KR100822047B1 - Natural synthesis lacquering composition and the manufacturing method - Google Patents

Abstract

The present invention relates to a natural synthetic lacquer composition and a method for manufacturing the same, the conventional traditional lacquer is bad for toxicity, coating workability, economic feasibility to the human skin, and in the case of the most popular Kash synthetic lacquer in recent years has a smell of free formaldehyde There is a problem that is toxic.

In order to solve this problem, the present invention uses a cashew oil containing purified cardanol with a purity of 90 to 95%, but uses reactive plant oil (kin oil, linseed oil), rosin or rosin derivative in a certain temperature range. After the reaction to secure a constant viscosity and then cooled, the reaction resin is diluted with natural oils (orange oil, terebin oil) to obtain a high molecular weight synthetic resin, and the paint additives are mixed with the high molecular weight synthetic resin. have.

Cardanol, cashew oil, paint additives, rosin derivatives, natural oils.

Description

Natural synthesis lacquering composition and the manufacturing method

The present invention does not use formaldehyde derivatives (formaldehyde, hexamine, formarin, etc.), which are not friendly to humans and the environment, to polymerize natural cashew oil and reactive plant oils to use environmentally friendly and human-friendly natural raw materials. A composition for natural synthetic lacquer and a process for producing the same.

Conventional techniques known in the art have been studied on lacquer production, harvesting, and purification of lacquer, and are responsible for separating the components of the lacquer or molecular genetic studies on the polymerase laccase, and focusing on traditional functional holders. As a result, functional techniques of refining technology and painting technology have been developed.

In addition, Kash synthetic lacquer, which is a condensation reaction of formaldehyde derivatives (Hexamine, Paraformaldehyde, formaline…) and other organic compounds with Cashew oil produced in India, Africa, America, etc., is a disadvantage of high price of natural lacquer. Overcoming workability and dryness, we have pioneered an area that can be used universally in the fields of woodworking furniture and woodworking.

However, in the conventional technology, it can be said that the development of environment-friendly and human-friendly technology is still at the original level.

The main components of traditional lacquer are different depending on the place of origin (China, Japan, Vietnam, Korea), but they are composed of urushiol (C12H22O2), lacchol (C23H36O2) and rubber (polysaccharides, enzymes). Toxic at the time of skin contact is very strong, causing skin allergy phenomenon, workability (humidity control when drying) is difficult, and the price has a disadvantage (high price).

In particular, Kash synthetic lacquer has overcome many of the disadvantages of traditional lacquer, but because of obtaining high molecular weight synthetic resin by using hexamine or formaldehyde derivatives, it causes environmental problems in Kash synthetic lacquer manufacturing process and remains in the coating film after coating and drying. Unreacted free formaldehyde has the disadvantage of being unfriendly to the environment and human body.

That is, Table 1 shows the points that have not been solved in the related art and the contents to be solved through the present invention.

Difference between conventional technology and invention Traditional lacquer Kash Synthetic Paint Natural synthetic paint (invention) Remarks Environmentally friendly ○ X ○ Human-friendly X X ○ Free formaldehyde ○ X ○ Painting workability X ○ ○ Economics X ○ ○ After drying ◎ ◎ ◎

 (Legend-◎: Very good, ○: Good, X: Poor)

It inherits the advantages of traditional lacquer and Kashu synthetic lacquer, which is the conventional technology, and manufactures natural synthetic resin using natural materials that are environmentally friendly and human-friendly. In particular, formaldehyde derivatives in the composition can be used without the use of formaldehyde derivatives. The purpose of the present invention is to approach the physical properties.

In order to achieve this object, in the present invention, as a composition, by reacting the cashew oil, reactive plant (kerosene, linseed oil), rosin or rosin derivative containing purified cardanol with a purity of 90 to 95% at a temperature of 180 to 230 ℃ After securing a constant viscosity (15.0 to 25.0 poise at 125 ° C) and cooling, the above-mentioned conventional problems could be solved by obtaining a high molecular weight synthetic resin by diluting the reaction resin with natural oils (orange oil and terebin oil). .

96 wt% of the high molecular weight synthetic resin prepared as above, cobalt-octonate (purity 5%) 1.0 wt%, manganese-naphthenate (purity 5%) 1.5 wt%, zirconium-octonate (purity 12%) 1.0wt %, Methyl ethyl ketoxim (purity 98% or more) 0.5wt% by mixing the natural synthetic lacquer of the present invention is characterized by its characteristics.

The present invention is a purified raw material of cardanol (Canol: C6H4 (OH) C15H27) component of the natural vegetable oil CNSL (Cashew Nut Shell Liquid) extracted from the fruit skin of the cashew (Cashew) belonging to the family use.

