KR102081265B1 - Environmental―friendly waterproof paint compositions - Google Patents

Abstract

The present invention relates to an eco-friendly water-soluble waterproof paint composition and, more specifically, to an eco-friendly water-soluble waterproof paint composition comprising: a silicone resin emulsion; a latex emulsion; silica; titanium dioxide; and a phosphorus-based organic compound. The eco-friendly water-soluble waterproof paint composition according to the present invention comprises no toxic substances such as volatile organic compounds (VOCs) and formaldehyde. The adhesion, waterproofness, corrosion resistance, flame retardancy or non-combustibility, and construction convenience are excellent. In addition, the durability of a paint film is excellent and semi-permanent use is possible.

Description

Eco-friendly water-soluble waterproof coating composition {ENVIRONMENTAL-FRIENDLY WATERPROOF PAINT COMPOSITIONS}

The present invention relates to an environment-friendly water-soluble waterproof coating composition, and more particularly, to an environment-friendly water-soluble waterproof coating composition that is applied to the surface of the metal material to provide excellent waterproof, anticorrosive, salt water resistance, acid resistance, durability and the like.

In general, as well as buildings, a large number of metal raw materials are used in various fields such as civil structures or ships.

Since these metal raw materials are easily rusted or corroded, it is necessary to perform antirust treatment in order to function stably over a long period of time. However, many of the rust-preventive materials remain weak, such as poor adhesion to the material to be treated, and cumbersome coating process.

In addition, such a metal raw material may be troublesome that the waterproofing, acid resistance, and salt water resistance may be prevented by repainting the waterproofing paint after treatment of the antirust coating.

In addition, conventional anti-corrosive coating compositions for metals include organic resins and organic solvents, and most of them include toxic substances such as VOCs and formaldehyde. When absorbed into the human body, these toxic substances affect the central nervous system and act as a threat to the health of workers or users. In addition, there are cases where photo-luminescent compounds containing heavy metals such as chromium or lead (red lead), zinc chromate, lead cyanide, strontium chromate, etc. are used as rust preventive pigments. Many not only pose a huge threat to the health of workers and consumers, but also cause environmental pollution.

In order to improve this problem, many water-based rust-preventive coatings have been recently developed. As the aqueous rust-preventive paints, water-soluble alkyd resins or condensation reaction products of acrylic resins and amino resins are known. Such rust-preventive paint compositions contain emulsifiers and water-soluble components added for the stabilization of paints and pigment dispersion effects. Due to the use of a water-soluble resin having a large amount of hydrophilic groups introduced into the dispersant and the polymer backbone, there is a problem of poor corrosion resistance of the coating film.

As an example of the water-soluble rust-preventive coating, Korean Patent No. 10-0816522 No. 30 to 50% by weight of the composite binder resin; Zinc powder 40 to 50% by weight; And a water-soluble rust-preventive paint comprising 10 to 20% by weight of extender pigments. In addition, the Republic of Korea Patent No. 10-1079778, polyvinylidene chloride copolymer emulsion 30 to 50 parts by weight, inorganic nano binder 1 to 20 parts by weight, inorganic rust preventive agent 2 to 10 parts by weight, sieving pigment 15 to 25 parts by weight and film formation A water-soluble rust-preventive coating composition comprising 1 to 5 parts by weight of the formulation was proposed.

However, these pre-registered patents also had a disadvantage in that physical properties as anti-corrosive paints, that is, corrosion resistance is not sufficient enough to be used as a rust-preventive paint. There was also the hassle of having to paint a separate waterproofing paint.

KR 10-0816522 B1 KR 10-1079778 B1

Accordingly, an object of the present invention is to provide an environmentally friendly water-soluble waterproof coating composition that does not contain toxic substances such as volatile organic compounds (VOCs) and formaldehyde, and which is excellent in water resistance, corrosion resistance and flame retardancy or nonflammability.

