KR20170120531A - Eco-friendly lacquer varnish compositions and preparation method thereof - Google Patents

Abstract

The present invention relates to an environmentally friendly varnish composition and a method for producing the same. More specifically, the present invention relates to an environmentally friendly varnish composition having excellent physical properties and workability as well as minimizing bleaching phenomenon and volatile organic compound (VOCs) In particular, the solvent used in the present invention is a volatile organic compound regulated exempt material corresponding to Article 2, Item 10 (3) (Notification Criteria) of the Atmosphere Environmental Preservation Act Article 2 of the Air Pollution Control and Preservation Act, and its photochemical ozone generating ability is negligible. , It is a material that has the technical necessity and substitution effect of the environment-friendly paint and can be exempted from the obligation to install the air pollution prevention facility because it is the raw material which can improve the occupational safety and health, work environment and air pollution. The method for preparing an environmentally friendly varnish composition according to the present invention comprises the steps of: preparing a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate; Preparing acetone and tert-butyl acetate; And 43 to 55 wt% of the modified alkyd acrylic resin, 17 to 23 wt% of the acetone and 28 to 34 wt% of the tert-butyl acetate, with stirring.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an eco-friendly lacquer varnish composition,

The present invention relates to an environmentally friendly varnish composition and a method for producing the same. More specifically, the present invention relates to an environmentally friendly varnish composition having excellent physical properties and workability as well as minimizing bleaching phenomenon and volatile organic compound (VOCs) .

Generally, a varnish or a lacquer varnish is a paint prepared by diluting a resin in a solvent. There are various kinds of resins and solvents used in a varnish. Examples of such varnishes or lacquer varnishes include varnishes for wood inside or outside of a building, wood for interior or exterior use of buildings, which require gloss and durability, and varnish for interior wood, such as wood varnishes, It is a water resistant spa varnish diluted with solvent by heat bonding with oil as main material, and it requires varnish and durability. Interior and exterior wooden parts of interior and exterior wood, furniture varnish, wood varnish for oxidation, alkyd resin for oxidation and alkyd with volatile solvent as main ingredients And varnishes mainly used for wood and steel parts inside and outside of buildings by resin varnishes.

For example, in the case of a thermoplastic resin such as polyethylene, since the solvent can be dissolved in various solvents, the solvent is volatilized and the solvent has a relatively low physical property on the surface of the substrate.

In another example, a thermosetting resin such as a polysulfonate is dissolved only in a relatively high-performance solvent to degrade processability, but has a physical property capable of protecting the surface of the substrate relatively well after the solvent is volatilized.

As in the above-mentioned examples, it is very important to select a resin and an appropriate solvent that can protect the surface of the substrate after removing the solvent with excellent processability. The importance of selecting such a solvent is not only the processability due to the reaction with the resin, This is because the physical properties, workability, and whitening phenomenon can be removed depending on the amount of the compound added to the solvent, and pollution caused by the pollutants generated by the volatilization of most of the solvents can be said.

In other words, since most of the solvent releases volatile organic compounds during the volatilization process in the air, it also releases harmful toxic substances to the human body. Therefore, the toxicity of the solvent is enough to cause deterioration of the working environment and environmental problems. And organic solvents which mainly perform the role of dissolving the resin have such a problem. Such an organic solvent is a typical carcinogen, and not only the manufacturing process of the varnish but also the varnish or lacquer produced at the work site is used, which causes severe damage to the environment of the workplace.

As a prior art document related to the above, there is a method of manufacturing a thermosetting resin varnish (Publication No. 10-2003-0040069), wherein a solid type aromatic polysulfone resin such as powder or pellets and a resin such as toluene or xylene And a varnish prepared by mixing an aromatic hydrocarbon solvent.

100 parts by weight of a modified alkyd acrylic resin containing a modified alkyd resin prepared by the reaction of phthalic anhydride, glycerin, pentaerythritol and soybean fatty acid, and 100 parts by weight of a modified alkyd resin , And 80 to 150 parts by weight of dimethyl carbonate. However, since the coupling with the resin is not stable, dimethyl carbonate as the exemption material for volatile organic compounds (VOCs) is used, but it is somewhat inadequate to be environmentally friendly .

As is apparent from these prior art documents, most of the solvents required for manufacturing varnishes or lacquers are carcinogens, which are extremely harmful to the human body, and various research and development studies are urgently required for the improvement thereof have.

Published Patent No. 10-2003-0040069 Patent No. 10-0928140

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the problems of the prior art, and it is an object of the present invention to provide an environmentally friendly varnish or lacquer composition which not only exerts excellent physical properties and workability but also minimizes bleaching phenomenon and volatile organic compound (VOCs) I would like to provide.

To achieve the above object, an eco-friendly lacquer varnish composition according to one embodiment of the present invention comprises 10 to 99 parts by weight of a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate; 1 to 90 parts by weight of acetone; And 1 to 90 parts by weight of tert-butyl acetate, and is coated on the surface of the metal and has a rust-preventive function.

Wherein the modified alkyd acrylic resin comprises 10 to 40 parts by weight of a modified alkyd resin; 10 to 40 parts by weight of dimethyl carbonate; 1 to 50 parts by weight of styrene; 1 to 50 parts by weight of butyl acrylate; 1 to 50 parts by weight of methylmethacrylate; And 0.5 to 3 parts by weight of benzoyl peroxide.

Also, the modified alkyd resin may include 10 to 50 parts by weight of soybean fatty acid; 1 to 30 parts by weight of glycerin; 1 to 30 parts by weight of phthalic anhydride; 5 to 30 parts by weight of pentaerythritol; 0.5 to 2.5 parts by weight of xylene; And 10 to 70 parts by weight of dimethyl carbonate.

