KR100952124B1 - Preparation method of metallic glitter power for mininizing formaldehyde remainder - Google Patents

Abstract

PURPOSE: Metallic glitter particles are provided to ensure excellent chemical resistance, coating performance, coatbility, glossiness and hardness and to be variously used as environmentally friendly materials in clothing and interior fields. CONSTITUTION: A method for manufacturing metallic glitter particles for minimizing formaldehyde remainder comprises the steps of: performing pyrolysis of ethylene diamine and urea to prepare an ethylene-urea resin; reacting the ethylene-urea resin with a melamine-formaldehyde resin to prepare a particle coating solution containing a urea-formaldehyde compound represented by chemical formula 1: CH2N(CH2OH)C(=O)N(CH2OH)CH2; and coating a base film with the particle coating solution and curing, aging and pulverizing the coated base film to prepare metallic glitter particles.

Description

Preparation method of metallic glitter power for mininizing formaldehyde remainder}

The present invention relates to a method for producing metal gloss particles having 20 ppm or less of formaldehyde remaining on the surface of the metal gloss particles and having excellent physical properties such as chemical resistance, coating property, glossiness, and hardness.

The coating of the substrate surface is useful for practical purposes such as aesthetic effect and corrosion protection. Coating compositions tend to use coating materials that, during coating treatment and after coating, preferably less release organic volatiles.

In order to express the effect of metallic luster, melamine resins are used in various fields such as paints for construction and furniture, wallpaper, floorboards, clothes, printed materials, and the like.

Melamine resins used for coating are generally added formaldehyde component in the production process during the manufacturing process, and other problems are always pointed out. Therefore, various methods for reducing formaldehyde contained in an adhesive or the like have been proposed to solve such problems. However, when formaldehyde is not added or its amount is reduced, productivity and physical properties cannot be stabilized. .

In particular, formaldehyde is used in excess, so formaldehyde generally remains on the surface of the coated substrate.

Formaldehyde is a chemical substance widely used for preservatives, adhesives, plywood processing, etc., formed by oxidizing methyl alcohol. Formaldehyde is known to be a carcinogen causing serious effects on the nervous system and organs when exposed to the body for a long time.

For this reason, the allowable exposure concentration of formaldehyde in the atmosphere is regulated.

In addition, concentration restrictions on products coated with formaldehyde-containing products are being tightened.

Nevertheless, melamine-formaldehyde resin is used as a coating solution in various fields because of its excellent properties such as solvent resistance, hardness, glossiness, and curability.

Therefore, there is an urgent need for a method capable of reducing the amount of formaldehyde remaining on the surface after coating. In many countries, regulatory limits on the amount of formaldehyde remaining on the coating surface vary, but are allowed in almost all countries as long as they are approximately 20 ppm or less.

The present invention is a formaldehyde, characterized in that to form a particle coating solution containing a urea-formaldehyde compound obtained by reacting an ethylene- urea resin and a melamine-formaldehyde resin prepared by pyrolysis reaction of ethylene diamine and urea to the base film An object of the present invention is to provide a method for producing metallic gloss particles in which residual amount is minimized.

It is another object of the present invention to provide metallic gloss particles having a formaldehyde content of 20 ppm or less.

The solution to the problem of the present invention is not limited to those mentioned above, and other solutions not mentioned can be clearly understood by those skilled in the art from the following description.

1. pyrolysis reaction of ethylene diamine and urea to produce an ethylene-urea resin; Reacting the ethylene-urea resin and the melamine-formaldehyde resin to prepare a particle coating solution including the urea-formaldehyde compound represented by Chemical Formula 1 below; And coating, curing, aging, and pulverizing the particle coating solution on the base film to produce metal gloss particles.

CH ₂ N (CH ₂ OH) C (= 0) N (CH ₂ OH) CH ₂

2. according to the above 1, the pyrolysis reaction is a method for producing metal gloss particles to minimize the amount of formaldehyde residual is performed for 5 to 8 hours at 230 to 270 ℃.

3. The method of claim 1, wherein the ethylene-urea resin is a solution of a metal gloss particles is minimized formaldehyde residual dissolved in a solvent selected from acetone, methanol, methyl-ethyl-ketone and toluene.

4. The method of claim 1, wherein the melamine-formaldehyde resin solution is a method for producing metal gloss particles in which the amount of formaldehyde remaining containing formaldehyde 3 to 6 molar ratio with respect to 1 mol of melamine is minimized.

