KR100608334B1 - Non-polluting high temperature baking type fluorine coating composition - Google Patents

Abstract

The present invention relates to a non-polluting high temperature calcined fluorine coating composition, and more particularly, to an organic / inorganic composite composition composed of an organic binder composed of a polyvinylidene fluoride resin and a thermoplastic acrylic resin, an alkyl silicate inorganic compound compound, and the like. When this coating is applied, an organic-inorganic composite layer of a thin film is formed on the upper part of the dry coating film to maintain the surface of the coating film in a high energy state (hydrophilic coating film), which is difficult to attach lipophilic contaminants, and contaminants adhered to the surface The present invention relates to a non-polluting hot fluorine-containing fluorine coating composition that is naturally deposited and removed by rain because it is not deposited on the membrane and thus retains long-term plastering function as well as long-term durability.

Description

Non-polluting high temperature baking type fluorine coating composition

The present invention relates to a non-polluting high temperature calcined fluorine coating composition, and more particularly, to an organic / inorganic composite composition composed of an organic binder composed of a polyvinylidene fluoride resin and a thermoplastic acrylic resin, an alkyl silicate inorganic compound compound, and the like. When this coating is applied, an organic-inorganic composite layer of a thin film is formed on the upper part of the dry coating film to maintain the surface of the coating film in a high energy state (hydrophilic coating film), which is difficult to attach lipophilic contaminants, and contaminants adhered to the surface The present invention relates to a non-polluting hot fluorine-containing fluorine coating composition that is naturally deposited and removed by rain because it is not deposited on the membrane and thus retains long-term plastering function as well as long-term durability.

Recently, the importance of protecting the environment is widely recognized, and acid rain and various air pollutants are emerging as the main causes of complex deterioration and complex pollution of social overhead capital, general housing, and high-rise buildings.

Even if you try to design landscapes using exterior finishing materials with excellent weather resistance in the exterior of buildings, you cannot maintain the aesthetics in a severe air pollution environment caused by pollutants in urban and industrial areas. Tumbled into.

In buildings such as houses, mansions, office buildings, and commercial buildings, the asset value and corporate image are deteriorated.In public structures such as highways, bridges, and port facilities, the preservation of the urban landscape and harmony with the surrounding environment, It is true that many complaints are caused by environmental comfort.

Therefore, fluorine paint, which has been recognized as the best quality among existing paints based on high durability and weatherability due to the high rise of buildings, asset value evaluation, and preservation of urban landscape, has been developed in various construction structures and social overhead capital. The market is rapidly expanding and creating new markets.

However, the paints (mostly acrylic or urethane) used for the existing building exterior materials deteriorate the surface of the coating under conditions such as ultraviolet rays, moisture, and acid rain, resulting in chalking, and the contaminated coatings are naturally removed. Although the cleaning effect can be obtained, there is a problem in that labor and maintenance cost are large because continuous repair and additional coating are required because durability and weather resistance are inferior. In addition, the existing fluorine coating film has a relatively high water repellency and a strong CF bond energy in the resin skeleton, thus forming a strong coating film, which is excellent in resistance to ultraviolet rays, moisture, acids and alkalis, and has a low deterioration of the coating film. There is a need for maintenance and management costs such as the need for regular cleaning to remove contamination of buildings.

Therefore, in the metropolitan area, as the demand from so-called 'material abundance' to 'practical abundance' expands, such as aesthetics, harmony with the urban landscape, environmental comfort, and color harmonization, the required performance of exterior materials is also long-term durability function for large buildings. In addition, the market situation is changing due to the tendency to emphasize the function of long-term plastering that does not harmonize or damage the urban buildings and surrounding areas.

Conventional high temperature fired fluorine paint is used for exterior building materials (curtain wall, aluminum window frame, etc.) of buildings because it can be stored for a long time with high durability, chemical resistance and weather resistance. However, pollution of buildings (lipophilic pollutants, the main cause of film contamination) in urban areas and industrial areas becomes more serious, and due to the thermoplastic properties of high-temperature fluorine-based fluorine paints, pollutants are deposited on the film and contaminated. Also, since the cleaning is not easy, there is a problem that excessive cost and effort are required to maintain and manage the periodic cleaning for the decontamination.

