KR20200109708A - Incombustible coating composition for pre-coated metal color steel sheet - Google Patents

Abstract

The present invention relates to a non-combustible paint composition comprising: a silicone-modified polyester resin; and a melamine resin, wherein the silicone-modified polyester resin is a reaction product of a silicone intermediate and a polyester resin, and the mass ratio of the silicone intermediate : the polyester resin is 30 : 70 to 80 : 20. The non-combustible paint composition of the present invention can be used for a PCM color steel sheet, and the non-combustible performance as a non-combustible material according to a test method of the Ministry of Land, Infrastructure and Transport Notification No. 2018-771 (KS F ISO 1182, KS F 2271) is exhibited.

Description

Non-flammable paint composition for PCM color steel sheet {INCOMBUSTIBLE COATING COMPOSITION FOR PRE-COATED METAL COLOR STEEL SHEET}

The present invention relates to a non-combustible coating composition for PCM color steel sheet exhibiting non-combustible performance and mass production according to the test method set forth in Article 2 of Notification No. 2018-771 of the Ministry of Land, Infrastructure and Transport (KS F ISO 1182, KS F 2271).

Methods of painting metal include a pre-coating method that paints before molding and a post-coating method that paints after molding. The steel plate painted by the pre-coating method is called PCM (Pre-coated Metal) or color steel plate, and the paint used for this is called PCM paint.

There are two types of metal sheets used for color steel sheets: a sheet form cut into a certain size and a coil form. Most of the color steel sheet production processes adopt a coil coating method that automatically and continuously coats metal coils. This color steel sheet has the advantage of pursuing process rationalization, quality stability, resource saving, pollution measures, energy saving, construction period shortening, and cost reduction.

The general manufacturing method of colored steel sheet is to paint the bottom and top coat on the entire surface or finish the top coat after painting the bottom and middle coat. The color steel sheet may include a printing roll in which a pattern is formed through a printing process of a gravure offset method and a printing steel sheet in which the pattern is transferred using a transfer roll. Also, if necessary, there may be a steel plate coated with a paint for the back surface.

The most common color steel sheet used for building materials is to paint an average of 5 µm for the undercoat and an average of 15 to 20 µm for the top coat and 5 to 10 µm for the back side of the metal substrate that has been pretreated for chemical conversion. .

These colored steel sheets have a colorful appearance and do not need reprocessing, such as various colors and patterns, and have been widely used in home appliances such as washing machines, refrigerators, and TVs, construction materials, and commercial vehicles, and the market has expanded for indoor and outdoor interior applications. Has become.

The main component of paint for color steel sheet is provided in the form of mixing and dispersing a pigment and an additive in a binder in which an organic resin, a hardener, and a solvent are mixed. When the paint is painted on the substrate and then baked, the solvent is volatilized and the organic resin is cured by thermal reaction to form a coating film. At this time, the natural performance of the color steel sheet is exhibited.

On the other hand, with the increasing social interest in fire and fire safety in recent years, the demand for non-combustible color steel sheets in the color steel sheet industry is increasing. According to the performance test standards pursuant to Article 2 of Notification No. 2018-771 of the Ministry of Land, Infrastructure and Transport, it can be recognized as a non-combustible material only after passing both the non-combustible test corresponding to KS F ISO 1182 and the gas hazard test corresponding to KS F 2271. In the case of color steel sheet, molding processability is a very important physical property requirement, and as mentioned above, most PCM paints are designed in the form of forming a film by mixing a pigment with an organic resin. However, in the non-flammability test corresponding to KS F ISO 1182, the organic resin or pigment component is ignited and the performance test does not pass. Therefore, its performance is not recognized as a non-combustible material, and there is a limitation that it cannot be used in the field where non-combustible materials must be constructed.

In addition, the technical difficulty is very high to satisfy the non-combustible performance according to the non-combustible material test method while maintaining the physical properties such as color, gloss, durability, etc. required as a color steel sheet, coating workability, and molding quality, so there are not many commercial cases. White and beige colors, which are commonly used as interior/exterior materials, have not yet been commercialized in the domestic color steel sheet industry.

In order to overcome the above problems, many researches and developments are underway in the industry, and recently, Patent Publication No. 10-2018-0002136 (non-combustible or flame-retardant color steel sheet, and a manufacturing method thereof) has been introduced. However, the composition provided in the patent is a water-soluble ceramic paint, which is inadequate for application to the existing color steel sheet manufacturing line designed and operated for oil-based paint. For example, there is a limitation in realizing the color (white, beige, silver, etc.) and physical properties of color steel sheets that are commonly distributed in the existing interior material market, and the manufacturing cost is general color because the price of paint is expensive and high-speed coating workability is not secured. Very high compared to steel plate. Due to such limitations, the conventional non-combustible color steel sheet is not commercially commercialized even if technically non-combustible performance is secured.

Republic of Korea Patent Publication No. 10-2018-0002136

An object of the present invention is to overcome the technical limitations of the conventional PCM paint described above, and at the same time realize the color, physical properties, high-speed workability, and manufacturing cost equivalent to that of the conventional colored steel plate for building materials, and at the same time as announced by the Ministry of Land, Infrastructure and Transport. It is to provide a non-combustible coating composition that satisfies the requirements of the non-combustible material performance test specified in Article 2 of 2018-771.