According to another aspect of the present invention, there is provided a process for preparing an environmentally friendly varnish composition, comprising: preparing a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate; Preparing acetone and tert-butyl acetate; And 10 to 99 parts by weight of the modified alkyd acrylic resin, 1 to 99 parts by weight of acetone, and 1 to 90 parts by weight of tert-butyl acetate.

The step of preparing the modified alkyd acrylic resin comprises the steps of adding 10 to 40 parts by weight of a modified alkyd resin and 3 to 18 parts by weight of dimethyl carbonate to the reactor, When the temperature is raised to 80 to 100 ° C., the reactor is charged with 10 to 50 parts by weight of styrene, 1 to 50 parts by weight of butyl acrylate, 1 to 50 parts by weight of methyl methacrylate, And 0.44 to 2.4 parts by weight of benzoyl peroxide, heating the mixture to 90 to 100 캜, and maintaining the temperature for a predetermined time; 0.05 to 0.5 parts by weight of benzoyl peroxide and 1 to 2 parts by weight of dimethyl carbonate are mixed in a reactor maintained in a temperature range of 90 to 100 DEG C for a predetermined time, Maintaining a time; Adding 0.005 to 0.05 part by weight of benzoyl peroxide to the reactor, and maintaining the mixture for a predetermined time; Adding 0.005 to 0.05 part by weight of benzoyl peroxide to the reactor, and then maintaining the mixture for a predetermined period of time; Adding 5 to 10 parts by weight of dimethyl carbonate to the reactor to cool the reactor; And when the cooled temperature reaches 80 캜 or less, 1 to 5 parts by weight of a plasticizer and 1 to 10 parts by weight of dimethyl carbonate are added to react.

The modified alkyd resin in the step of preparing the modified alkyd acrylic resin may be prepared by adding 10 to 50 parts by weight of soybean fatty acid, 1 to 30 parts by weight of glycerin, 1 to 30 parts by weight of phthalic anhydride 1 To 30 parts by weight of pentaerythritol and 5 to 30 parts by weight of pentaerythritol, and stirring the mixture while performing nitrogen blowing to raise the temperature; 0.5 to 2.5 parts by weight of xylene is added when the temperature is raised to 200 to 220 DEG C, and the mixture is refluxed while maintaining a temperature of 200 to 220 DEG C and dehydrating; And adjusting the viscosity by adding 10 to 70 parts by weight of dimethyl carbonate to the reactor when the cooling temperature reaches 90 to 110 ° C.

If necessary, the step of dehydrating and regulating the viscosity may further include the step of recovering the entire amount of xylene when the acid value reaches the range of 4 to 5.

The environmentally friendly lacquer varnish composition according to the present invention enhances the environmental friendliness of the conventional varnish BY VN 600 (Patent No. 10-0928140), minimizes whitening due to physical properties, workability, and climate change, It is possible to manufacture a rust-preventive lacquer varnish which can be used for exporting steel pipes (black pipe, white pipe) and iron products.

Particularly, the solvent used in the present invention is a volatile organic compound regulated exempt material corresponding to the Article 3 (Designated Criteria) Article 2 (10) of the Atmospheric Environment Conservation Act, and its photochemical ozone generating ability is negligible. Therefore, it has the effect of being exempted from the obligation to install the air pollution prevention facility because it is a material that has the technical necessity and substitution effect of the environment-friendly paint and can improve the safety and health of worker, work environment and air pollution.

Prior to this, the present invention optimizes physical properties desired by end users such as non-volatility, viscosity, specific gravity, coating film thickness and water miscibility of solid components, maintains workability such as maintenance of drying speed and prevention of bleaching, The present invention relates to a varnish for exemption of the prevention facilities among air exhaust facilities as well as achievement of environmental / health hygiene by using all of the exempted substances of VOCs and a method of manufacturing the varnish.

The varnish according to the present invention can be applied to steel pipes for the purpose of preventing corrosion due to salinity and the like encountered during marine transportation for the export of steel pipes and for preventing the corrosion of steel pipes during use in order to develop shale gas and oil, It can be called lacquer varnish.

Hereinafter, the present invention will be described in more detail with reference to the preferred embodiments.

The environmentally friendly lacquer varnish composition according to a preferred embodiment of the present invention comprises 10 to 99 parts by weight of a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate; 1 to 90 parts by weight of acetone; And 1 to 90 parts by weight of tert-butyl acetate, and is preferably applied to the surface of the metal to have a rust-preventive function.

Preferably, 43 to 55 wt% of modified alkyd acrylic resin containing modified alkyd resin and dimethyl carbonate, 17 to 23 wt% of acetone and 28 to 34 wt% of tert-butyl acetate. However, it is more preferable that the dimethyl carbonate of the modified alkyd acrylic resin is contained in the range of 20 to 26 wt% in the total wt% of the environmentally friendly varnish composition.

Alkyd resin is broadly defined as a dendritic substance produced by the combination of alcohol and acid (a compound of cid (kyd) of Al + Al + Acid), which was named by Kienle in 1927. This is generally referred to as Polyester. In a narrow sense, an alkyd resin used in a common painting technology field is a condensate of a polybasic acid such as phthalic anhydride and a polyhydric alcohol such as glycerin as a skeleton It is a resin modified with oil or fatty acid.

Therefore, it is also called an oil-changeable alkyd resin, and it is general to include it in the range of an alkyd resin that is modified with a rosin, a phenol resin, a polymerizable monomer or the like. All physical properties of alkyd resins are mainly determined by the type of denatured oil (concentration of double bonds, presence or absence of conjugated double bonds), whey, and denaturation.

Alkyd resins can be classified into solvent type alkyd resins, receptive type alkyd resins and powder type alkyd resins. When the solvent type alkyd resins are broadly classified, they are classified into a rubidic alkyd resin, an oil free alkyd resin (referred to as a polyester) ), And a modified alkyd resin modified with a modified resin.