The inventors of the present invention have excellent durability and weather resistance and at the same time, the pollution prevention property is extremely superior to the existing high-temperature fluorine-type fluorine paint, and it has a ratio of self-cleaning property in which the pollutants on the surface of the coating film are washed by rain by rain. Research efforts have been made to develop contaminant hot burning fluorine paints. As a result, in order to solve the problem of fouling of the coating film and fixation of contaminants, an organic / inorganic composite layer of a thin film is formed on the upper layer of the coating film to maintain the surface of the coating film in a high energy state (hydrophilic coating film). The present invention was completed by introducing a function that is difficult to attach, as well as a contaminant adhered to the surface is not deposited on the coating film, and is naturally cleaned and removed due to rain.

The present invention is 40 to 60% by weight of a binder comprising a polyvinylidene fluoride resin and a thermoplastic acrylic resin in an 80/20 to 50/50 weight ratio; 40 wt% or less of a pigment selected from calcined ceramic pigments, metallic pigments, and mica pigments; 0.2 to 2% by weight of a pigment precipitation inhibitor; 30 to 55% by weight of a solvent mixture selected from hydrocarbon-based, ethylene glycol-based, high-boiling ester-based and isophorone-based; And a non-polluting high temperature calcined fluorine coating composition containing 2 to 10% by weight of an alkyl silicate inorganic composite compound.

When described in more detail the technical configuration and effect of the present invention as follows.

As a binder of the coating composition according to the present invention, a mixture in which a polyvinylidene fluoride (PVDF) resin and a thermoplastic acrylic resin are mixed in a weight ratio of 80/20 to 50/50 is used. If the mixing ratio of PVDF resin and thermoplastic acrylic resin is larger than the 80/20 weight ratio, there is a problem in uniform formation of coating film, resulting in poor appearance, and the bonding strength between resins decreases, resulting in poor adhesion to the coating and mechanical properties of the coating film. When the mixing ratio becomes smaller than 50/50 weight ratio, the thermoplastic acrylic resin, which is less weatherable and durable than the PVDF resin, is exposed to the surface of the coating film, and thus the chemical resistance, corrosion resistance, and weather resistance are deteriorated. The value of highly weathering fluorine paint will be lost. In the present invention, PVDF resin was applied to KYNAR500 ™ (manufactured by Elf Atochem North America Inc.) or HYLAR5000 ™ (manufactured by AUSMONT USA, Inc.), and Paraloid B-44 ™ (Rohm and Haas Company) was used as the thermoplastic acrylic resin. Applied.

In the present invention, the pigment contains 40 wt% or less of one or two or more selected from calcined ceramic pigments, metallic pigments and mica pigments. However, in the case of transparent paints, the use of pigments is prohibited. Calcined ceramic pigments are inorganic pigments prepared by calcining metal oxides at high temperatures to form a coating film with a binder to impart color and to maintain excellent weather resistance, chemical resistance and durability. Dioxide, cobalt aluminate, kappa chromite, cobalt chromite, chromium antimony titanium, lead chromate and the like are used. Aluminum paste is used as metallic pigment. As mica pigments, colored mica, MICA, Iriodine and the like can be used.

Pigment sedimentation inhibitors are included to prevent sedimentation and agglomeration of pigmented pigments to maintain storage stability, smooth paintability, and beautiful appearance of paints. The total paint composition is 2% by weight or less, preferably 0.2 to 2% by weight. It contains%. In the present invention, an organic clay (hectorite; Bentone Powder ™), a high molecular acid ester and an unsaturated polyamine amide salt solution (BYK-chemie GmbH, Anti-TERRA-U ™) and the like are used alone or as mixed pigment inhibitors. do.