Another object of the present invention is an environmentally friendly water-soluble waterproof coating composition having excellent coating properties and adhesiveness, and can be applied to an rust-removing site without additional rust removal without the need to apply an antirust coating. To provide.

Environment-friendly water-soluble waterproof coating composition of the present invention for achieving the above object is characterized in that it comprises a silicone resin emulsion, latex emulsion, silica, titanium dioxide and phosphorus organic compounds.

The silicone resin emulsion is at least one selected from the group consisting of an alkyl (Alkyl) silicone resin, a tri-ethoxy silicone resin and an alkylalkoxy silicone resin, the latex emulsion is At least one selected from the group consisting of an acrylic emulsion and a vinyl acetate emulsion, the phosphorus organic compound is characterized in that the triphenyl phosphate or tricresyl phosphate.

The silicone resin emulsion is characterized in that it comprises 25 to 35% by weight, latex emulsion 25 to 35% by weight, silica 20 to 30% by weight, titanium dioxide 4 to 10% by weight and phosphorus-based organic compounds 0.1 to 0.5% by weight.

It is characterized in that it further comprises 1 to 10% by weight of antifoaming agent, 1 to 10% by weight of adhesion promoter, 0.1 to 1% by weight of thickener, 0.1 to 1% by weight of anti-coat agent and 1 to 5% by weight of silane coupling agent.

The adhesion promoter is hydrocarbon, the thickener is hydroxyethyl cellulose or methyl cellulose, and the anti-coat agent is at least one selected from the group consisting of silicone oil and oxime 2-butanone. It is done.

Eco-friendly water-soluble waterproof coating composition according to the present invention, does not contain toxic substances such as volatile organic compounds (VOCs) and formaldehyde, has the advantage of excellent adhesion, waterproof, anticorrosive, flame retardant or non-flammable and construction convenience. . In addition, the durability of the coating film has the advantage that it can be used semi-permanently.

Hereinafter, the present invention will be described in detail.

Conventionally, the coating composition for metal materials has to apply an rust-preventive paint, and then apply a waterproof paint again, and the site where the rust occurs has had to be completely removed and constructed. In addition, the antirust and waterproof coatings are not sufficient adhesiveness with the metal base material, there was also a problem that caused environmental pollution due to toxic substances such as various volatile organic compounds (VOCs) and formaldehyde.

Accordingly, the present invention solves this problem, and provides a water-soluble, water-soluble, waterproof coating composition mainly composed of silicone resin emulsion and latex emulsion.

The present invention is applied to the surface of the metal material to exhibit excellent adhesion, as well as excellent waterproof, rust-proof and flame-retardant or non-flammable properties, but also excellent resistance to salt water, acid, alkali, rust, waterproof, flame retardant or non-combustible It can be used as a paint. Moreover, even if a deformation | transformation arises in a metal base material, it is a characteristic that there is no cut | disconnection of a coating film by the outstanding tensile force.

In addition, the coating composition of the present invention can be applied as it is without removing the rust of the metal material in which the rust is conventional, it is characterized in that the convenience of construction is also excellent, when the coating film is formed on the inner and outer surfaces, such as steel pipe, loss due to frictional force It is also characterized by low.

Such an environmentally friendly water-soluble waterproof coating composition of the present invention is characterized in that it contains a silicone resin emulsion, a latex emulsion, silica, titanium dioxide and a phosphorus organic compound.

The silicone resin emulsion is a main component constituting the coating composition of the present invention together with a latex emulsion, provides impermeability to the coating film, expresses physical properties such as acid resistance and alkali resistance, and enhances adhesion to metal materials. to be. The silicone resin emulsion may be one or more selected from the group consisting of an alkyl (Alkyl) silicone resin, a tri-ethoxy silicone resin, and an alkylalkoxy silicone resin.

At this time, the active ingredient (silicone polymer) content of the silicone emulsion is preferably 40 to 80% by weight, which is less than 40% by weight of the active ingredient, the adhesion to the metal surface is lowered, if it exceeds 80% by weight This is because the surface strength of the coating film decreases due to the decrease in curing reaction.