In general, an alkyd resin has excellent durability and weatherability, and is flexible, strong, and maintains glossiness. In addition, there is an advantage that the coating film having a good color tone retention property, a good pigment dispersibility, an excellent painting workability and a sufficiently dried coating film is excellent in resistance to hydrocarbon solvents and heat resistance.

The advantages of such alkyd resins are advantageous compared with other general paints, but they are not resistant to alkalis such as cement and concrete, and are resistant to strong solvents such as esters and ketones. .

It has been used in automobiles, household appliances, metal systems, vehicles and other fields. Recently, various studies for improving the functionality of alkyd resins have been continued and expected to be developed in the future.

As mentioned above, the alkyd resin is composed of three kinds of basic constituents, that is, a polyfunctional group, a polyhydric alcohol, and an oil (or fatty acid). By changing the kind and amount of these raw materials, have. In this way, the possibility of denaturation is very large, and the alkyd resin is used alone, and compatibility with other vehicles is given depending on the degree of denaturation, and mixed with other resins in many cases.

Examples of the modified alkyd resin that can be used in the present invention include a urethane-modified alkyd resin using a urethane-based modifier, an epoxy-modified alkyd resin using an epoxy modifier, and a silicone-modified alkyd resin using a silicone modifier. The alkyd resin which can be used in the present invention will be described in more detail as follows.

Alkyd resin is broadly defined as a dendritic substance produced by the bond between alcohol and acid (a compound of cid (kyd) of Al + Al + Acid). This is generally referred to as Polyester. An alkyd resin commonly used in the paint industry is a condensation product of a polybasic acid such as anhydrous phthalic acid and a polyhydric alcohol such as glycerin, Denatured resin.

In this sense, it is also referred to as a rubidic alkyd resin, and it is general to incorporate it into an alkyd resin which is further modified with a rosin, a phenol resin, a polymerizable monomer or the like. The physical properties of the alkyd resin are mainly determined by the type of denatured oil (concentration of double bond, presence or absence of conjugated double bond), whey, kind of denaturation, and the like.

When the alkyd resin is classified according to the type of the paint, it can be classified into a solvent type alkyd resin, a receiving type alkyd resin and a powder type alkyd resin.

The solvent type alkyd resin may be further classified into three types: a rubidic alkyd resin, an oil free alkyd resin (also referred to as a polyester), and a modified alkyd resin modified with a modified resin.

Such alkyd resin paints are excellent in durability and weatherability and are flexible and strong. In addition, it has good gloss retention (sustaining property), good color retentivity, good pigment dispersion and good painting workability. In addition, a sufficiently dry film has a high resistance to hydrocarbon solvents, a relatively good heat resistance, and a low cost.

Considering the advantages of these alkyd resin coatings, it has advantages over other conventional paints, but it can not be used in places where alkali is strong, such as cement or concrete because of its low alkaline resistance, and resistance to strong solvents such as esters and ketones There are low disadvantages. Therefore, it is mainly used in automobiles, household appliances, metal systems, vehicles, and other fields.

As mentioned above, the alkyd resin is composed of three basic constituents, that is, a polyfunctional group, a polyhydric alcohol, and an oil (or fatty acid). By varying the specific kinds and amounts of these raw materials, have.

Since the possibility of denaturation is very large in this way, not only the alkyd resin can be used alone but also the compatibility with other vehicles depending on the degree of denaturation can be imparted, and it is often used in combination with other resins . For this reason, alkyd resins are known to be the most used in synthetic resins, and more than 90% of the alkyd resin production is used in the paint industry.

First, we will look at 'oil (oil or fatty acid)' among the basic constituents of alkyd resin. A coating film of a polyester resin composed only of a polybasic acid and a polyhydric alcohol is relatively hard and easy to be crumbled and has a disadvantage that it is difficult to dissolve in a solvent. However, since long-chain aliphatic compounds such as oil are flexible and easily soluble in hydrocarbon solvents, the fatty acid or the oil-modified alkyd resin imparts long chain aliphatic properties while the average number of functional groups (average number of functional groups) To reduce the gelation in the reaction with the resin.

In the case of an alkyd resin modified with a drying oil fatty acid (a drying oil fatty acid), it is dried at room temperature like a drying apparatus for drying oil in the air.

The properties of the alkyd resin (paint) are largely influenced by the type of oil or fatty acid that is denatured and the relative amount of polyester that is the skeleton, that is, the oil length. When classified by whey, Heavy oil and long oil.

It is used for hardening oil of long oil type alkyd, Nitrocellulose lacquer, but also used for heat curing by using it with amino resin.

Short oil (oil: 35 ~ 45%) is used in heat-drying type paint mixed with alkyd resin synthesized by using non-drying oil or semi-drying oil. It has little whey and is not dried at room temperature.

It has the broadest application in the case of heavy oil (45 ~ 55% of whey). It is used for drying enamel at room temperature alone by using drying oil or semi-drying oil. It is also used for heat drying type enamel by mixing 20% of melamine resin. do.

The alkyd resin synthesized by using drying oil has a good air-drying property and the coating film has good flexibility and is used for anti-corrosive coating of large structures.

Next, we will look at polyvalent alcohol (Glycol). In general, the dihydric alcohol forms a polymer having a linear structure, so that the interior of the resin is used for internal plasticization. In this case, the distance of the water period, that is, the greater the number of carbon atoms, do.

The presence of hydrocarbon groups in the oil or branch or side chain (eg, propylene glycol) improves the solubility in the hydrocarbon solvent, but the nonpolar side chain lowers the hardness of the resin. This is thought to be because the resin interferes with making a dense crystal structure. In addition, dihydric alcohols are used in combination with trihydric alcohols as regulators for molecular weights. Alcohol having trihydric or more is likely to have a crosslinked structure due to ester bonding, and the resulting resin is also easy to obtain a quick-drying and hard-hardened resin.