In order to achieve the above object, the present invention,

As a non-flammable coating composition comprising a silicone-modified polyester resin and a melamine resin, the silicone-modified polyester resin is a reaction product of a silicone intermediate and a polyester resin, and the silicone intermediate: polyester resin has a mass ratio of 30:70 to 80: It provides a non-flammable coating composition of 20.

It is preferable that the non-combustible coating composition further includes any one selected from the group consisting of pigments, flame retardants, organic solvents, additives, and mixtures thereof.

In addition, the non-flammable coating composition of the present invention includes 5 to 40% by weight of the silicone-modified polyester resin, 1 to 20% by weight of melamine resin, 5 to 40% by weight of pigment, 5 to 40% by weight of flame retardant, 30 to 80% by weight of organic solvent , It is preferable to include 1 to 10% by weight of additives.

In this case, the pigment is preferably one selected from the group consisting of ceramic inorganic pigments, titanium dioxide, yellow iron oxide, iron oxide, and mixtures thereof.

In this case, the flame retardant is preferably a metal hydroxide-based inorganic flame retardant.

In addition, the additive is preferably any one selected from the group consisting of a leveling agent, an adhesion promoter, an acid catalyst, a wax, a matting agent, and a mixture thereof.

The present invention also includes a first composition comprising a silicone-modified polyester resin and a melamine resin; And a second composition consisting of a polyester resin, a block isocyanate resin, a pigment, a flame retardant, an organic solvent and an additive, wherein the silicone-modified polyester resin is a reaction product of a silicone intermediate and a polyester resin, wherein the silicone intermediate: poly It provides a non-flammable coating composition in which the mass ratio of the ester resin is 30:70 to 80:20.

At this time, the second composition is polyester resin 10 to 50% by weight, block isocyanate resin 1 to 20% by weight, pigment 1 to 30%, flame retardant 1 to 40% by weight, organic solvent 30 to 80% by weight and additive 0.1 to It is preferably composed of 5% by weight.

In addition, it is preferable that the non-combustible paint composition of the present invention satisfies the criteria for a non-combustible material performance test method according to Article 2 of Notification No. 2018-771 of the Ministry of Land, Infrastructure and Transport.

In addition, the non-combustible coating composition of the present invention is preferably used for a PCM color steel sheet.

The non-flammable paint composition of the present invention overcomes the technical limitations of the conventional PCM paint, and when the paint composition of the present invention is used, the color, physical properties, high-speed coating workability, and molding processability are equivalent to that of the conventional color steel sheet for construction materials. At the same time, it can satisfy the requirements of the non-combustible material performance test specified in Article 2 of Notification No. 2018-771 of the Ministry of Land, Infrastructure and Transport. In addition, the paint composition according to the present invention is composed of oil-based, one-component paint suitable for the existing PCM color steel sheet line, so there is no problem in using it on the seal line at all times, and has the same level of color and gloss as the existing PCM paint for color steel sheet. Since it provides physical properties such as variety of products, durability against long-term use, excellent painting workability, and molding quality, it is a technological advancement compared to the conventionally introduced non-flammable color steel sheet paint, and has a high degree of completion.

Hereinafter, the present invention will be described in detail.

The description of the constitutional requirements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

The non-flammable coating composition of the present invention comprises a silicone-modified polyester resin and a melamine resin, and the silicone-modified polyester resin is a reaction product of a silicone intermediate and a polyester resin, and the silicone intermediate: polyester resin has a mass ratio of 30:70. It is preferably ~80:20.

The silicone-modified polyester resin constituting the top coat layer is a major component of the coating film composition and is a major constituent component that reacts with the melamine resin as a curing agent to form a coating film.

The silicone-modified polyester resin is a material obtained by copolymerization of a silicone intermediate and a polyester resin, and the silicone intermediate generally has an average molecular weight of about 400-10,000, and a polysiloxane resin having a reactive group such as a hydroxyl group or an alkoxy group in the molecule. to be. In addition, as the silicone intermediate, one or more commercially available products may be used. Non-limiting examples of such commercially available products include Dow Corning's DC Z-3074, DC Z-3037, DC Z-6188, DC Z-6018, or WACKER's SILRES SY-231.

The mass ratio of the silicone intermediate: polyester resin is preferably 30:70 to 80:20, more preferably 50:50 to 80:20, and most preferably 60:40 to 80:20. Specifically, in the silicone-modified polyester resin, the proportion of the silicone intermediate may be 30 to 80% by weight, more preferably 50 to 80% by weight, and most preferably 60 to 80% by weight. When the content ratio of the silicone intermediate is less than 30% by weight, processability is improved, but the heat resistance is lowered and the non-flammable performance is lost, so there is a problem that the expected performance of the paint does not appear, and when the content ratio of the silicone intermediate exceeds 80% by weight, it is non-flammable. Although the performance is improved, the degree of hardening is low, and adhesion and workability are deteriorated, which causes problems in high-speed painting work and molding processability.