In the raw material called Cardanol, `` 3-Pentadecenyl-8 ', 11', 14'Phenol (less than 30%), `` 3-Pentadecenyl-8 ', 11' Phenol (less than 20%) '' , 5-Pentadecenyl Phenol (less than 4%) is present.

Cardanol is the most similar to Urushiol of traditional lacquer, and its chemical structure is similar and is essential material in terms of physical properties (heat resistance, chemical properties, mechanical properties, gloss) after drying (curing).

Cashew oil is a mixture of several components such as cardanol, anacardic acid cardol, anacardol, and the like. In the present invention, purified cardanol having a purity of 90 to 95% is used. Reactive vegetable oils that may be used with sesame oil, corn oil, cottonseed oil, castor oil, rock oil, kerosene oil, soybean oil, linseed oil, perilla oil, rapeseed oil, rice bran oil, Olive oil, etc. These vegetable oils contain radical acids (oleic acid, linoleic acid, linolenic acid, ricinolic acid, eleostearic acid) that can react with unsaturated bonds in the alkyl group of Cardanol. Copolymerization can make high molecular weight synthetic resin.

In particular, the cashew oil, which has not been purified to less than 90% cardanol purity, is not constant in reactivity, and it is difficult to obtain a desired level of viscosity. The desired level of Viscosity is ICI Cone & Plate viscometer at 15.0 Poise at 25.0 Poise at 125 ℃, and resin with viscosity less than 5.0 Poise at 125 ℃ at viscometer temperature is late in drying of paint properties, soft film hardness and chemical resistance The properties were also insufficient compared to conventional Kash synthetic lacquer and natural lacquer. The resin having a high viscosity of 30.0 Poise or higher at a viscometer temperature of 125 ° C. had a poor solubility in natural diluents and had very poor fluidity and workability.

In the present invention, in the case of cashew oil, those containing cardanol purified at a purity of 90 to 95% are used, and among the reactive vegetable oils used together, copper oil or linseed oil is selected from eleostearic acid (CH 3 (CH 2) 3 ( It contains CH = CH) 2 (CH2) 7COOH) and oleic acid (CH3 (CH2) 7CH = CH (CH2) 7COOH), so that not only polymerization reactivity to increase the molecular weight but also the length of the carbon chain of the molecule is longer (C15 or more). It is a key raw material that can secure the flexibility of the coating film and brighten the color of the synthetic resin.

In particular, sufficient unsaturated bonds contained in eleostearic acid and oleic acid contribute partly to secure high molecular weight during radical copolymerization reaction, but they are made of paint and then subjected to oxidation reaction with oxygen in the air during drying after coating It is also a key raw material of the present invention because it also contributes to obtaining.

By using a certain amount of rosin or rosin derivative (rosin ester resin) among the raw materials utilized in the present invention, the physical properties of the paint could be improved.

Rosin (Pale yellow or dark brown transparent natural resin obtained by steam distillation of small pieces of live pine or pine, also called colophonium) is added to cardanol and reactive plant oil in cashew oil containing 90-95% purified cardanol. The resin obtained by the reaction is a resin acid mixture having a molecular formula (C20H30O2) such as abienic acid, α, B-pymaric acid, which increases the hardness of the dried coating film after coating and shortens the drying time.

Resin (Polymer) synthesized by a constant reaction temperature and reaction catalyst has high viscosity (Viscosity). Synthetic coating (paint) has to be diluted with diluent after the reaction type of high viscosity synthetic resin. Painting, brush painting, roller coating, etc.).

Diluents include organic solvents such as petroleum, mineral spirits, methanol, ethanol, butanol, xylene, toluene, butylacete, methylacetate, butylcellosolve, ethylcellosolve and methylcellosolve. Although it can be used in the present invention, it is prepared using environmentally friendly and human-friendly natural plant oils, orange oil and terebin oil. Dilution ratios are optionally applied in the range of 30% to 50% wt.

The raw materials used to make the paints are less than 5% of metal salts called desiccants. Toxic lead (pb) was not used in the present invention and the paint was prepared using less than 5% paint additives (defoamers, anti-filming agents, leveling agents).

Desiccants and paint additives are those used for the production of Kash synthetic paints.

As mentioned above, the composition of the natural synthetic lacquer was mentioned, and the following describes the manufacturing method.

Into a five-necked synthetic flask, "cardanol", reactive vegetable oil (flax oil), rosin, and a reaction catalyst are added, and the temperature is raised while stirring slowly under a stream of nitrogen (N2) gas.

