203B) meteor
Natural dry fluorine
varnish
(AK fron) Self crosslinkable acrylic
Copolymer resin 7 17 27 Pigment 20 20 20 Water soluble solvent 3.5 2.5 1.5 water 9.8 10.8 11.8 Wet Dispersant One One One Antifoam 0.8 0.8 0.8 antifreeze 0.5 0.5 0.5 Wetting agent 0.5 0.5 0.5 Thickener 2.5 2.5 2.5 Plasticizer 3 3 3 antiseptic 0.2 0.2 0.2 pH regulator 0.1 0.1 0.1 Surfactants 1.1 1.1 1.1

Physical property test

Epoxy zinc undercoat (AK zinc EZP-10W, AK ChemTech) was painted with a thickness of 75 μm on a dry film thickness and dried for 1 day on the hot rolled steel sheet most similar to the steel surface used in the steel coating site. (S) # 200, AK ChemTech Co., Ltd.) was coated with a dry film thickness of 100 µm and dried for 1 day. Thereafter, the coating compositions of Examples 1 to 3 and Comparative Examples 2 and 3 were coated with a dry coating thickness of 40 μm and tested for physical properties of the coating film.

In addition, a water-soluble epoxy coating material (AKUAPOXY (W) # 100, AK ChemTech Co., Ltd.) was coated with a dry coating thickness of 40 μm on a slate plate most similar to the concrete surface and dried for one day, followed by Examples 1 to 3 and Comparative Example 1 A coating composition of ˜3 was coated with a dry coating thickness of 40 μm and the physical properties of the coating film were tested.

1. Dryability

The coating compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were applied to a glass plate with a wet coating film thickness of 5 Mil to evaluate dryness.

2. Adhesion

When the coating film formed on the hot rolled steel sheet and the slate plate is crossed by 2 mm intervals to reach the surface of the test specimen by using a razor, 100 graduations are made, and when the scotch tape of KS-S 1528 standard is sufficiently compressed, pulled in 90 ° direction. The coating film peeling state of was observed.

3. Salt water spray resistance

The coating film formed on the hot-rolled steel sheet was dried for 7 days after the top coat, and salt water spray resistance test was performed for 240 hours according to ASTM D 2247,714. Measurement was carried out within 10 seconds after the test piece was taken out at low temperature.

4. Chemical resistance

Tested in accordance with ASTM D1308, water resistance was xylene, alkali resistance was saturated calcium hydroxide solution, acid resistance was 5% aqueous solution of sulfuric acid, and the test was carried out for 240 hours on completely dried specimens. Observed.

5. Weather resistance

QUV tester type B, an accelerated weathering tester, was observed as a gloss retention and color change after 1000 hours.

division Object: Slate Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Drying ○ ○ ○ ○ ○ ○ Adhesion ◎ ◎ ◎ ○ ◎ ◎ of mine
about
Width
castle water ○ ○ ○ ○ ○ ○ Xylene ○ ○ ○ △ ○ ○ Calcium hydroxide
Aqueous solution ○ ○ ○ ○ ○ ○ Sulfuric acid solution ○ ○ ○ ○ ○ ○ Weatherability (ΔE) 0.9 1.2 1.8 8.5 1.6 1.3 (◎; Excellent, ○; Good, △; Lack, X; Poor)

division Work: Hot Rolled Steel Sheet Example 1 Example 2 Example 3 Comparative Example 2 Comparative Example 3 Drying ○ ○ ○ ○ ○ Adhesion ◎ ◎ ◎ ◎ ◎ Salt water spray resistance ○ ○ ○ ○ ○ of mine
about
Width
castle water ○ ○ ○ ○ ○ Xylene ○ ○ ○ ○ ○ Calcium hydroxide
Aqueous solution ○ ○ ○ ○ ○ Sulfuric acid solution ○ ○ ○ ○ ○ Weatherability (ΔE) 0.9 1.2 1.8 1.6 1.3 (◎; Excellent, ○; Good, △; Lack, X; Poor)

As can be seen in Tables 2 to 3, the coating film formed of the coating composition of the present invention showed excellent results in weatherability than the coating film formed of the water-based acrylic paint of Comparative Example 1, and showed excellent results in terms of adhesion and solvent resistance. It was. The oil-based acrylic urethane paint of Comparative Example 2 forms a coating film obtained by curing acrylic polyol with an isocyanate curing agent, and the oil-based fluorine paint of Comparative Example 3 forms a coating film obtained by curing a copolymer of polyfluoro and acrylic monomer with an isocyanate curing agent. It is excellent in stain resistance, but it is inconvenient to use as a two-component paint, and it is difficult to cope with the regulation of volatile organic compounds.

After all, the water-soluble fluorine coating composition of the present invention is an environmentally friendly one-component water-based paint having properties such as weather resistance and fouling resistance or more equivalent to conventional oil-based two-component acrylic urethane paints or oil-based two-component fluorine paints. It could be confirmed that it is usefully applicable.

Claims (6)

10 to 60% by weight of acrylic modified fluorine emulsion resin;
5 to 30% by weight of a self-crosslinkable acrylic copolymer resin;
Pigments 15-30 wt%;
Water soluble solvent 1-15 wt%; And
Water 5-15 wt%;
Water-soluble fluorine coating composition comprising a.
The method of claim 1, wherein the acrylic modified fluorine emulsion resin is vinylidene fluoride, vinyl fluoride, trifluoroethylene, cyclotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) and hexafluoropropylene (HFP A water-soluble fluorine coating composition characterized by polymerizing and dispersing methyl methacrylate and ethyl acrylate at the end of a homopolymer or copolymer composed of one or more monomers selected from:
The water-soluble fluorine according to claim 1, wherein the acrylic modified fluorine emulsion resin is polymerized by dispersing methyl methacrylate and ethyl acrylate at the terminal of the copolymer of vinylidene fluoride and hexafluoroflopylene. Paint composition.
The method of claim 1, wherein the self-crosslinkable acrylic copolymer resin is NCO prepolymer reacted with hexamethylene diisocyanate and isophorone diisocyanate, 2-hydroxy ethyl methacrylate, methyl methacrylate, ethyl acrylate and styrene A water-soluble fluorine coating composition characterized by polymerizing, neutralizing and dispersing two or more selected from monomers.
The water-soluble fluorine coating composition according to claim 1, wherein the pigment is at least one selected from titanium dioxide, calcium carbonate, magnesium silicate, aluminum silicate, cobalt aluminate and cobalt chromite.
The method of claim 1, wherein the water-soluble solvent is at least one selected from ethyl cell solution, butyl cell solution, methyl carbitol, ethyl carbitol, butyl carbitol, ethyl alcohol, methyl alcohol, butyl alcohol and isobutyl alcohol Water-soluble fluorine coating composition.