The silicone-modified polyester resin may be included in 5 to 40% by weight based on the total weight of the composition.If the content of the silicone-modified polyester resin is less than 5% by weight, there are problems such as low curing degree and poor processability, and 40% by weight If exceeded, the non-flammable performance is lost, so the expected performance of the paint does not appear.

The melamine resin serves as a curing agent to facilitate curing with the silicone-modified polyester resin, which is the main resin, inside and outside the coating film.

The melamine resin is a material obtained by polymerization of alcohol and formaldehyde, for example, methoxy melamine resin obtained by polymerization of methanol and formaldehyde; And butoxy melamine resin obtained by polymerization of iso-butanol or normal butanol and formaldehyde. In addition, the melamine resin may be one or more commercially available products. Non-limiting examples of melamine resins usable in the present invention include CYMEL-303, CYMEL-325, CYMEL-327, CYMEL-350, CYMEL-370 (CYTEC), RESIMINE-7550, RESIMINE-717, RESIMINE-730, RESIMINE-747, RESIMINE-797 (SOLUTIA), BE-3717, BE-370, BE-3747 (BIP), BE-630, BE-692 (BIP), RESIMINE-7512, RESIMINE-750 (SOLUTIA) ), RESIMINE-755, RESIMINE-757, RESIMINE-751 (SOLUTIA), CYMEL-1168, CYMEL-1170, CYMEL-232 (CYTEC), and the like.

The melamine resin may be included in an amount of 1 to 20% by weight based on the total weight of the composition, and there is a problem such as poor durability due to low curing degree of which the content of the melamine cured resin is less than 1% by weight, and when it exceeds 20% by weight, processability decreases And the non-flammable performance is lost, so the expected performance of the paint does not appear.

The non-flammable coating composition of the present invention may further include any one selected from the group consisting of pigments, flame retardants, organic solvents, additives, and mixtures thereof in addition to the silicone-modified polyester resin and melamine resin.

The non-flammable coating composition of the present invention includes 5 to 40% by weight of a silicone-modified polyester resin, 1 to 20% by weight of a melamine resin, 5 to 40% by weight of a pigment, 5 to 40% by weight of a flame retardant, 30 to 80% by weight of an organic solvent, and 1 It may contain ~ 10% by weight.

The pigment should not be ignited at a temperature of 750℃ or higher in order to exhibit performance that meets the quality standards for non-combustible materials specified in Article 2 of the Ministry of Land, Infrastructure and Transport Notification No. Therefore, excellent ceramic inorganic pigments having heat resistance, corrosion resistance, and chemical resistance are recommended.

Inorganic pigments include zinc oxide, titanium dioxide, lithopone, basic lead carbonate, iron oxide, carbon black, lead chromate, yellow iron oxide, gwangmyeong coal, basic lead carbonate, bismuth oxychloride, mica titanium, copper anoxide, and zinc. One or more types of may be selectively used, but are not limited thereto.

Pigment may be used in 5 to 40% by weight based on the total weight of the paint composition.If the composition of the pigment is less than 10% by weight, the hiding power is low, so it is difficult to implement the desired color, and if it exceeds 40% by weight, the processability is poor. , There may be problems such as an increase in the price of the product.

The flame retardant is non-halogen-based, and one or more types of phosphorus-based compounds, sulfur-based compounds, magnesium-based compounds, and aluminum-based compounds may be selectively used as long as there is no problem in non-flammable performance and quality of the paint. Preferably, it may be selected from the group consisting of metal hydroxides and derivatives thereof, and aluminum hydroxide, magnesium hydroxide, and mixtures thereof may be used. In addition, the flame retardant may be included in a powder form, and preferably aluminum hydroxide powder, magnesium hydroxide powder, or a mixture thereof may be used.

The flame retardant may be included in 5 to 40% by weight based on the total weight of the paint composition.If the content of the flame retardant is less than 5% by weight, the non-flammable performance is deteriorated, and if it exceeds 40% by weight, the viscosity of the paint is too high, causing problems in workability. Alternatively, there may be problems such as deterioration of the workability of the coating film.

In an embodiment of the present invention, as long as the organic solvent does not have an appropriate viscosity lowering effect and surface appearance problem, a conventional organic solvent known in the art may be used, but it is preferable to use an organic solvent having a boiling point of 120 to 250°C. desirable.

Non-limiting examples of the organic solvent include aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents and acetate-based solvents. The organic solvent may be used alone, or may be used in combination of two or more. Examples of the aromatic hydrocarbon-based solvent include toluene, xylene, and cocosol (product name: #100 or #150) manufactured by SK Energy. The ester solvent or acetate solvent is, for example, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl acetate, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl Ether, ethylene glycol monoethyl ether, 3-methoxybutyl acetate, etc. are mentioned. Examples of the glycol ether solvent include methyl cellosolve, ethyl cellosolve, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether. Examples of the ketone-based solvent include acetone, acetonitrile, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the alcohol-based solvent include ethanol, isopropanol, n-butanol, amyl alcohol, and cyclohexanol. In addition, as the organic solvent, chloroform, cresol, hexane, tetrahydrofuran, isophorone, dibasic ester, and the like can also be used.