The viscosity is measured to confirm the degree of the reaction while maintaining the temperature by raising the temperature from room temperature to the main reaction temperature (180 ℃ to 230 ℃ range) within 2 hours.

Viscosity measurement is carried out using ICI Cone & Plate Viscometer (RESEARCH EQUIPMENT LTD., UK) and setting the viscometer measurement temperature to 125 ℃ and measuring the viscosity at 30 minute intervals.

If the viscosity is in the range of 15.0 Poise ~ 25.0Poise while cooling the temperature to remove the unreacted material for 30 minutes in a vacuum (Vaccum, 500mmHg) and a diluent is added below 120 ℃ to prepare a high molecular weight synthetic resin having fluidity at room temperature.

Kash synthetic lacquer manufacturing method according to the prior art is a formaldehyde derivative is used to induce the methylation, methylolation reaction of the cashew oil and phenol (phenol) to obtain a polymer resin and then using an organic solvent as a diluent in the environment Without using any formaldehyde derivatives and phenols, which are not friendly, induce radical reactions to unsaturated bonds contained in oils to obtain polymer resins and dilute them with environmentally friendly vegetable oils, orange and terebin oils. It is characterized by producing a synthetic resin having a molecular weight.

Suitable composition ratios of the composition used in the present invention are as follows.

① Refined cashew oil containing purified cardanol with purity of 90-95% and reactive plant oil (Linseed oil, Tung oil) is used in an appropriate amount mixture, where the above-mentioned cashew oil is 100Wt% ~ 70Wt%, reactive plant Use oil from 0% to 30Wt%.

   When more than 30% of reactive plant oil is used, the cured coating performance is lower than that of natural lacquer and synthetic cashew, and the gloss, coating hardness, heat resistance, and chemical properties are lower, and less than 30% is used because it may cause gelation during the synthesis reaction. It is suitable to do.

② When used in combination with appropriate amount of natural rosin, the properties of drying and coating hardness can be improved, so it can be used less than 30% Wt with respect to the amount of cashew oil containing purified cardanol with purity of 90-95%.

At this time, when more than 30Wt% is used, it is appropriate to use less than 20Wt% because the smoothness is insufficient in the coating film properties and the dry film is easily broken.

③ Initially mix the Kash oil, reactive plant oil and rosin containing purified cardanol with a purity of 90-95% and radical reaction at 180 ℃ ~ 230 ℃.

If the reaction temperature is less than 180 ℃ reaction rate is too slow, and 230 ℃ or more reaction rate is too fast, it is difficult to control the temperature range of 180 ℃ ~ 230 ℃ is suitable.

In order to maintain the properties of the paint, the viscosity at the end of the reaction is a standard viscometer (ICI Cone & Plate, set temperature 125 ℃) is suitable from 15.0 Poise to 25.0 Poise.

Resin having a viscosity of less than 10.0 Poise has a low drying, coating hardness, and chemical resistance of paints in comparison with conventional Kash synthetic lacquer and natural lacquer.

In addition, the resin having a high viscosity of 30.0 Poise or more was poorly soluble in natural diluents and had very poor fluidity and workability.

(4) The diluents used in the present invention are natural orange oil and terebin oil. It is one of the features of the present invention to use environmentally friendly and human-friendly oils that are not toxic compared to conventional synthetic cashews.

Dilution after completion of the polymer reaction is suitable to ensure the workability when dilution at 30 ~ 50% Wt ratio with respect to the reaction resin, in particular, the non-volatile content of the diluted resin is in the range of 50% to 70%.

Example  One

55Wt% of cashew oil containing 15-95% purified cardanol and 15Wt% of crude oil were mixed with a stirrer, a condenser, and a vacuum reactor equipped with a vacuum device while stirring under a stream of nitrogen (N2) gas. Slowly raise the temperature.

When the temperature inside the reactor reaches the main reaction temperature of 180 ° C, the reaction is maintained at this temperature.

During the maintenance reaction, take a sample of the reaction resin at 30-minute intervals and measure the viscosity using a standard viscometer (E.ICI Cone & Plate Viscometer, set temperature: 125 ℃), and if the measured viscosity is 15.0 ~ 25.0 poise, vacuum level 500 After cooling for 30 minutes by mmHg pressure.

20Wt% of terebin oil and 10Wt% of orange oil were added to the reactor at an internal temperature of 150 ° C. or lower to obtain a high molecular weight synthetic resin.