As a solvent, 1 type, or 2 or more types chosen from a hydrocarbon type, an ethylene glycol type, a high boiling point ester type, and an isophorone type can be used within 30 to 55 weight%. At this time, the solvent selection and the mixing ratio are determined by the slow drying of the coating during the painting work, the increase of the content of the fast-drying hydrocarbon solvent when the flow is defective, the poor fusion of the coating film during the baking and the cracking phenomenon (Mud). When cracks occur, the content of high boiling point solvent should be increased and used in proper combination. In the present invention, xylene, toluene, cocosol-100 (Kocosol-100 ™, manufactured by Yugong Co., Ltd.), cocosol-150 (Kocosol-150 ™, manufactured by Yugong Co., Ltd.), etc. are used as the hydrocarbon solvent. Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, and the like are used, and 1,2-benzenedicarboxylic acid dimethyl ester and the like are used as the high boiling point ester system.

The alkyl silicate inorganic composite compound is contained in order to impart antifouling properties and self-cleaning property to the coating, and is contained in the range of 2 to 10% by weight in the total coating composition. When the alkyl silicate inorganic compound compound is used at less than 2% by weight, the antifouling property and self-cleaning property of the coating film are inferior, and when it is used in excess of 10% by weight, the material adhesion, impact resistance, chemical resistance, weather resistance, durability, The repainting interlayer adhesion is inferior, the appearance and gloss of the coating film is lowered.

The composition of the alkyl silicate inorganic composite compound is 50 to 99% by weight of the alkyl silicate, 0.1 to 3.0% by weight of the silane coupling agent, 0.001 to 0.5% by weight of the organometallic compound, and a composite compound synthesized by methanol or ion exchange water through a separate process. It should be manufactured and used to obtain pollution prevention and self-cleaning film. The reason for this is that the alkyl group in the alkylsilicate composite compound formed on the surface of the coating film reacts with moisture in the air to form a hydroxyl group, and the hydroxyl group makes the surface of the coating film hydrophilic. This hydrophilic property suppresses adhesion of lipophilic contaminants and facilitates contact with rainwater during rainfall, so that lipophilic contaminants are removed from the floating film. In addition, alkyl silicates may be used without a separate compounding treatment, but the non-pollution property and self-cleaning property may be degraded, and the expression time may be delayed, and thus, the holding force may be extremely short. In addition, there is a problem that a large amount of the alkyl silicate is volatilized together with the solvent in the course of baking and drying at a high temperature (230 ~ 250 ℃).

Herein, the configuration and manufacturing method of the alkyl silicate inorganic composite compound will be described in detail.

1. Composition of Alkyl Silicate Inorganic Compound

(A) As the alkyl silicate, one or two or more selected from ethyl silicate and methyl silicate may be used. Specific examples thereof include ethyl silicate 28 ™, ethyl silicate 40 ™ and methyl from Colcoat Co., Ltd. Silicate 51 ™, Methyl silicate 56 ™, methyl silicate 57 ™, etc. may be used.

(B) As the silane coupling agent, β- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl trimethoxy silane, γ-glycidoxypropyl methyl diethoxy silane, methyl diethoxy Silane, γ-glycidoxypropyl triethoxy silane, γ-methacryloxypropyl methyl dimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyl diethoxy silane, γ-methacryl Oxypropyl triethoxy silane, N-β- (aminoethyl) γ-aminopropyl methyl dimethoxy silane, N-β- (aminoethyl) γ-aminopropyl trimethoxy silane, γ-aminopropyl trimethoxy silane and One or more selected from γ-aminopropyl triethoxy silanes can be selected and used.

(C) As the organometallic compound, tin-containing organic compounds may be used, and specific examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, zinc octoate, zinc naphthenate, and the like. You can choose to use species or more,

(D) Ion-exchanged water and (e) Methanol may be used by appropriately adjusting the input amount as needed in the preparation of the silicate composite compound.

2. Preparation method of alkyl silicate inorganic compound

1) 0.1 to 3.0% by weight of the silane coupling agent and 0.001 to 0.5% by weight of the organometallic compound, with agitator and a cooling device mounted on a clean, washed round flask, with 50 to 99% by weight of alkyl silicate being added thereto. 0.1-3.0 weight% of ion-exchange water, and 1-45 weight% of methanol are thrown in small amounts.