The organic solvent may be used in an amount of 30 to 80% by weight based on the total weight of the paint composition.If the composition of the organic solvent is less than 30% by weight, the viscosity may be too high and workability may be deteriorated, and if it exceeds 80% by weight, the viscosity is too high. This may cause problems in long-term storage, such as poor coating workability or accelerated precipitation of additives during long-term storage of the paint.

The additive may include at least one selected from the group consisting of a leveling agent, an adhesion promoter, a matting agent, an acid catalyst, a wax, and a mixture thereof.

The leveling agent may include siloxane and derivatives thereof, polyacrylate, polysiloxane, or a combination thereof. Specifically, it may include DSM's DD27 of polyacrylate (acrylic polymer) or FTC's LA-45, etc., and BYK's BYK-322, TECH POLYMER's TECH-2080 and mixtures thereof made of polysiloxane It may include one or more selected from the group consisting of, but is not limited thereto.

In an exemplary embodiment of the present invention, when a silicone-modified polyester resin having a high silicone content is used to exhibit a desired non-flammable performance, the resin content is lower than that of a general paint, and molding processability may be weak. In this case, a polysiloxane-based leveling agent may be preferably used, thereby improving heat resistance and lubricity, and supplementing molding processability.

The content of the leveling agent can be used within a range that does not cause problems in workability or physical properties of the coating film, but it is preferable to use as little as possible because the more it is used, the higher the manufacturing cost of the coating material is.

The adhesion promoter may be selected from a phosphate epoxy ester compound and a derivative thereof, but is not limited thereto. The content of the adhesion enhancer can be used within a range that does not cause any problems in non-flammable performance or physical properties of the coating film, but it is preferable to use as little as possible because the more it is used, the higher the manufacturing cost of the paint is.

The matting agent can be used for the purpose of realizing the desired gloss on the surface of the coating film, and amorphous silica, PMMA (poly (methyl methacrylate), polyacrylonitrile), polyamide (Polyamide) particles, and mixtures thereof are preferable. It can be used, but is not limited thereto.

By including the particles, it is possible to form a desired glossiness on the surface of the coating film of the top coat layer. For example, as amorphous silica, Syloid C807, Syloid C812, Syloid 622 (Grace, Germany), GASIL HP-260, GASIL HP-270 (PQ CORPERATION, USA), SS-415 (S-chemtech, Korea), etc. may be used. . As PMMA (polymethyl methacrylate) particles, SUNPMMA-S250, SUNPMMA-S400 (Sunjin Beauty Science, Korea), Diasphere® MH-15FD, Diasphere® MH-20FD, Diasphere® MH-25FD (Kolon Industries, Korea), etc. Can be used.

As polyacrylonitrile particles, TAFTIC™ A-20, TAFTIC™ ASF-7 (TOYOBO, Japan), and the like may be used. As polyamide particles, Orgasol 2002 ES5 NAT 3 (Akema, USA) or the like may be used.

The average particle diameter of the particles is not particularly limited, but is preferably 5 to 40 μm. If the average particle diameter of the particles is less than 5 μm, an excessively large amount of particles is added to meet the desired gloss, which is not desirable due to a problem of high viscosity or cost. If the average particle diameter exceeds 40 μm, the surface of the coating film is It is not preferable because it is too rough, or particles are attracted during the roll coating process, which adversely affects workability and appearance quality.

The content of the particles is not particularly limited, but in the case of 0.1 to 5% by weight based on the total weight of the coating composition, the glossiness, texture, and scratch resistance of the coating film surface may be more excellent.

The acid catalyst is used for the role of promoting crosslinking between the silicone-modified polyester resin and the melamine resin, which are the main resins, and sulfonic acid and derivatives thereof shielded with a material that can be dissociated by heat may be used, but is not limited thereto. As a non-limiting example of the sulfonic acid, P-toluenesulfonic acid, dodecylbenzenedisulfonic acid, dinonylnaphthalenedisulfonic acid, dinonylnaphthalenesulfonic acid, or a mixture thereof may be preferably used.

The wax may include at least one selected from the group consisting of aliphatic hydrocarbon-based, fluorine-based, and mixed-based, but is not limited thereto.

In the present invention, the wax is used for the purpose of imparting lubricity to the surface of the top coat to prevent surface stains and peeling (splitting) of the coating film caused by press machine mold marks that occur when molding the final color steel sheet. Non-limiting examples of aliphatic hydrocarbon-based waxes that can be used in the present invention include MP-22, MP-22XF, MP-22VF (US MPI), CERAFLOUR 913, CERAFLOUR 914, CERAFLOUR 990, CERAFLOUR 991 (BYK, Germany), and the like. It can be used preferably. Non-limiting examples of the fluorine-based wax include Fluo HT, Fluo 300 (US MPI), SST-1, SST-2, SST-3, SST-4 (US SHAMROCK), CERAFLOUR 981, CERAFLOUR 965 (Germany BYK) ) And the like can be preferably used. Non-limiting examples of mixed-type waxes include Polyfluo 150, Polyfluo 523XF, Polyfluo 535 (US MPI), CERAFLOUR 969, CERAFLOUR 996, CERAFLOUR 997, CERAFLOUR 998 (BYK, Germany), and the like.