The primary hydroxyl group is more easily esterified than the secondary hydroxyl group, which is advantageous in resin production. Since alcohols having four or more hydroxyl groups are highly functional, care must be taken to prevent gelation during resin production. Raw materials and characteristics that are relatively widely used in the production of alkyd resins are shown in Table 4-2. Characteristic is the standard comparison of glycerin. The rate of esterification of alcohol is in the order of first degree alcohol> second degree alcohol> third degree alcohol.

Specific examples of dihydric alcohols include glycols such as ethylene glycol (EG) propylene glycol (PG), diethylene glycol (DEG), and butyl glycol (BG).

Examples of trihydric alcohols include neopentyl glycol (NPG), glycerine, trimethylol ethane (TME), trimethylolpropanee (TMP), and 1,2,6-hexane triol. Pentaerythritol (PE) Sorbitol, Diglycerol, and Dipentaerythritol. Polyhydric alcohols include 1,4-cyclohexane dimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, hydroxypivalylhydroxypivalate, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol and 2-methyl-1,3-propanediol.

As the polybasic acid, phthalic anhydride is most widely used, but aromatic or aliphatic compounds may be used. For example, benzoic acid or p-tert butyl benzoic acid (PTBBA) is used as a monobasic acid, phthalic anhydride (PAn), iso-phthlic acid (IPA), tetraphthalic acid 3,6-endomethylene phthalic anhydride, succinic acid (anhydride), adipic acid or sebacic acid may be used as the polybasic acid, and 1,2,3,4-tetrahydrobenzoic acid 1,3-cyclohexane dicarbonic acid, 1,4-cyclohexane dicarbonic acid, hexahydrophthalic anhydride, or 5-sodiodulpho isophthalic acid.

The urethane type modifier, the epoxy type modifier and the silicon type modifier which are used for modifying the resin which can be used for modifying the resin can be selected and used from the raw materials of the modifiers shown in the following Table 1, respectively.

Urethane-based modifier TDI (Toluene Di-Isocyanate) MDI (Diphenylenemethane Di-Isocyanate) HDI (hexamethylene di-isocyanate) HMDI (Dicyclohexylenemethane Di-Isocyanate) IPDI (Isophorone Di-Isocyanate) XDI (Xylene Di-Isocyanate) Epoxy-based modifier Bisphenol A Type Epoxy Resin Bisphenol F Type Epoxy Resin Silicone-based modifier Methoxy functional Polysiloxane

In the production of the modified alkyd resin used in the present invention, the role and kind of the fatty acid used will be examined. First, let's look first at oil or fatty acids.

The coating film of a polyester resin composed only of a polybasic acid and a polyhydric alcohol has a drawback that it is relatively hard, is easy to break, and is difficult to melt in a solvent. However, since long-chain aliphatic compounds such as oil are flexible and easily soluble in hydrocarbon solvents, the fatty acid or the oil-modified alkyd resin imparts long chain aliphatic properties while the average number of functional groups in the reaction system Thereby reducing the gelation in the reaction with the resin.

Also, in the case of an alkyd resin modified with a drying oil fatty acid (a drying oil fatty acid), it becomes a normal-temperature drying type as in the air drying apparatus of a drying oil (drying oil).

The properties of the alkyd resin (paint) are largely dependent on the type of oil or fatty acid to be denatured and the relative amount of polyester which is the skeleton, that is, the oil length.

Specific examples of fatty acids having such functions include soybean oil fatty acid, tall oil fatty acid, coconut oil fatty acid, caster oil fatty acid, (Caffeine Oil Fatty Acid), Flaxseed Oil Fatty Acid, Dehydrated Caster Oil Fatty Acid, Rice Bran Oil Fatty Acid, Cotton Seed Oil Fatty Acid, Linseed Oil Fatty Acid, Safflower Oil Fatty Acid ) And fish oil fatty acid (Fish Oil Fatty Acid) may be used.

In the production of the modified alkyd resin used in the present invention, a polyhydric alcohol is used. Generally, bivalent alcohols form a polymer having a linear structure, so that the interior of the resin is used for internal plasticization. In this case, as the distance of the water period, that is, the number of carbon atoms, do. Those having a hydrocarbon group on the side chain (side chains) (for example, propylene glycol) have good solubility in the hydrocarbon solvent. However, non-polar side chains (side chains) lower the hardness of the resin. This is thought to be because the resin interferes with making a dense crystal structure. The dihydric alcohol is used as a molecular weight regulator in combination with a trihydric alcohol. An alcohol having three or more dihydric alcohols is likely to have a crosslinked structure due to ester bonding, and the resulting resin is also quick-drying and has a high hardness.

Since the primary hydroxyl group is more easily esterified than the secondary hydroxyl group, it is advantageous in resin production, and alcohol having four or more hydroxyl groups is highly functional, so care must be taken to prevent gelation during resin production. Specifically, the types of raw materials that are relatively widely used in the production of alkyd resins are shown in Table 2 below. The general rate of esterification of such polyhydric alcohols is in the order of primary alcohol> secondary alcohol> tertiary alcohol.

Types of polyhydric alcohols Concrete example Dihydric alcohol Glycol:
ethylene glycol (EG)
propylene glycol (PG)
diethylene glycol (DEG)
butyl glycol (BG) Trivalent alcohol Neopentyl glycol (NPG) Glycerine Trimethylol ethane (TME) Trimethylol propnae (TMP) 1,2,6-hexane triol 4-valent alcohol Pentaerythritol (PE) Sorbitol diglycerol dipentaerythritol

In the production of the modified alkyd resin used in the present invention, a polybasic acid may be used. Phthalic anhydride is the most commonly used, but other aromatic or aliphatic compounds can also be used and examples of polybasic acids that can be used in Table 3 below are given.