2) After the addition, the temperature of the flask contents is increased to 50 to 100 ° C by using a heater while stirring at about 50 to 300 rpm with a stirrer.

3) When the temperature rise is completed, the reaction is allowed to proceed for 4 to 8 hours while maintaining the temperature while stirring at about 50 to 300 rpm to complete the target alkylsilicate inorganic composite compound.

Such a present invention will be described in detail based on the following examples, but the present invention is not limited thereto.

Preparation Examples 1-2: Preparation of Alkyl Silicate Inorganic Composite Compound

A stirrer and a cooling device were mounted on a clean washed branched round flask, and a small amount of alkyl silicate, silane coupling agent, organometallic compound, ion-exchanged water, and methanol was added at a content ratio as shown in Table 1 below. After the addition, the temperature of the flask contents was raised to 50 to 100 ° C using a heater while stirring at about 50 to 300 rpm with a stirrer. When the temperature rise was completed, the reaction proceeded for 4 to 8 hours while maintaining the temperature while stirring at about 50 to 300 rpm to obtain an alkyl silicate inorganic compound.

TABLE 1

As a result of measuring the average molecular weight of the alkyl silicate inorganic composite compound synthesized through Preparation Examples 1 and 2 using gel permeation chromatography (hereinafter referred to as GPC), a weight average molecular weight of about 500 to 1,000 and a low molecular weight alkyl silicate compound It was confirmed that the mixture has a high molecular weight alkyl silicate compound having an average molecular weight of about 15,000 to 35,000. In addition, high molecular weight silicates were not measured in methyl silicate 51 and ethyl silicate 40 when measuring GPC, and the weight average molecular weight was only 400-800 low molecular weight silicate, which is a big difference from the alkyl silicate inorganic compound. Could confirm.

Example 1 and Comparative Example 1: Preparation of Paint

The paint was prepared using the composition components as shown in Table 1 below.

Thermoacrylic resin is added to the mixed solvent of (2) to (3) to dissolve it, and then, an antisettling agent and a coloring pigment are added and stirred to use a suitable disperser (for example, a red devil, sand mill, ball mill, dinomill, etc.). The dispersion 1 was prepared by dispersing to a particle size of 10 μm or less.

Dispersion 2 was prepared by dissolving thermoplastic acrylic resin in the mixed solvent of (9) to (14), dispersing PVDF resin, and dispersing to a particle size of 30 μm or less using a high speed stirrer.

The dispersion 1 and the dispersion 2 prepared above are mixed using a stirrer, and then the alkyl silicate inorganic composite compound, the alkyl silicate, and the quencher are sequentially added and stirred to form a uniform mixture.

Example 2 and Comparative Examples 2-3: Preparation of Paint

The paint was prepared using the composition components as shown in Table 1 below.

The thermoplastic acrylic resin was added to the mixed solvent of (9)-(14), and it disperse | distributed to the particle size of 30 micrometers or less using the high speed stirrer, and the dispersion liquid was prepared.

The dispersion solution prepared above was added to the mixed solvent of (2) to (3), and then the thermoplastic acrylic resin was added and mixed, and then the alkyl silicate inorganic composite compound, the alkyl silicate, and the quencher were sequentially added and stirred to give a uniform solution. When the mixture is prepared, the preparation of the paint is completed.

TABLE 2

Experimental Example

For paints prepared according to the above Examples and Comparative Examples, test specimens were prepared according to the following specimen preparation methods and test methods, and the prepared specimens were subjected to physical property evaluation tests after 7 days at room temperature. The results are shown in Table 3 below. However, in this experiment, the test specimen preparation and the physical property evaluation are the same as the conventional high temperature calcined fluorine paint, so it was briefly summarized.

Psalm Writing

1) In this experiment, the physical property test was carried out by using a chromate-treated aluminum specimen (1.0㎜ × 6.5㎝ × 15㎝ size) by applying high temperature small-type fluorine paint undercoat (Korea Chemical, Cofulux Primer YP130-L / YELLOW) based on the dry coating thickness. It coated with 5-10 micrometers. On top of that, the coating materials prepared in Example 1 and Comparative Example 1 were coated with 25 to 35 μm, respectively, and dried at a material surface temperature of 232 ° C. for 15 minutes to carry out physical property tests.