The present invention also,

A first composition comprising a silicone-modified polyester resin and a melamine resin; And a second composition consisting of a polyester resin, a block isocyanate resin, a pigment, a flame retardant, an organic solvent and an additive, wherein the silicone-modified polyester resin is a reaction product of a silicone intermediate and a polyester resin, wherein the silicone intermediate: poly The mass ratio of the ester resin provides a non-flammable coating composition of 30:70 to 80:20.

In a specific embodiment of the present invention, the second composition is a polyester resin 10 to 50% by weight, block isocyanate resin 1 to 20% by weight, pigment 1 to 30%, flame retardant 1 to 40% by weight, organic solvent 30 to 80% by weight , It may preferably contain 0.1 to 5% by weight of additives.

The polyester resin may be preferably transformed into a polyurethane resin, an acrylic resin, an alkyd resin, an epoxy resin, and the like, if necessary.

The polyester resin may be included in 10 to 50% by weight based on the total weight of the composition.If the content of the polyester resin is less than 10%, processability may be deteriorated, and if it exceeds 50% by weight, there may be a problem in non-flammable performance. have.

The block isocyanate resin may be selected and used in various ways depending on the type of the blocking agent and the isocyanate type. In general, when manufacturing PCM paint, it can be selectively used among commercially available block isocyanate resins. Examples of usable block isocyanate resins include BL3165, BL3175, BL3272, BL3475, BL4265 (BAYER), BI7951, BI7981, BI7984, BI7990 ( BAXENDEN), etc. are mentioned.

The block isocyanate resin may be included in an amount of 1 to 20% by weight based on the total weight of the composition.If the content of the block isocyanate resin is less than 1%, the curing degree of the coating film cannot be sufficiently obtained, so that there may be problems in workability or physical properties. If it exceeds %, there may be a problem with non-flammable performance.

The pigment should not be ignited at a temperature of 750℃ or higher in order to exhibit performance that meets the quality standards for non-combustible materials specified in Article 2 of the Ministry of Land, Infrastructure and Transport Notice No. Therefore, ceramic inorganic pigments with excellent heat resistance, corrosion resistance, and chemical resistance are recommended. Inorganic pigments include zinc oxide, titanium dioxide, lithopone, basic lead carbonate, iron oxide, carbon black, lead chromate, yellow iron oxide, gwangmyeong coal, basic lead carbonate, bismuth oxychloride, mica titanium, copper anoxide and zinc. It may include, but is not limited thereto.

In addition, the pigment of the present invention may be used by additionally mixing a rust inhibitor pigment to implement corrosion resistance. As an example of a rust inhibitor, a chromic acid-based rust inhibitor may be mixed and used.

The pigment may be used in a range of 1 to 30% by weight based on the total weight of the coating composition.If the composition of the pigment is less than 1% by weight, the hiding power is low, so it is difficult to achieve the desired color when the top coat is painted, and the desired level of corrosion resistance It cannot be implemented, and if it exceeds 30% by weight, there may be problems such as poor workability and an increase in product price.

The flame retardant is non-halogen-based, and one or more types of phosphorus-based compounds, sulfur-based compounds, magnesium-based compounds, and aluminum-based compounds may be selectively used as long as there is no problem in non-flammable performance and quality of the paint. Preferably, it may be selected from the group consisting of metal hydroxides and derivatives thereof, and aluminum hydroxide, magnesium hydroxide, and mixtures thereof may be used. More preferably, a powder form of a metal hydroxide may be used.

The flame retardant may be included in an amount of 1 to 40% by weight based on the total weight of the paint composition.If the content of the flame retardant is less than 1% by weight, the non-flammable performance is deteriorated, and if it exceeds 40% by weight, the viscosity of the paint is too high, causing problems in workability. There may be problems such as deterioration of workability of the coating film and the like.

The organic solvent may be a conventional organic solvent known in the art as long as there is no problem in the appropriate viscosity lowering effect and surface appearance, but it is preferable to use an organic solvent having a boiling point of 120 to 250°C.

Non-limiting examples of the organic solvent include aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents and acetate-based solvents. The organic solvent may be used alone, or may be used in combination of two or more. Examples of the aromatic hydrocarbon-based solvent include toluene, xylene, and cocosol (product name: #100 or #150) manufactured by SK Energy. The ester solvent or acetate solvent is, for example, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl acetate, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl Ether, ethylene glycol monoethyl ether, 3-methoxybutyl acetate, etc. are mentioned. Examples of the glycol ether solvent include methyl cellosolve, ethyl cellosolve, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether. Examples of the ketone-based solvent include acetone, acetonitrile, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the alcohol-based solvent include ethanol, isopropanol, n-butanol, amyl alcohol, and cyclohexanol. In addition, as the organic solvent, chloroform, cresol, hexane, tetrahydrofuran, isophorone, dibasic ester, and the like can also be used.