Types of polybasic acids Concrete example 1 base acid
Benzoic acid p-tert butyl benzoic acid (PTBBA) Dibasic acid phthalic anhydride (PAn) iso-phthlic acid (IPA) tetraphthalic acid (TPA) tetra hydro phthalic anhydride (THPAn) Maleic anhydride (MAn) Fumaric acid Sebacic acid Adipic acid Chlorendic (HET) anhydride 3 6-endomethylene phthalic anhydride Succinic acid (anhydride)

In a preferred embodiment of the present invention, a modified alkyd resin can be prepared by using such a raw material, wherein the modified alkyd resin comprises 10 to 50 parts by weight of a soybean fatty acid; 1 to 30 parts by weight of glycerin; 1 to 30 parts by weight of phthalic anhydride; 5 to 30 parts by weight of pentaerythritol; 0.5 to 2.5 parts by weight of xylene; And 10 to 70 parts by weight of dimethyl carbonate.

More preferably, the modified alkyd resin comprises 25 to 35 parts by weight of soybean fatty acid, 1 to 10 parts by weight of glycerin, 15 to 25 parts by weight of phthalic anhydride, 5 to 15 parts by weight of pentaerythritol, 0.5 to 2.5 parts by weight of xylene, And 35 to 45 parts by weight of a carbonate.

As described above, the soybean fatty acid is intended to induce denaturation of the alkyd resin, and it is preferably contained in an amount of 10 to 50 parts by weight, preferably 25 to 35 parts by weight, and most preferably 29.96 parts by weight, It is difficult to induce denaturation of the alkyd resin, while if it exceeds 50 parts by weight, the alkyd resin may be excessively denatured.

Glycerine (94%) is a polyhydric alcohol and is used as a raw material for an alkyd resin. In order to satisfy the physical properties of the modified alkyd resin, 1 to 30 parts by weight, preferably 1 to 10 parts by weight, May be added in the range of 6.04 parts by weight.

The phthalic anhydride is a polyvalent acid and is used as a raw material for an alkyd resin in the same manner as glycerin. The phthalic anhydride is also added in an amount of 1 to 30 parts by weight, preferably 15 to 25 parts by weight, in order to satisfy the properties of a modified alkyd resin such as glycerin Part, and more preferably 18.86 parts by weight.

Pentaerythritol (95%) is a polyhydric alcohol and can serve as a stabilizer to stabilize the alkyd resin. When the pentaerythritol is less than 5 parts by weight, the properties of the modified alkyd resin are stabilized , And when the amount is more than 30 parts by weight, the effect of stabilizing the physical properties of the modified alkyd resin is not exerted as compared with the case where the amount is less than 5 parts by weight, preferably 5 to 30 parts by weight, preferably 5 to 15 parts by weight, By weight, and most preferably 9.72 parts by weight.

Xylene is a volatile organic compound (VOC) regulated substance that is used as a reflux solvent to smoothly remove resin (condensate) and smooth reaction of the resin during reaction. However, when the reaction is completed, Therefore, it is preferable that the reactor is vacuumed to recover 100%. The initial amount to be charged is preferably in the range of 0.5 to 2.5 parts by weight (more preferably 1.93 parts by weight) in consideration of 100% recovery.

Dimethyl carbonate is used as a diluting solvent to control viscosity of modified alkyd resin and is a volatile organic compound (VOC) regulated exempt material. This is to replace the toluene solvent in the existing product with the volatile organic compound-exempt material, especially dimethyl carbonate is more soluble than acetone or tert-butyl acetate, which is exempted from other VOCs. The amount is preferably 10 to 70 parts by weight, preferably 35 to 45 parts by weight, more preferably 40.00 parts by weight in consideration of solubility.

This is because an amount less than 10 parts by weight of dimethyl carbonate is insignificant to control the viscosity of the modified alkyd resin and more than 70 parts by weight of the amount of dimethyl carbonate is less effective than viscosity of the modified alkyd resin to be.

The modified alkyd acrylic resin is obtained through a secondary reaction and comprises 10 to 40 parts by weight of a modified alkyd resin; 10 to 40 parts by weight of dimethyl carbonate; 1 to 50 parts by weight of styrene; 1 to 50 parts by weight of butyl acrylate; 1 to 50 parts by weight of methylmethacrylate; And 0.5 to 3 parts by weight of benzoyl peroxide.

More preferably, 18 to 25 parts by weight of a modified alkyd resin, 25 to 45 parts by weight of dimethyl carbonate, 10 to 30 parts by weight of styrene, 5 to 15 parts by weight of butyl acrylate, 1 to 10 parts by weight of methyl methacrylate, Oxide of 0.5 to 3 parts by weight may be used as the modified alkyd acrylic resin.

The modified alkyd resin serves as the base of the modified alkyd acrylic resin. As described above, 10 to 50 parts by weight of soybean fatty acid, 1 to 300 parts by weight of glycerin, 1 to 30 parts by weight of phthalic anhydride, 5 to 30 parts by weight of pentaerythritol 0.5 to 2.5 parts by weight of xylene and 10 to 70 parts by weight of dimethyl carbonate are preferably used and the amount of the component is 10 to 40 parts by weight and preferably 18 to 25 parts by weight in view of the mixing ratio with other components , And more preferably 21.92 parts by weight.

The dimethyl carbonate used for the production of the modified alkyd acrylic resin is used as a solvent for the modified alkyd acrylic resin to facilitate not only the dissolution but also the dilution. When the amount is less than 10 parts by weight, the modified alkyd acrylic resin is insufficient, The amount of dimethyl carbonate is excessively increased and a large amount of other components must be added correspondingly. Therefore, it is more preferable to add dimethyl carbonate in an amount of 10 to 40 parts by weight.