2) Specimen preparation of Example 2, Comparative Example 2 and Comparative Example 3 was coated with the same coating on the same specimen as in 1), and the conventional high-temperature small-type fluorine paint (Korea Chemical, Cofulux Top Coat Metallic Silver YJ2443 ( S) -MB101) was coated with 25 to 30 μm and dried at a material surface temperature of 232 ° C. for 15 minutes. Then, the paint prepared in Example 2, Comparative Example 2 and Comparative Example 3 was coated with 15 to 20 μm, respectively, to provide a material surface temperature. It dried for 15 minutes at 232 degreeC and carried out the physical property test.

3) The test specimen for outdoor exposure was prepared by the same method as 1) and 2), but was used as a 0.7 mm × 30 cm × 60 cm size specimen in consideration of the characteristics of the experiment.

Property test method

[Property evaluation method]

TABLE 3

Property evaluation result

Acrylic or urethane paints used for existing building exterior materials deteriorate the coating surface under conditions such as ultraviolet rays, moisture, and acid rain, resulting in chalking. As a result, labor and repair costs were a big problem.

In addition, the existing fluorine coating film has a relatively high water repellency and a strong CF bond energy in the resin skeleton, thus forming a strong coating film, which is excellent in resistance to ultraviolet rays, moisture, acids and alkalis, and has a low deterioration of the coating film. Excessive maintenance and management costs, such as the need for regular cleaning to remove contamination of the building, were excessive.

In order to solve this problem, the present invention possesses excellent durability and weather resistance, and at the same time, pollution prevention is extremely superior to that of the existing high-temperature fluorine-type fluorine paint, and contaminants on the surface of the coating film are washed by rain (rain). As self-cleaning is imparted, so-called 'material abundance' such as 'material abundance' such as long-term aesthetic maintenance of buildings, harmony with the urban landscape, environmental comfort, and color harmonization, which cannot be realized by conventional high temperature baking type fluorine paint It is possible to meet the demand for 'richness' and to reduce the cost and effort for maintaining and managing periodic cleaning for decontamination.

Claims (4)

40 to 60 wt% of a polyvinylidene fluoride resin and a thermoplastic acrylic resin in a composition ratio of 80/20 to 50/50 by weight; 40 wt% or less of a pigment selected from calcined ceramic pigments, metallic pigments, and mica pigments prepared by calcining a metal oxide at a high temperature; 0.2 to 2% by weight of a pigment precipitation inhibitor; 30 to 55% by weight of a solvent mixture selected from hydrocarbon-based, ethylene glycol-based, high-boiling ester-based and isophorone-based; And 50 to 99% by weight of the alkyl silicate, 0.1 to 3.0% by weight of the silane coupling agent, 0.001 to 0.5% by weight of the organometallic compound, and 2 to 10% by weight of the alkyl silicate inorganic composite compound containing methanol or ion-exchanged water Non-polluting hot burning type fluorine coating composition, characterized in that it contains. The non-polluting hot burning type fluorine coating composition according to claim 1, wherein the alkyl silicate is ethyl silicate, methyl silicate or a mixture thereof. The silane coupling agent according to claim 1, wherein the silane coupling agent is β- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl trimethoxy silane, γ-glycidoxypropyl methyl diethoxy silane, Methyl diethoxy silane, γ-glycidoxy propyl triethoxy silane, γ-methacryloxypropyl methyl dimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyl diethoxy silane, γ -Methacryloxypropyl triethoxy silane, N-β- (aminoethyl) γ-aminopropyl methyl dimethoxy silane, N-β- (aminoethyl) γ-aminopropyl trimethoxy silane, γ-aminopropyl trimeth Non-polluting high-temperature fluorine-type fluorine coating composition, characterized in that one or more selected from oxy silane and γ-aminopropyl triethoxy silane. The method according to claim 1, wherein the organometallic compound is one or two or more selected from dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, zinc octoate and zinc naphthenate. Contaminated hot calcined fluorine coating composition.