The organic solvent may be used in an amount of 30 to 80% by weight based on the total weight of the paint composition.If the composition of the organic solvent is less than 30% by weight, the viscosity may be too high and workability may be deteriorated, and if it exceeds 80% by weight, the viscosity is too high. This may cause problems in long-term storage, such as poor coating workability or accelerated precipitation of additives during long-term storage of the paint.

The additive may include one or more selected from the group consisting of adhesion promoters, leveling agents, and metal catalysts.

The adhesion promoter may include at least one selected from a phosphate epoxy ester compound and a derivative thereof, but is not limited thereto.

The leveling agent is made of acrylate (acrylic polymer) DSM company DD27 or FTC company LA-45, siloxane and derivatives thereof, preferably BYK's BYK-322, TECH POLYMER's TECH-2080, etc. made of polysiloxane It may include one or more selected from the group of, but is not limited thereto.

The metal catalyst may include a tin-based or non-tin-based catalyst. Typical tin-based catalysts include dibutyltin dilaurate (DBTDL), and non-tin-based catalysts include XC-8212, XK-601, and XC-9213 (KING).

The non-flammable coating composition of the present invention can be prepared by a method known in the art. An example is a method of mixing and dispersing the components of the paint by a sand mill, a basket mill, a ring mill, or the like.

The non-combustible paint composition of the present invention satisfies the non-combustible material performance test criteria according to Article 2 of the Ministry of Land, Infrastructure and Transport Notification No. 2018-771.

The non-combustible coating composition of the present invention can be used for PCM color steel sheets. In a specific embodiment of the present invention, the first composition of the non-flammable coating composition may be used as a top coat of the steel sheet, and the second composition may be used as a bottom coat, but is not limited thereto.

The PCM color steel sheet may be manufactured by a method known in the art to which the present invention pertains. As an example, the PCM color steel sheet may be manufactured by sequentially stacking a chemical conversion layer, a lower coat layer, and a top coat layer on at least one side of a metal base steel sheet, and a chemical conversion layer and a back layer on the opposite side of the base steel sheet It can be produced by laminating.

In addition, as a coating method of the non-flammable coating composition of the present invention, a conventional coating method known in the art can be applied. For example, it can be formed using a continuous roll coating method. At this time, the heating temperature is not particularly limited as long as the coating film is formed and there is no abnormality in physical properties, but it is preferable that the maximum temperature of the material metal plate surface (PMT Peak Metal Temperature) is in the range of 200 to 250°C. In addition, the firing time can be changed according to the firing conditions. The coating thickness of the undercoat layer is preferably 1 to 10 µm, more preferably 2 to 5 µm. The coating thickness of the top coat layer is preferably 5 to 30 µm, more preferably 10 to 15 µm.

The present inventors confirmed that the PCM color steel sheet manufactured by using the non-combustible coating composition of the present invention exhibits a performance suitable for the quality standards of non-combustible materials specified in Article 2 of Notification No. 2018-771 of the Ministry of Land, Infrastructure and Transport. In addition, when the present inventors worked on the non-combustible paint composition prepared according to the present invention in a continuous coating-type color steel plate coating line, high-speed coating of 130m/min or more, which is the same line speed as the conventional coating operation conditions of PCM paint for construction materials. It was confirmed that the physical properties and workability were stably exhibited even under conditions.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.

Example

1. Preparation of the first non-flammable coating composition

(1) Example 1

15% by weight of silicone modified polyester resin, 3% by weight of melamine resin, 25% by weight of pigment, 15% by weight of flame retardant, 36% by weight of organic solvent, 3% by weight of leveling agent (TECH-2080 of TECH POLYMER), adhesion promoter (CFC) TANPOL 9000S) 1% by weight, acid catalyst (dinonylnaphenalenesulfonic acid) 1% by weight, wax (Polyfluo 523XF, US MPI) 0.5% by weight, matting agent (Orgasol 2002 ES5 NAT 3, US Akema) 0.5% by weight are mixed Thus, a first non-flammable coating composition was prepared. As the silicone-modified polyester resin, DC Z-3074 manufactured by Dow Corning in the United States is used as a silicone intermediate, and a silicone-modified polyester manufactured by Samwha Paint Industries Co., Ltd. so that the content ratio of the silicone intermediate and the polyester resin is 65:35. Resin CERASTER 796 resin was used. The melamine resin used was CYMEL-303 (manufactured by Cytec, USA), which is a hexamethoxymethylmelamine resin having a solid content of 98%. As the organic solvent, a mixture of cyclohexanone, cocosol #100 (SK Energy Co., Ltd.), xylene and butanol was used. The pigment was used in combination of titanium dioxide, yellow iron oxide, and iron oxide to realize a desired color. As the flame retardant, aluminum hydroxide in the form of fine particles was used.

(2) Comparative Examples 1 to 6

Compositions of Comparative Examples 1 to 6 were prepared using the same materials and methods as in Example 1, except that the content was changed to the content shown in Table 1. In Comparative Example 5, polyacrylate (LA-45, FTC (Korea)) used in Reference Example was used as a leveling agent.