Styrene used in the production of modified alkyd acrylic resins is an intermediate raw material (monomer) for the production of polymer synthesis products. Styrene is contained in 35 kinds of substances to be regulated as volatile organic compounds (VOCs) And the volatile organic compound is not contained in the final synthetic resin. Such styrene is preferably added in an amount of 1 to 50 parts by weight, preferably 10 to 30 parts by weight, more preferably 24.72 parts by weight, in consideration of the reactivity in the polymerization reaction.

Butyl acrylate (BA) is a monomer used for paint adhesion and synthesis. It is included in 35 kinds of substances to be regulated as volatile organic compounds (VOCs) like styrene. However, in the polymerization reaction, The volatile organic compound is not contained in the final synthetic resin. Such butyl acrylate is also preferably added in an amount of 1 to 50 parts by weight, preferably 5 to 15 parts by weight, more preferably 8.98 parts by weight, in consideration of the reactivity.

Methyl methacrylate (MMA) is a monomer for acrylic synthesis reaction. Like methylene stearate and butylacrylate, methyl methacrylate (MMA) is included in 35 substances to be regulated as volatile organic compounds (VOCs). However, The polymer is changed into a polymer so that volatile organic compounds are not contained in the final synthetic resin. It is preferable that such methyl methacrylate is also added in an amount of 1 to 50 parts by weight, preferably 1 to 10 parts by weight, more preferably 5.61 parts by weight, in consideration of the reactivity.

The monomer for acrylic synthesis is not limited to the above-mentioned methyl methacrylate but may be exemplified by methyl acrylate, ethyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl N-hexyl methacrylate, lauryl methacrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl methacrylate, isobutyl methacrylate, Acrylamide, diacetone acrylamide, glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate and acrylonitrile as well as acrylonitrile, methacrylonitrile, It is also possible to use at least one or more combinations selected from the group consisting of

The benzoyl peroxide (BPO 98%) is preferably added as a synthesis initiator for the viscosity of the modified alkyd acrylic resin in the range of 0.5 to 3 parts by weight. If it is less than 0.5, it is difficult to impart a viscosity to the modified alkyd acrylic resin. If it exceeds 3 parts by weight, the physical properties of the modified alkyd acrylic resin may be deformed. Therefore, it is preferable that benzoyl peroxide is added in an amount of 0.5 to 3 parts by weight.

The synthetic initiator is not limited to benzoyl peroxide, but it is also possible to use AIBN (azo bis iso-butyronitrile), di-tert-butyl peroxide, tert-butyl perbenzoate and the like.

The environmentally friendly lacquer varnish composition according to the present invention comprises 10 to 99 parts by weight of a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate; 1 to 90 parts by weight of acetone; And 1 to 90 parts by weight of tert-butyl acetate, and is applied to the surface of the metal and has a rust-preventive function.

Preferably, the environmentally friendly lacquer varnish composition of the present invention comprises 43 to 55 wt% of a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate, 17 to 23 wt% of acetone, and 28 to 34 wt% of tert-butyl acetate. Lt; / RTI >

The dimethyl carbonate of the modified alkyd acrylic resin is more preferably contained in the range of 20 to 26 wt% in the total wt% of the environmentally friendly varnish composition. The diluting solvents of dimethyl carbonate, acetone and tert-butyl acetate are eco- It is a volatile organic compound (VOC) regulation exempt substance announced by the National Institute of Environmental Research.

The modified alkyd acrylic resin is preferably used in the range of 10 to 99 parts by weight, preferably 43 to 55% by weight, in order to maximize physical properties of the environmentally friendly varnish. When the amount of the modified alkyd acrylic resin is less than 10 parts by weight, the environmentally friendly varnish composition is difficult to function. When the amount of the modified alkyd acrylic resin is more than 99 parts by weight, the amount of added acetone and tert- To 99 parts by weight, preferably 43 to 55% by weight.

Here, the dimethyl carbonate is added to the environmentally friendly varnish composition in order to maximize the role of the solvent as a solvent, and is a volatile organic compound (VOC) -regulated material. If the amount of dimethyl carbonate is less than 20 wt%, the amount of other components constituting the environmentally friendly varnish composition is insufficient. When the amount of dimethyl carbonate is more than 26 wt%, the amount of other components other than dimethyl carbonate is decreased, and the physical properties of the final environmentally friendly varnish composition are not improved. The amount of dimethyl carbonate is preferably in the range of 20 to 26 wt%.

Acetone is a volatile organic compound (VOC) regulated substance that not only binds resin but also serves as a solvent for dilution. The acetone is preferably added in an amount of 1 to 90 parts by weight, preferably 17 to 23% by weight, in order to improve the bonding strength of the resin.

Tert-butyl acetate (T-BA: tertiary butyl acetate) also acts as a solvent for resin binding and dilution, and is a volatile organic compound (VOC) regulated exempt material. It is preferable that the amount of the tert-butyl acetate is 1 to 90 parts by weight, preferably 28 to 34% by weight, in order to sufficiently perform the role of the resin binding and diluting solvent.

Meanwhile, a method for producing a modified alkyd resin, a modified alkyd acrylic resin, and an environmentally friendly varnish composition will be described in detail below.

(1) denaturation Alkyd resin  Produce

First, 10 to 50 parts by weight of soybean fatty acid, 1 to 30 parts by weight of glycerin, 1 to 30 parts by weight of phthalic anhydride and 5 to 30 parts by weight of pentaerythritol are added to the reactor, and then nitrogen is blown and stirred do.

Next, 0.5 to 2.5 parts by weight of xylene is introduced into the reactor at a temperature of 200 to 220 DEG C, and the reactor is heated to 200 to 220 DEG C while being refluxed.