The silicone resin emulsion is contained in 25 to 35% by weight with respect to 100% by weight of the coating composition, if the content is less than 25% by weight is difficult to form a coating film, when it exceeds 35% by weight, excellent waterproof due to the decrease in surface strength This is because the effect cannot be exerted.

The latex emulsion is a main component to form a coating film, provides eco-friendliness, and expresses physical properties such as water resistance, acid resistance, saline resistance, alkali resistance, and accelerated weather resistance. In addition, it provides excellent adhesion, as well as absorbs rust and exhibits excellent adhesion even when applied directly to rusty areas.

As the latex emulsion, one or more selected from the group consisting of an acrylic emulsion and a vinyl acetate emulsion may be used. Such an acrylic emulsion or a vinyl acetate emulsion may be an acrylic monomer composition or a vinyl acetate monomer composition in the presence of a polyvinyl alcohol-based material. Can each be prepared by emulsion polymerization in an aqueous medium (eg water). The acrylic monomer composition may include an acrylic monomer, and the vinyl acetate monomer composition may include a vinyl acetate monomer. The acrylic monomer composition and the vinyl acetate monomer composition may further include other components, respectively. The vinyl acetate monomer may include vinyl acetate, and the acrylic monomer may include ethyl acrylate, ethyl methacrylate, methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, and butyl acrylate. , Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, alkoxyethyl acrylate or combinations thereof. The other components are monomers (eg, divinylbenzene, divinyl adipate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth)) copolymerizable with the vinyl acetate monomer and the acrylic monomer, respectively. Acrylates); Water-soluble oligomers (eg 2-methacrylamide-2-methylpropanesulfonic acid copolymer, sodium methacrylate-4-styrenesulfonate copolymer, polyvinylpyrrolidone, poly (meth) acrylate); Polymerization initiators (eg, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide); Polymerization regulators (eg, methanol, ethanol, propanol, acetone, dodecyl mercaptan); Emulsifiers (eg, sodium lauryl sulfate) and combinations thereof.

The active ingredient (latex resin) of the latex emulsion is also preferably included in 40 to 80% by weight, but is not necessarily limited thereto.

The latex emulsion is contained in 25 to 35% by weight relative to 100% by weight of the coating composition, if the content is less than 25% by weight is difficult to form a coating film, there is a disadvantage that the durability is lowered when it exceeds 35% by weight Because.

The silica is used as a sedimentation inhibitor in the coating composition, it prevents sedimentation to ensure storage stability, and serves to improve physical properties such as increasing the durability of the coating film. The silica is economical to use fumed silica, but is not limited thereto.

The silica is contained in 20 to 30% by weight in 100% by weight of the coating composition, if the content is less than 20% by weight its effect is insignificant, if it exceeds 30% by weight is excessive, rather waterproof, corrosion-resistant This is because there is a disadvantage.

The titanium dioxide is used as a photocatalyst, reacts with ultraviolet light, is harmless to the human body, and is a physicochemically stable material.

Such titanium dioxide is contained in 4 to 10% by weight in 100% by weight of the coating composition, if the content is less than 4% by weight, the effect is insignificant, and if it exceeds 10% by weight, it becomes excessive and the waterproofing and corrosion resistance are reduced. .

The phosphorus-based organic compound is to impart flame retardancy or non-flammability to the coating composition, and to adjust the content thereof to produce a flame retardant or non-flammable product.

In this case, the phosphorus-based organic compound may be triphenyl phosphate or tricresyl phosphate, but is not necessarily limited thereto.

The phosphorus-based organic compound is contained in 0.1 to 0.5% by weight relative to 100% by weight of the coating composition, the content is less than 0.1% by weight, the effect is insignificant, if it exceeds 0.5% by weight overall physical properties of the coating film rather deteriorated This is because there is a problem.