(3) Reference Example 1

The composition of the top coat for PCM building materials used in the prior art is shown in Table 1 below as Reference Example 1. The silicone-modified polyester resin 1 used in the preparation of the composition of Reference Example 1 has a content ratio of 25:75 between the silicone intermediate and the polyester resin. Polyacrylate (LA-45, FTC (Korea)) was used as the leveling agent. Other materials and methods were carried out in the same manner as in Example 1 to prepare a resin composition of Reference Example 1.

division Reference Example 1 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Silicone Modified Polyester Resin 1 25 Silicone Modified Polyester Resin2 15 45 15 15 15 15 15 Melamine resin 5 3 3 25 3 3 3 3 Pigment 40 25 25 25 3 25 25 25 Flame retardant 15 15 15 15 3 15 15 Organic solvent 27 36 6 14 58 48 38 37 Leveling 1 One One Leveling 2 3 3 3 3 3 3 Adhesion enhancer One One One One One One Acid catalyst One One One One One One One One Wax 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Quencher One 0.5 0.5 0.5 0.5 0.5 0.5 0.5 system 100 100 100 100 100 100 100 100

(Unit: wt%)

2. Preparation of the second non-flammable coating composition

(1) Examples

As shown in the table below, polyester resin (CERASTER 431, Samwha Paint Industries Co., Ltd.) 20% by weight, block isocyanate resin (SUPER RESIN 1129 (solid content 62% by weight, HDI TRIMER type, MEKO block agent), Samwha Paint Industries Co., Ltd.) 5 weight %, titanium dioxide 5% by weight, strontium chromate 5% by weight, flame retardant (magnesium hydroxide and aluminum hydroxide in the form of fine particles are used in a 1:1 weight ratio) 20% by weight, organic solvent 40% by weight, phosphate epoxy, DBTDL, TECH- A second non-flammable coating composition was prepared by mixing 5% by weight of an additive comprising a mixture of 2080 (TECH POLYMER). As the organic solvent, a mixture of cyclohexanone, cocosol #100 (SK Energy Co., Ltd.), xylene and butanol was used.

(2) Reference example

The composition of the conventional PCM polyester primer composition used in the art is shown in Table 2 below. Materials used to prepare the composition of the reference example were the same as those of the example.

division Reference example Example Polyester resin 30 20 Melamine resin 10 Block isocyanate resin 5 Inorganic pigment 10 5 Antirust pigment 5 5 Flame retardant 20 Organic solvent 40 40 additive 5 5 system 100 100

(Unit: wt%)

3. Property evaluation

The second non-flammable coating composition according to the embodiment of Table 2 of the present invention was applied with a wire rod bar coater on the surface of a chromium pretreated hot dip galvanized steel sheet having a material thickness of 0.4 mm to 0.5 mm, and dried to have a thickness of 3 µm. After forming the undercoat layer, the first non-flammable coating composition according to Example 1 of Table 1 and the coating composition according to Comparative Examples 1 to 6 were respectively applied to the surface of the undercoat layer with a bar coater and dried to form a top coat layer having a thickness of 12 μm. After formation, the physical properties of the formed coating film were evaluated and shown in Table 3 below. Likewise, a primer for general PCM construction material according to the reference example in Table 2 used in the related art was applied with a wire rod bar coater on the surface of a pre-treated hot-dip galvanized steel sheet with a material thickness of 0.4 mm to 0.5 mm and dried. After forming a 5 µm-thick undercoat layer, the coating composition according to Reference Example 1 in Table 1 was applied with a bar coater and dried to form a 15 µm-thick top coat layer, and then the physical properties of the formed coat were evaluated. It is shown in 3.

<Performance test evaluation method>

1. Non-flammability test: According to the method of performance test of non-combustible materials in Article 2, Subparagraph 1 of the Ministry of Land, Infrastructure and Transport Notification No. 2018-771, and the Korean Industrial Standards established in accordance with Article 4 of the 「Industrial Standardization Act」 As a result of the test according to KS F ISO 1182 (Incombustibility Test Method of Building Materials), the maximum temperature in the furnace for 20 minutes after the start of the heating test should not rise above the final equilibrium temperature by 20K. If it is not reached, the average temperature for the last minute is the final equilibrium temperature), and the mass reduction rate of the specimen should be 30% or less after heating is complete.

2. Gas Hazard Test: Gas hazard test corresponding to the Korean Industrial Standard KS F 2271 (Flame retardancy test method of interior materials and structures of buildings) in accordance with the Ministry of Land, Infrastructure and Transport Notification No. 2018-771 No. As a result, the average stoppage time of the experimental mice should be 9 minutes or longer.

3. Painting workability: In the painting process by the continuous roll painting method commonly used in the industry, when working at a high speed line speed of 130m/min or more, there should be no defects by evaluating the pick-up property of the paint and the appearance of the coating.

4. Molding processability: When pressing in the press mold for interior materials, no defects should occur on the top coat surface.

5. Color: The desired color was measured compared to the reference plate by using a color difference meter such as CR400, CM700D (Minolta, Japan) or Color-Eye® 7000A (X-Rite, USA).

6. T-bendability: This is the level of cracking of the coating film after T-bending at room temperature. After 2T-bending at room temperature, attach it with scotch tape to check whether or not peeling has occurred.