This means that when the temperature is elevated to 210 ° C in the previous step, xylene is added to reflux and maintained at 210 ° C to dehydrate.

Here, xylene is used as a solvent for reflux in order to smoothly remove the product 'water (condensate)' during the reaction of the resin and the reaction, and when the reaction is completed, Is 100% recovered.

However, when the acid value of xylene reaches 4 to 5, the reaction is terminated and 100% is recovered (for example, when 1.93 parts by weight of xylene is added to the reactor, 1.93 parts by weight It means to be recovered).

Next, 10 to 70 parts by weight of dimethyl carbonate is added to the reactor to adjust the viscosity.

That is, when the reaction is completed in the previous step and reaches a cooling temperature (100 ° C or less) of 90-110 ° C, the viscosity is adjusted and dimethyl carbonate is added for dilution to adjust the size and finish.

In this case, dimethyl carbonate is used as a viscosity control agent and a diluting solvent, and is exempt from the regulation of volatile organic compounds (VOCs). The dimethyl carbonate is most soluble in regulated exempt materials and is added to the first reaction for producing a modified alkyd resin.

(2) denaturation Alkyd acrylic resin (acrylic modified alkyd resin)

First, 10 to 40 parts by weight of a modified alkyd resin and 3 to 18 parts by weight of dimethyl carbonate are added to the reactor one or two times, and the temperature is raised while stirring.

Next, when the temperature is raised to 80 to 100 ° C, 10 to 50 parts by weight of styrene, 1 to 50 parts by weight of butyl acrylate, 1 to 15 parts by weight of methyl methacrylate and 0.44 to 2.4 parts by weight of benzoyl peroxide And the temperature is raised to 90 to 100 캜 and maintained for a predetermined time.

When the temperature reached 90 ° C, monomers of styrene, butyl acrylate, methyl methacrylate and benzoyl peroxide were uniformly mixed in the reactor, and the mixture was dropped for 3 hours. The reaction is maintained for 1 hour while the temperature is raised.

In addition, since styrene, butyl acrylate, and methyl methacrylate are volatile organic compounds (VOCs) regulated substances, they change into polymers that are polymeric in the course of the polymerization reaction. Therefore, the environmentally friendly varnish composition contains volatile organic compounds (VOCs) It is not.

Next, 0.05 to 0.5 parts by weight of benzoyl peroxide and 1 to 2 parts by weight of dimethyl carbonate are mixed in a reactor in which the temperature is raised, and the reactor is charged into the reactor a plurality of times and maintained for a predetermined time.

In order to obtain a precise viscosity and to facilitate dissolution, a small amount of benzoyl peroxide and a small amount of dimethyl carbonate were uniformly mixed at 10 minute intervals after 1 hour maintenance reaction in the previous step, and the mixture was added to the reactor four times in total, The reaction is maintained for 1 hour and 30 minutes. It is preferable to divide the reaction mixture into the reactor, but it is also possible to add a small amount of benzoyl peroxide and dimethyl carbonate to the reactor at a time without dividing the mixture into the reactor.

Next, 0.005 to 0.05 part by weight of benzoyl peroxide is once added to the reactor, followed by a step of maintaining the same for a certain period of time. After maintaining the reaction for 1 hour and 30 minutes, a small amount of benzoyl peroxide, which is a synthetic initiator for reaching the standard value of viscosity, is added, and the reaction is maintained for 1 hour and 30 minutes.

Next, 0.005 to 0.05 part by weight of benzoyl peroxide is once added to the reactor once, and the step of holding the mixture again for a predetermined time is carried out. After the maintenance reaction for 1 hour and 30 minutes, a small amount of benzoyl peroxide is added again and the reaction is maintained for 1 hour and 30 minutes.

The step of adding a small amount of benzoyl peroxide can be omitted if necessary, and it is also possible to put the benzoyl peroxide into the reactor at a time.

Next, 5 to 10 parts by weight of dimethyl carbonate is once added to the reactor, followed by cooling. That is, it can be said that after cooling for 2 hours, dimethyl carbonate is added and cooled for simultaneous dilution.

Next, when the cooled temperature reaches 80 캜 or less, 1 to 5 parts by weight (more preferably, 2.73 parts by weight) of a plasticizer and 1 to 10 parts by weight (more preferably, 6.90 parts by weight) of dimethyl carbonate are added Followed by a reaction step.

That is, when the cooling temperature reaches 80 ° C or less, NEO-T, which is a plasticizer capable of smoothly mixing the monomer and the solvent, and dimethyl carbonate as a resin diluting solvent are added to adjust the size and finish the reaction.

(3) Environmentally friendly Lakka Varnish  Preparation of composition

First, a step of producing a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate is carried out. However, since the modified alkyd resin and the modified alkyd acrylic resin including dimethyl carbonate in this step have been described above in detail, the repeated explanation will be omitted here.

Next, a step of preparing acetone and tert-butyl acetate is carried out. Three diluting solvents for dimethyl carbonate, acetone and tert-butyl acetate are environmentally-friendly diluents which are exempted from the VOCs regulated by the National Institute of Environmental Research, .

10 to 99 parts by weight, preferably 43 to 55% by weight (including 20 to 26% by weight of dimethyl carbonate) of a modified alkyd acrylic resin; 1 to 99 parts by weight, preferably 17 to 23% by weight, of acetone; And 1 to 90 parts by weight, preferably 28 to 34% by weight, of tert-butyl acetate are mixed with stirring.