5. The method according to the above 1, wherein the particle coating solution is minimized formaldehyde residual amount containing 1 to 1.2 molar ratio of ethylene-urea resin with respect to 1 mol of melamine-formaldehyde resin.

6. In the above 5, with respect to 100 parts by weight of the particle coating solution, 0.2 to 15 parts by weight of dye, 0.1 to 1 parts by weight of polyester resin, 0.1 to 0.5 parts by weight of fluorine-based dye dispersion and surface releaving agent, and urea-modified poly Method for producing metal gloss particles is minimized formaldehyde residual amount further comprises 0.1 to 0.3 parts by weight of the urethane-based resin.

7. In the above 1, the particle coating solution is a method of producing a metal gloss particles is minimized formaldehyde residual concentration of 30 to 55% by weight.

8. In the above 1, wherein the base film is a polyester or aluminum vapor deposition polyester film formaldehyde residual amount of the method of producing a metallic gloss particles is minimized.

9. according to the above 1, wherein the curing is carried out at 180 to 200 ℃ for 10 to 60 seconds formaldehyde residual amount is minimized manufacturing method of the metal gloss particles.

10. In the above 1, the method of producing a metal gloss particles is minimized formaldehyde residual amount is carried out for 2 to 3 days at 80 to 100 ℃.

11. In the above 1, the metal gloss particles is a method of producing a metal gloss particles to minimize the amount of formaldehyde residual having a coating layer of 0.8 to 2.5 ㎛ thickness on one side of the base film.

12. pyrolysing ethylene diamine and urea to prepare an ethylene-urea resin; And reacting the ethylene-urea resin with the melamine-formaldehyde resin to prepare a urea-formaldehyde compound represented by Chemical Formula 1 below.

[Formula 1]

CH ₂ N (CH ₂ OH) C (= 0) N (CH ₂ OH) CH ₂

Metallic gloss particles produced according to the present invention can be easily exported to overseas by maintaining the residual amount of formaldehyde 20 ppm or less.

Metallic gloss particles produced according to the present invention can be utilized in various ways as an environmentally friendly material in a field close to human life, such as clothing, interior, such as a low human hazard.

The effects of the present invention are not limited to those mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention relates to a method for producing metal gloss particles having 20 ppm or less of formaldehyde remaining on the surface of the metal gloss particles and having excellent physical properties such as chemical resistance, coating property, glossiness, and hardness.

Hereinafter, the present invention will be described in detail.

Method for producing a metal gloss particles in which the residual amount of formaldehyde of the present invention is minimized comprises the steps of pyrolyzing ethylene diamine and urea to produce an ethylene-urea resin; Reacting the ethylene-urea resin and the melamine-formaldehyde resin to prepare a particle coating solution including the urea-formaldehyde compound represented by Chemical Formula 1 below; And coating, curing, aging, and pulverizing the particle coating solution on the base film to prepare metal gloss particles.

[Formula 1]

CH ₂ N (CH ₂ OH) C (= 0) N (CH ₂ OH) CH ₂

The manufacturing method of the metallic gloss particle of this invention is demonstrated step by step.

As shown in Scheme 1, ethylene diamine and urea are pyrolyzed to prepare ethylene-urea resin.

Scheme 1

NH ₂ CH ₂ CH ₂ NH ₂ + NH ₂ C (= O) NH ₂ --------> CH ₂ NH ₂ C (= O) CH ₂ NH ₂

Ethylene diamine and urea react in the same molar ratio, but in order to improve the efficiency of the reaction, it is preferable to use an excess of 1.1 to 1.3 times the ethylene diamine.

The pyrolysis reaction is carried out at 230 to 270 ° C. for 5 to 8 hours. If the reaction temperature is too low, many unreacted substances remain or the reaction time is long. If the reaction temperature is too high, it is preferable to maintain the above range because there is a danger when the reaction is performed. The reaction temperature is performed while increasing slowly, for example, it is preferable to maintain the rate of rise of 10 ℃ / 20 minutes.

Ammonia generated during the pyrolysis reaction is preferably discharged in consideration of the efficiency and safety of the reaction.

The ethylene-urea resin formed by the pyrolysis reaction is obtained in the form of a milky white solution having high viscosity at about 180 ° C. The unreacted ethylene diamine is then separated under reduced pressure.