Example  2

Nitrogen (N2) by mixing 55Wt% of cashew oil, 5Wt% of kerosene oil and 5Wt% of linseed oil, with a stirrer, condenser and a vacuum reactor (heating and cooling) with purified cardanol with a purity of 90-95% The temperature is gradually increased while stirring under a gas stream.

When the temperature inside the reactor reaches the main reaction temperature of 200 ° C, the reaction is maintained at this temperature.

Viscosity is measured using a standard viscometer (E. ICI Cone & Plate Viscometer, set temperature: 125 ℃) at 30 minutes intervals during the maintenance reaction. When the measured viscosity is 15.0 ～ 25.0 Poise level, After cooling for 30 minutes at 500 mmHg pressure.

30Wt% of turpentine oil and 5Wt% of orange oil were added to the reactor at an internal temperature of 150 ° C. or lower to obtain a high molecular weight synthetic resin.

Example  3

Nitrogen was mixed with 55Wt% of cashew oil containing 5 to 95% of purified cardanol, 5Wt% of castor oil, and 10Wt% of rosin (2w) in a synthetic reactor equipped with a stirrer, a condenser, and a vacuum device (heating and cooling). (N2) The temperature is gradually increased while stirring under a gas stream.

When the temperature inside the reactor reaches the main reaction temperature of 220 ° C, the reaction is maintained at this temperature. Reaction samples are taken at 30-minute intervals during the maintenance reaction. Viscosity is measured using a standard viscometer (E.ICI Cone & Plate Viscometer, set temperature: 125 ℃), and if the measured viscosity is 15.0∼25.0 Poise level, the degree of vacuum is 500. After cooling for 30 minutes by mmHg pressure.

25Wt% of turpentine oil and 5Wt% of orange oil were added to the reactor at an internal temperature of 150 ° C. or lower to obtain a high molecular weight synthetic resin.

Example  4

Stir under a stream of nitrogen (N2) gas by mixing 65Wt% of cashew oil and 0.5Wt% sulfuric acid containing 90-95% purified cardanol with a stirrer, condenser and vacuum reactor. While slowly raising the temperature.

When the temperature inside the reactor reaches the main reaction temperature of 230 ° C., the reaction is maintained at this temperature. In the maintenance reaction, take a sample of the reaction resin at 30-minute intervals and measure the viscosity by using a standard viscometer (E.ICI Cone & Plate Viscometer, set temperature: 125 ℃), and if the measured viscosity is 15.0∼25.0 Poise, After cooling for 30 minutes by mmHg pressure.

30Wt% of turpentine oil and 4.5Wt% of orange oil are added to the reactor at a temperature of 150 ° C. or lower to obtain a high molecular weight synthetic resin.

Comparative example  One

65Wt% of cashew oil (CNSL), 5Wt% of hexamine, and 5Wt% of phenol were added to a stirrer, condenser, and a synthetic reactor equipped with a vacuum device (heating and cooling), and the temperature was gradually increased while stirring under a stream of nitrogen (N2) gas.

When the internal temperature of the reactor reaches the main reaction temperature of 130 to 140 ℃, the reaction is maintained at this temperature.

Samples of the reaction resin are collected at 30-minute intervals during the maintenance reaction. Viscosity is measured using a standard viscometer (English ICI Cone & Plate Viscometer, set temperature: 125 ℃). After cooling for 30 minutes by mmHg pressure. 25Wt% of mineral spirits are added at a temperature of 120 ° C. or lower to obtain a high molecular weight synthetic resin.

Comparative example  2

55Wt% of cashew oil (CNSL), 10Wt% of linseed oil, and 5Wt% of hexamine are added to a stirrer, condenser, and a synthetic reactor equipped with a vacuum device (heating and cooling), and the temperature is gradually increased while stirring under a stream of nitrogen (N2) gas.

When the internal temperature of the reactor reaches the main reaction temperature of 130 to 140 ℃, the reaction is maintained at this temperature.

Reaction samples are taken at 30-minute intervals during the maintenance reaction. Viscosity is measured by a standard viscometer (E.ICI Cone & Plate Viscometer, set temperature: 125 ℃), and if the measured viscosity is 10.0 ~ 15.0 Poise level, the degree of vacuum is 500. After cooling for 30 minutes by mmHg pressure. 25Wt% of mineral spirit is added at a temperature of 120 ° C. or lower to obtain a high molecular weight synthetic resin.

After the coating (coating) was prepared using a high molecular weight synthetic resin prepared as described above, the physical properties of the coating (coating) were compared to Table 2.