As described above, 25-35% by weight of silicone resin emulsion, 25-35% by weight of latex emulsion, 20-30% by weight of silica, 4-10% by weight of titanium dioxide and 0.1-0.5% by weight of phosphorus-based organic compound The composition is coated with a metal material, that is, a metal raw material, as well as a metal structure, for example, a sash, steel pipe, steel structure, steel roof, etc., exhibiting excellent waterproof, flame retardant or non-flammable, anti-rust properties, and excellent tensile strength, Even if deformation occurs in the phosphorous metal, there is no cutting (cracking), swelling, etc., and there is an advantage in that a semi-permanent coating film having excellent physical properties such as acid resistance, alkali resistance, saline resistance, and accelerated weather resistance can be formed.

In addition, there is no need for a separate rust removal operation during construction, absorbing rust when applied to the rusting area to exhibit a strong adhesive force, it is also possible to apply on the existing aging coating has the advantage of excellent construction convenience.

Meanwhile, the coating composition of the present invention may further include an antifoaming agent, an adhesion promoter, a thickener, an anti-filming agent, and a silane coupling agent. Such additives are intended to enhance physical properties such as adhesion of the coating film.

The antifoaming agent is used to remove harmful bubbles, it is possible to use a polysiloxane-based compound, for example, a polyester siloxane copolymer emulsion containing hydrophobic silica. The antifoaming agent is preferably used in 1 to 10% by weight relative to 100% by weight of the coating composition.

The adhesion promoter is to further increase the adhesion of the coating film, it may be used a hydrocarbon resin (Hydrocarbon resin). The adhesion promoter is preferably used in 1 to 10% by weight relative to 100% by weight of the coating composition.

The thickener is to improve the applicability by increasing the viscosity, cellulose derivatives (cellulose derivatives) which is a powdery thickener may be used. As the cellulose derivative, hydroxyethyl cellulose or methyl cellulose may be used. The thickener is preferably used 0.1 to 1% by weight based on 100% by weight of the coating composition.

The anti-coat agent is to prevent the film from forming during the storage of the paint, it may be used one or more selected from the group consisting of silicone oil and oxime 2-butanone. The anti-coat agent is preferably used 0.1 to 1% by weight based on 100% by weight of the coating composition.

The coupling agent may be used a silane coupling agent usually used in the coating composition, it is preferably used 1 to 5% by weight based on 100% by weight of the coating composition.

In addition, in addition to the extender pigment may further comprise 0.1 to 2% by weight, the extender pigment is sufficient to use a known one.

The coating composition of the present invention configured as described above can be prepared in the same manner as the method for producing an aqueous coating composition, the production method according to a known method. In addition, it can be applied by various methods such as a brush, roller, spray, etc., it is natural that it is also possible to apply after applying the primer before the coating, it is natural that it is also possible to paint a plurality of times.

Hereinafter, the present invention will be described in more detail with reference to the accompanying examples.

(Example 1)

To prepare a coating composition of the composition as shown in Table 1.

division Compounding ratio (wt%) Silicone resin emulsion Active ingredient 50% alkyl system
(Degussa Tegosivin HE-328) 30 Latex emulsion 50% active ingredient, acrylic
(BASF, Acronal S559) 30 Silica Fumed silica powder 25 Titanium dioxide - 5 Phosphorus Organic Compound Triphenylphosphate (Daihachi) 0.5 Antifoam Tego Airex 902 W 3 Adhesion promoter Hydrocarbon resin
(Regalite R1100) 3 Thickener Methylcellulose 0.3 Anti-Skin Agent Oxime 2-butanone 0.2 Silane coupling agent Methacrylosilane (OFS-6030, Xiameter) 3

Then, the two-part epoxy primer (EP170-2263) was applied to an iron plate having a thickness of 20 mm in an amount of 0.2 kg / m 2, and the coating composition was applied in an amount of 1 kg / m 2, and then dried at room temperature for 12 hours.

(Comparative Example 1)

The same procedure as in Example 1, except that silicone resin emulsion was used in place of latex emulsion and adhesion promoter.