(Evaluation: If the coating film is partially peeled off, it is defective, and if the coating film is not peeled off, it is good)

7. Solvent resistance: As a MEK rubbing method, measure the number of times until the moment when the underlying coating is peeled off by soaking MEK in a general medical gauze and performing reciprocating friction with a load of 1kg.

(Evaluation: If the coating film is peeled off when rubbing more than 50 times and the material is not visible, it is good if the coating film is not peeled off, and if the coating film peels off at least partly, it is bad)

8. CET (6mm): After making 100 grids by drawing 11 scales vertically and horizontally with a cutter knife at 1mm intervals on the coated steel sheet, extrude 6mm from the back side of the steel sheet toward the front with an Ericsson tester, and then measure the scale part. After strongly attaching and rubbing with an adhesive tape, the tape was pulled upward and then the swelling or peeling of the coating film was measured and evaluated.

(Evaluation: If the coating film is partially peeled off, it is defective, and if the coating film is not peeled off, it is good)

9. Pencil Hardness: Measure the degree to which fine marks remain on the film by scratching the surface of the coating film at a constant speed under a load of 750g, using Mitsubishi Japan's “Uni Pencil” and erasing it with an eraser. Usually low hardness is 2B, B, HB, F, H, 2H, 3H, in order of high hardness.

(Evaluation: If the pencil hardness is higher than H, it is good, and if it is lower than H, it is evaluated as poor.)

10. Boiling water resistance: To measure the water resistance of the applied paint, immerse the applied steel sheet in boiling water and leave it for 1 hour, then take it out and remove the water. After that, it was evaluated whether there were any abnormalities such as swelling and discoloration of the exterior of the coating film.

division Reference Example 1 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 1. Non-flammability test Bad Good Bad Bad Bad Bad Good Good 2. Gas hazard test Good Good Bad Bad Good Good Good Good 3. Painting workability Good Good Bad Bad Good Good Good Good 4. Molding processability Good Good - Bad Good Good Bad Good 5.Color Good Good Good Good Bad Good Good Good 6.T-bendability Good Good Bad Bad Good Good Good Bad 7. Solvent resistance Good Good Bad Good Good Good Good Bad 8.CET(6mm) Good Good - Good Good Good Good Good 9. Pencil hardness Good Good Bad Bad Good Good Good Good 10. Boiling water resistance Good Good Bad Bad Good Good Good Good

As can be seen in Table 3, in the reference example using a silicone-modified polyester resin conventionally used in the art as a top coat of the coating film, the non-flammable performance is not satisfied at all. In addition, as in Comparative Examples 1 to 6, when outside the composition range of the first non-combustible coating composition of the present invention, it was found that the physical properties for use as a PCM coating for non-combustible color steel sheets were not satisfied. On the other hand, in the case of Example 1, which is a coating film coated with the non-combustible coating composition of the present invention, it was confirmed that all of the physical properties for use as a PCM coating for a non-combustible color steel sheet were satisfied.

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention. will be.

Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning of the claims and the concept of the scope should be interpreted as being included in the scope of the present invention.

Claims (9)

As a non-flammable coating composition comprising a silicone-modified polyester resin and a melamine resin,
The silicone-modified polyester resin is a reaction product of a silicone intermediate and a polyester resin, and the silicone intermediate: a non-combustible coating composition having a mass ratio of the polyester resin of 30:70 to 80:20. The non-flammable coating composition according to claim 1, further comprising any one selected from the group consisting of pigments, flame retardants, organic solvents, additives, and mixtures thereof. The method of claim 2, wherein the silicone-modified polyester resin 5 to 40% by weight, melamine resin 1 to 20% by weight, pigment 5 to 40% by weight, flame retardant 5 to 40% by weight, organic solvent 30 to 80% by weight, additive 1 Non-flammable coating composition comprising ~ 10% by weight. The non-flammable coating composition according to claim 2, wherein the pigment is one selected from the group consisting of ceramic inorganic pigments, titanium dioxide, yellow iron oxide, iron oxide, and mixtures thereof. The non-combustible coating composition according to claim 2, wherein the flame retardant is a metal hydroxide-based inorganic flame retardant. The non-flammable coating composition according to claim 2, wherein the additive is any one selected from the group consisting of a leveling agent, an adhesion promoter, an acid catalyst, a wax, a matting agent, and a mixture thereof. A first composition comprising a silicone-modified polyester resin and a melamine resin; And
Including; a second composition consisting of a polyester resin, a block isocyanate resin, a pigment, a flame retardant, an organic solvent and an additive,
The silicone-modified polyester resin is a reaction product of a silicone intermediate and a polyester resin, and the silicone intermediate: a non-combustible coating composition having a mass ratio of the polyester resin of 30:70 to 80:20. The method of claim 7, wherein the second composition comprises 10 to 50% by weight of polyester resin, 1 to 20% by weight of block isocyanate resin, 1 to 30% of pigment, 1 to 40% by weight of flame retardant, 30 to 80% by weight of organic solvent, and Non-flammable coating composition consisting of 0.1 to 5% by weight of additives. The non-combustible coating composition according to any one of claims 1 to 8, wherein the non-combustible coating composition is for a PCM color steel sheet.