The ethylene-urea resin solution is washed with water and dried to produce a white ethylene-urea resin powder.

As shown in Scheme 2, formaldehyde of ethylene-urea resin and melamine-formaldehyde resin is reacted to prepare a particle coating solution including the urea-formaldehyde compound of formula (1).

Scheme 2

CH ₂ NH ₂ C (= O) CH ₂ NH ₂ + 2HCHO --------> CH ₂ N (CH ₂ OH) C (= O) N (CH ₂ OH) CH ₂

Melamine-formaldehyde resin is preferably mixed to include 1 to 1.2 molar ratio of ethylene-urea resin per mole.

In addition, additives may be mixed to improve the physical properties of the metal coating particles and the stability of the coating.

Specifically, 0.2 to 15 parts by weight of dye, 0.1 to 1 part by weight of polyester resin, 0.1 to 0.5 part by weight of fluorine dye dispersant and surface refrigerating agent, and 0.1 to 0.3 of urea-modified polyurethane resin based on 100 parts by weight of particle coating solution It may further comprise parts by weight.

Melamine-formaldehyde resin is generally used in the art, but is not particularly limited, but for example, 1 mol of melamine and 3-6 mol of formaldehyde are reacted with methanol in an alkaline atmosphere, followed by excess alcohol and hydroxyl catalyst at pH 4-5. Preference is given to those prepared by etherification.

The ethylene-urea resin and the melamine-formaldehyde resin are reacted in solution. The solution is preferably selected in consideration of the solubility of ethylene-urea resin and melamine-formaldehyde resin as solvents in which both can be dissolved.

Particle coating solution comprising an ethylene-urea resin and melamine-formaldehyde resin is preferably maintained at a concentration of 30 to 55% by weight in consideration of coating properties.

For example, one or a mixture of two or more selected from acetone, methanol, methyl-ethyl-ketone, and toluene may be used.

The mixed solution may be prepared by preparing an ethylene-urea resin solution and a melamine-formaldehyde resin solution, respectively, and then mixing the same, or simultaneously dissolving the ethylene-urea resin and melamine-formaldehyde resin in a solvent.

The reaction is carried out at room temperature for 10 to 40 minutes.

The prepared particle coating solution is coated on a base film, cured, aged and pulverized to prepare metal gloss particles.

The base film is generally used in the art and is not particularly limited. For example, it is preferable to use a polyester or aluminum vapor deposition polyester film.

Coating, curing and aging are commonly used in the art and are not particularly limited.

Coatings are suitable using, for example, flow casting and application methods such as air knife, gravure, reverse roll, kiss roll, spray or blade. It can be applied directly by development, dried and laminated.

Curing is carried out using a hot oven, for example, at 180 to 200 ° C. for 10 to 60 seconds.

Aging is carried out using a hot oven, for example, at 80 to 100 ° C. for 2-3 days.

Metal gloss particles produced as described above is a coating layer of 0.8 to 2.5 ㎛ thickness is formed on one side of the base film.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

Preparation Example 1 Preparation of Urea Resin

135 g of ethylenediamine was added to a three-necked flask equipped with a cooler, a heating mantle, and a vacuum pump, and the mixture was stirred and boiled. Then, small amounts of 90 g of urea were added and reacted at 250 ° C. for about 6 hours. The ammonia gas generated during the reaction was discharged through a cooler, and the reaction was performed at 10 ° C. every 20 minutes.

A milky high viscosity solution was formed at 180 ° C and the residual ethylenediamine was extracted under reduced pressure with a vacuum pump. The remaining reaction solution was heated to 250 ° C. and cooled to terminate the pyrolysis reaction. The reactant was washed with water and then dried in a dry oven to prepare about 120 g of a white ethylene-urea resin (melting point was about 130 ° C., molecular weight was about 86.0).

Example 1 Preparation of Metallic Glossy Particles

20 g of methanol and 20 g of toluene were added to the dissolving machine, and 30 g of ethylene-urea resin of Preparation Example 1, a melamine-formaldehyde resin solution (solid content of 30% by weight, melamine: formaldehyde = 1: 3 molar ratio) 60 g, dye 0.5g, 0.2g of polyester resin, 0.2g of dye dispersion and surface relubricating agent, and 0.1g of urea-modified polyurethane-based resin were added and mixed to prepare a particle coating solution.