(Comparative Example 2)

The same procedure as in Example 1, except that latex emulsion was used in place of silicone resin emulsion and adhesion promoter.

(Test Example 1)

This was then commissioned by the Korea Institute of Chemical Convergence Testing to measure basic properties. The results were as shown in Table 2 below.

Test Example 1 Results Test Items Example 1 Comparative Example 1 Comparative Example 2 Test Methods Neutral salt water test (168h, red rust) clear Red rust occurrence Red rust occurrence KS D 9502: 2009 Accelerated weathering test (*) clear - - KS M ISO 16474-2: 2013 Appearance (swelling, splitting, falling) clear clear clear - Adhesion Strength (Mpa) 2.0 0.8 1.0 KS M ISO 4624: 2016 (**) Thermal shock test clear clear clear (***) After liquid resistance (5% HCl, 168h)
Swelling, cracking, falling clear Slight swelling Slight swelling KS M ISO 2812-1: 2007 After liquid resistance (5% NaOH, 168h)
Swelling, cracking, falling clear Slight swelling Slight swelling KS M ISO 2812-1: 2007 * Accelerated weathering test conditions
Light Source: 12000W Xenon Arc, Irradiance: 0.52W / ㎡
BPT: 63 ℃ ± 3 ℃, Humidity: 50% ± 5% RH
Inner / Outer Filter: Borosilicate,
Spray Cycle: 18min / 120min, Exposure Time: 168h

** Test speed: 1 MPa / s or less
Test equipment: PosiTest AT (DEFELSKO-USA)

*** Test condition: ((-10 ± 2) ℃, 6h-> (60 ± 2) ℃, 6h) × 4cycles, then check for abnormalities in appearance

As can be seen in Table 2, the neutral salt spray test, accelerated weathering test, appearance, adhesion strength, thermal shock test, liquid resistance (HCl, NaOH) test all showed excellent results, but Comparative Example 1 , 2 is a neutral salt spray test, the liquid resistance is poor, the adhesion strength was also confirmed to be poor.

(Test Example 2)

The content test of the volatile organic compounds of the coating composition of Example 1 was carried out, and the results are shown in Table 3 below. The test method for the content of volatile organic compounds was conducted according to EPA 5021 (Headspace), GC / MS method.

Test Example 2 Results (mg / kg) Test items Method detection limit (MDL) result Benzene One N.D. O-Xylene One N.D. Styrene One N.D. N.D. = Not detected (<MDL)

As shown in Table 3, the anti-corrosive coating composition according to the present invention was confirmed that the content of VOCs is N.D.

As mentioned above, although this invention was demonstrated in detail using the preferable embodiment, the scope of the present invention is not limited to a specific embodiment and should be interpreted by the attached Claim. In addition, those of ordinary skill in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

Claims (5)

25 to 35 weight percent of silicone resin emulsion, 25 to 35 weight percent of latex emulsion, 20 to 30 weight percent of silica, 4 to 10 weight percent of titanium dioxide, and 0.1 to 0.5 weight percent of phosphorus organic compound,
The silicone resin emulsion is at least one selected from the group consisting of an alkyl (Alkyl) silicone resin, a tri-ethoxy silicone resin and an alkylalkoxy silicone resin,
The latex emulsion is one or more selected from the group consisting of an acrylic emulsion and a vinyl acetate emulsion,
The phosphorus organic compound is triphenyl phosphate or tricresyl phosphate,
It further comprises 1 to 10% by weight of antifoaming agent, 1 to 10% by weight of adhesion promoter, 0.1 to 1% by weight of thickener, 0.1 to 1% by weight of anti-coat agent and 1 to 5% by weight of silane coupling agent,
The adhesion promoter is hydrocarbon,
The thickener is hydroxyethyl cellulose or methyl cellulose,
The anti-coat agent is an environmentally friendly water-soluble waterproof coating composition, characterized in that at least one selected from the group consisting of silicone oil and oxime 2-butanone. delete delete delete delete