10 to 99 parts by weight, preferably 43 to 55% by weight, more preferably 49% by weight, of a modified alkyd acrylic resin is added to the reactor. 1 to 99 parts by weight, preferably 17 to 23% by weight, more preferably 20% by weight, of acetone; And 1 to 90 parts by weight, preferably 28 to 34% by weight, and more preferably 31% by weight of tetra-butyl acetate are mixed and mixed while stirring to obtain an environmentally friendly locker varnish composition.

The results of VOCs detection of the varnish according to the present invention are as follows.

As shown in the following Table 4, the VOCs of the conventional varnishes were as high as 181.25 g / L, while the VOCs of the varnishes of the present invention were as low as 4.98 g / L. Accordingly, it can be confirmed that the varnish of the present invention is environmentally friendly because the VOCs, which are volatile organic compounds, are detected less.

product Experiment Experimental Method VOCs detection amount [g / L] Existing lacquer varnish
(BY VN 600) Korea Construction & Environment Testing Institute KS M ISO 11890-2: 2007 181.25 The environmentally friendly lacquer varnish Pukyong National University Collaborative Laboratory Habits 4.98

As described above, according to the present invention, it is possible to enhance the environmental friendliness of the conventional varnish BY VN 600 (Patent No. 10-0928140), minimize the whitening phenomenon due to physical properties, workability, and climate change, (Black pipe, white pipe), steel products, and the like can be manufactured.

In particular, the solvent or solvent used in the present invention is a volatile organic compound regulated exempt material corresponding to the Article 3, Article 2 (Designated Criteria) Article 2 (10) of the Air Quality Preservation Act, and its photochemical ozone generating ability is negligible. It is insignificant. Accordingly, the solvent or solvent is exempted from the obligation to install the air pollution prevention facility since it is a material having the technical necessity and substitution effect of the environmentally friendly paint and can improve the occupational safety and health, work environment and air pollution.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention may be embodied otherwise without departing from the spirit and scope of the invention.

Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to illustrate them, and the scope of the technical idea of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be construed according to the claims, and all technical ideas within the scope of the claims should be construed as being included in the scope of the present invention.

Claims (7)

10 to 99 parts by weight of a modified alkyd acrylic resin containing a modified alkyd resin and dimethyl carbonate;
1 to 90 parts by weight of acetone; And
1 to 90 parts by weight of tert-butyl acetate,
An environmentally friendly lacquer varnish composition coated on the surface of metal and having a rust inhibitive function. The acrylic resin composition according to claim 1, wherein the modified alkyd acrylic resin
10 to 40 parts by weight of a modified alkyd resin; 10 to 40 parts by weight of dimethyl carbonate; 1 to 50 parts by weight of styrene; 1 to 50 parts by weight of butyl acrylate; 1 to 50 parts by weight of methylmethacrylate; And 0.5 to 3 parts by weight of benzoyl peroxide, based on the total weight of the composition. The method according to claim 1, wherein the modified alkyd resin
10 to 50 parts by weight of soybean fatty acid; 1 to 30 parts by weight of glycerin; 1 to 30 parts by weight of phthalic anhydride; 5 to 30 parts by weight of pentaerythritol; 0.5 to 2.5 parts by weight of xylene; And 10 to 70 parts by weight of dimethyl carbonate. Preparing a modified alkyd acrylic resin comprising a modified alkyd resin and dimethyl carbonate;
Preparing acetone and tert-butyl acetate; And
Mixing 10 to 99 parts by weight of the modified alkyd acrylic resin, 1 to 99 parts by weight of acetone, and 1 to 90 parts by weight of tert-butyl acetate with stirring. ≪ / RTI > 5. The method of claim 4,
The step of preparing the modified alkyd acrylic resin comprises:
Adding 10 to 40 parts by weight of a modified alkyd resin and 3 to 18 parts by weight of dimethyl carbonate to the reactor, and heating the mixture while stirring;
When the temperature is raised to 80 to 100 ° C., the reactor is charged with 10 to 50 parts by weight of styrene, 1 to 50 parts by weight of butyl acrylate, 1 to 50 parts by weight of methyl methacrylate, And 0.44 to 2.4 parts by weight of benzoyl peroxide, heating the mixture to 90 to 100 캜, and maintaining the temperature for a predetermined time;
0.05 to 0.5 parts by weight of benzoyl peroxide and 1 to 2 parts by weight of dimethyl carbonate are mixed in a reactor maintained in a temperature range of 90 to 100 DEG C for a predetermined time, Maintaining a time;
Adding 0.005 to 0.05 part by weight of benzoyl peroxide to the reactor, and maintaining the mixture for a predetermined time;
Adding 0.005 to 0.05 part by weight of benzoyl peroxide to the reactor, and then maintaining the mixture for a predetermined period of time;
Adding 5 to 10 parts by weight of dimethyl carbonate to the reactor to cool the reactor; And
The method of claim 1, wherein, when the temperature is lower than 80 ° C., 1 to 5 parts by weight of a plasticizer and 1 to 10 parts by weight of dimethyl carbonate are added. 5. The method of claim 4,
In the modified alkyd resin in the step of producing the modified alkyd acrylic resin,
10 to 50 parts by weight of soybean fatty acid, 1 to 30 parts by weight of glycerin, 1 to 30 parts by weight of phthalic anhydride and 5 to 30 parts by weight of pentaerythritol were added to the reactor, Stirring and elevating the temperature while performing nitrogen blowing;
0.5 to 2.5 parts by weight of xylene is added when the temperature is raised to 200 to 220 DEG C, and the mixture is refluxed while maintaining a temperature of 200 to 220 DEG C and dehydrating; And
And adding 10 to 70 parts by weight of dimethyl carbonate to the reactor to adjust the viscosity of the mixture when the cooling temperature reaches 90 to 110 占 폚. The method according to claim 6,
Between the step of dewatering and the step of adjusting viscosity,
And recovering the entire amount of xylene when the acid value reaches the range of 4 to 5. The method of claim 1,