Aluminum was deposited on the polyester film deposited so that the thickness of the particle coating layer 3㎛, and then dried. After curing using a hot oven for 30 seconds at 180 ℃, aged for 2 days at 190 ℃ and pulverized to prepare a metal gloss particles.

Test Example

The physical properties of the metal gloss particles of the Examples and Comparative Examples were measured by the following method and the results are shown in Table 1 below.

[Measurement of physical properties]

1. Chemical resistance: When the cloth was rubbed with acetone solution (100%) and rubbed the coating surface for more than 40 times, it was confirmed as a phenomenon that the dye appeared or peeled off the adhesive surface.

2. Coating property: The surface was coated with a knife at 1mm intervals horizontally and vertically, and then scotch tape was applied to the surface.

3. Glossiness: Visually confirmed.

4. Hardness: confirmed by nail hardness.

5. Formaldehyde detection: The coated particles were pulverized in a pulverizer to form a powder, and then requested by SGS KOREA, an ingredient analysis institution (EPA8315A, HPLC method), to determine whether or not formaldehyde was detected.

division Chemical resistance Coating Luster Hardness Formaldehyde detection Example More than 60 times Good Good Good Not detected Comparative example 40 times Good Good Good 22.8 ppm

As shown in Table 1, the metal gloss particles prepared according to the present invention was confirmed that the residual amount of formaldehyde was significantly reduced while maintaining the physical properties such as chemical resistance, coating properties, glossiness, hardness, or the like.

The embodiments and drawings attached to this specification are merely to clearly show some of the technical ideas included in the present invention, and those skilled in the art can easily infer within the scope of the technical ideas included in the specification and drawings of the present invention. Modifications that can be made and specific embodiments will be apparent that both are included in the scope of the invention.

Claims (12)

Pyrolysing ethylene diamine and urea to produce an ethylene-urea resin; Reacting the ethylene-urea resin and the melamine-formaldehyde resin to prepare a particle coating solution including the urea-formaldehyde compound represented by Chemical Formula 1 below; And Coating, curing, aging, and pulverizing the particle coating solution on a base film to prepare metal gloss particles. Method for producing metallic gloss particles with minimal formaldehyde residues: [Formula 1] CH ₂ N (CH ₂ OH) C (= 0) N (CH ₂ OH) CH ₂ The method of claim 1, wherein the pyrolysis reaction is characterized in that it is carried out for 5 to 8 hours at 230 to 270 ℃ A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The ethylene-urea resin is a solution phase dissolved in a solvent selected from acetone, methanol, methyl-ethyl-ketone and toluene. A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The method of claim 1, wherein the melamine-formaldehyde resin solution contains 3 to 6 molar ratio of formaldehyde with respect to 1 mole of melamine. The method of claim 1, wherein the particle coating solution is characterized in that it comprises 1 to 1.2 molar ratio of ethylene-urea resin with respect to 1 mol of melamine-formaldehyde resin. A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The method according to claim 5, based on 100 parts by weight of the particle coating solution It is characterized in that it further comprises 0.2 to 15 parts by weight of dye, 0.1 to 1 parts by weight of polyester resin, 0.1 to 0.5 parts by weight of fluorine dye dispersant and surface relubricating agent, and 0.1 to 0.3 parts by weight of urea-modified polyurethane-based resin. A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The method of claim 1, wherein the particle coating solution is characterized in that the concentration of 30 to 55% by weight A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The method of claim 1, wherein the base film is a polyester or aluminum vapor deposition polyester film, characterized in that A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The method of claim 1, wherein the curing is characterized in that performed for 10 to 60 seconds at 180 to 200 ℃ A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The method according to claim 1, wherein the aging is characterized in that performed for 2 to 3 days at 80 to 100 ℃ A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. The method of claim 1, wherein the metallic gloss particles, characterized in that it has a coating layer of 0.8 to 2.5 ㎛ thickness on one side of the base film A method for producing metallic gloss particles in which formaldehyde residual amount is minimized. Pyrolysing ethylene diamine and urea to produce an ethylene-urea resin; And reacting the ethylene-urea resin with the melamine-formaldehyde resin to prepare a urea-formaldehyde compound represented by the following Chemical Formula 1. [Formula 1] CH ₂ N (CH ₂ OH) C (= 0) N (CH ₂ OH) CH ₂