At this time, the mixing ratio of the desiccant (metal salt) and additive used in the manufacture of the paint (chil) was high molecular weight synthetic resin 96Wt%, cobalt-octonate (purity 5%) 1.0Wt%, manganese-naphthenate (purity 5%) 1.5Wt% , Zirconium-octonate (purity 12%) 1.0Wt%, methyl ethyl ketoxim (purity 98% or more) 0.5Wt% of the mixture was further prepared to prepare a coating (paint) of the present invention.

The prepared paint (coating) was spray coated on a 0.5 mm thick tin plate and dried to coat at a final coating thickness of 75 μm, followed by drying at room temperature for 24 hours. The physical properties of the coating film are shown in Table 2 below.

(Paint Property Comparison Table) Example 1 Example 2 Example 3 Example 4 Synthetic Cashew Traditional clothes Comparative Example 1 Comparative Example 2 Drying (curing) property ○ ○ ◎ ○ ◎ ◎ △ Glossy (60 ℃) ◎ ○ ○ ◎ ◎ ○ ◎ Formaldehyde odor ◎ ◎ ◎ ◎ X X ◎ Dry Film Hardness ○ ○ ◎ ○ ◎ ○ ○ Color after drying ◎ ○ ◎ ○ △ ○ △ Water resistance ○ ◎ ◎ ◎ ◎ ◎ ◎ Acid resistance ○ ◎ ◎ ◎ ◎ ◎ ◎ Alkali resistance ○ ○ ○ ◎ ◎ ○ ○ Impact resistance ◎ ◎ ○ ◎ ○ ○ ◎ Image sharpness ○ ◎ ◎ ◎ ◎ ○ ◎ Organic solvents (voc) ◎ ◎ ◎ ◎ △ △ ◎ Painting workability ○ ○ ○ ○ ◎ ◎ X Weather resistance ○ ○ ○ ○ ○ ○ ○ Interlayer adhesion ◎ ◎ ○ ◎ ○ ○ ◎ Price (Economy ○ ○ ○ ○ ◎ ◎ X

(Legend-◎: Very good, ○: Good, △: Not enough, X: Not good)

As described above, the present invention does not contain any free formaldehyde (HCHO) component, which provides the cause of the controversial sick house syndrome, thus providing an environmentally friendly and human-friendly natural synthetic coating, and Even in terms of painting workability, it is not necessary to control the traditional humidity of traditional lacquer, and especially when painting traditional lacquer, there is no toxicity that affects the worker's skin, so it can be done safely and the hardened film is clear and bright after drying. The basic color is bright and it is possible to change the color of various kinds by adding dyes or pigments to it, and the unscented odor from the existing synthetic coating products is manufactured through the present invention. Is not found in natural synthetic lacquer. (Levin oil, orange oil) contains a fragrant smell, and also through the present invention, the biggest problem of traditional lacquer, the price is too high and the problem of painting workability, human skin allergy, etc. It is effective in solving problems such as environmental hazards and harmful effects on the human body by containing free formaldehyde (HCHO).

As described above, the present invention provides an environmentally friendly and human-friendly natural synthetic coating, but does not require humidity control during painting, and does not have any toxic effects on the skin of the worker so that the work can be safely performed and dried. The post hardened film has a clear and bright color, especially in wood grain. As the basic color is bright, it is obvious that it is a very useful invention that solves the problems to the environment and the human body, such as the addition of dyes or pigments to the advantage of changing various kinds of colors.

Claims (4)

In providing natural synthetic fills, 30 to 70 wt% of cashew oil containing purified cardanol with a purity of 90 to 95% and reactive vegetable oils such as linseed oil and tung oil or 0 to 30 wt% of natural rosin derivatives are added to a polymer resin obtained from the polymer resin 30 A natural synthetic lacquer composition, comprising:-40 wt% of natural terebin oil mixed with a paint additive. delete delete In the method for producing a natural synthetic coating composition, 100 to 70 wt% of cashew oil containing 90 to 95% purified cardanol and 0 to 30 wt% of reactive vegetable oils such as linseed oil or copper oil or 0 to 30 wt% of natural rosin derivatives are added to the reactor under a stream of nitrogen (N2) gas. The mixture was stirred and heated to a temperature of 180 ° C. to 230 ° C., and then polymerized under ionicity to obtain a high molecular weight synthetic resin having a viscosity (ICI Cone & Plate Viscometer, at 125 ° C.) of 15.0 to 25.0 Poise. 30-40 wt% of natural terebin oil was mixed with the above high molecular weight synthetic resin, and then a mixture of cobalt-octonate, manganese-naphthenate, zirconium-octonate and methylethyl ketoxim was added as a paint additive. Method for producing a natural synthetic lacquer, characterized in that the mixing.