KR100576137B1 - Enamel Alkyd Resin Composition For Construction and Method of Preparing The Same - Google Patents

Abstract

Disclosed are alkyd resin compositions for enamels used as architectural paints and methods for their preparation. The composition comprises fatty acids having an iodine in the range of 100-135, fatty acids having an iodine of at least 140, phthalic anhydride of 50-100% by weight of the total polyacid equivalent, and maleic anhydride of 0-30% by weight of the total polyacid equivalent. It is obtained by condensation of polyhydric alcohol which is a polyacid and a glycol compound, and has a weight average molecular weight in the range of 5,000 to 15,000. The naturally-dried enamel resin is condensed by iodine in a two-step reaction method using a small amount of 140 or more fatty acids, and its weight average molecular weight is 5,000 to 15,000. By increasing the molecular weight than the conventional enamel resin, the solidification drying and brush workability is improved, and in terms of workability, the viscosity rise time is shortened at the end of the reaction.

Description

Alkyd resin composition for architectural enamels and method for preparing the same {Enamel Alkyd Resin Composition For Construction and Method of Preparing The Same}

The present invention relates to an alkyd resin composition for building enamel excellent in dryness and brush workability and a manufacturing method by a two-step reaction thereof.

Generally used enamel resins can be classified into dry oil (iodine of 140 or more), semi-dry oil (iodine of 100-140), undried oil (of iodine of 100 or less), etc., depending on the type of fatty acid. Oily (more than 55% oil), heavy oil (45-55% oil), mono-oil (less than 45% oil) can be classified.

Most of the enamel paint for construction is a natural drying type, the iodine uses a dry oil of 100 or more, and the whey is a heavy oil resin composition is used a lot. Among them, paints using heavy oil-based alkyd resins using soybean fatty acid are most frequently used.

The following physical properties are calculated | required by the resin composition of architectural enamel coating. First, drying after painting should be fast. Preferred conditions are within 30 minutes of dry contact and within 6 hours of solidification. Second, gloss and brush work should be excellent. In addition, productivity and cost-effective workability can also be easily mass-produced.

The heavy oil-based alkyd resin using soybean fatty acid is mainly used for the enamel resin composition used so far. Enamel paint prepared from heavy oil-based alkyd resin using soybean fatty acid is excellent in the touch drying after coating and excellent in coating gloss and pigment miscibility, but has a problem of slow solidification drying (inner coating drying) and poor spreadability during brush painting. In large-scale construction works, not only surface drying but also internal drying are looking for fast-drying paints with excellent brush workability. Therefore, there is a demand for building enamel paints that accelerate the solidification of existing enamel resins and have excellent brush workability.

An object of the present invention is to provide a resin composition which can improve the slow solidification drying and weak brush workability, which is a problem of the existing building enamel resin composition.

Another object of the present invention is to provide a method for easily producing the above-described resin composition for architectural enamels by a two-step reaction.

In order to achieve the above object of the present invention, in the present invention, at least one iodine selected from the group consisting of soybean oil fatty acid, linseed oil fatty acid and rice bran fatty acid fatty acid, dehydrated castor oil fatty acid and paulownia oil artificial tablets in the range of 100 ~ 135 A polyacid comprising at least one iodine selected from the group consisting of fatty acids of at least 140, 50-100% by weight of phthalic anhydride, and 0-30% by weight of maleic anhydride, of the total polyacid equivalent And at least one glycol compound selected from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethol propane, 1,3-butylene glycol, methylpropanediol, neopentylglycol and pentaerythritol Phosphorus ene, obtained by condensation of polyhydric alcohols, with a weight average molecular weight in the range of 5,000 to 15,000 It provides for the alkyd resin composition.
In particular, it is preferable that the mixing ratio of the fatty acid having the iodine in the range of 100 to 135 and the fatty acid having the iodine at least 140 is in the range of 60 to 99: 1 to 40 in terms of equivalent ratio, preferably the fatty acid having the iodine in the range of 100 to 135 and the It is preferable that the mixing ratio of the fatty acid whose iodine is 140 or more is 80-99: 1-20 in equivalence ratio.
The fatty acid having an iodine of 140 or more is preferably artificially purified having a conjugated linoleic acid content of 50 to 60%, a saponification value of 200 to 220, a degree of neutralization of 195 to 200, and a hydroxy equivalent of 40 to 80.
It is also preferred that the total equivalents of the fatty acids and polyhydric acids and the equivalents of the polyhydric alcohols range from 1.0: 1.0 to 1.1.

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Another object of the present invention described above

Firstly reacting 50 to 80% of the total amount of fatty acids, polyacid and polyhydric alcohol; And

It is achieved by a method for producing an alkyd resin composition for architectural enamel comprising the step of adding the remaining amount of 20 to 50% of the fatty acid in a temperature range of 100 ℃ or less and secondary reaction.

In particular, the fatty acid having an iodine of 140 or more is preferably added during the secondary reaction.

And the equivalent of the fatty acid and polyhydric acid and the polyhydric alcohol in the first reaction is preferably in the range of 1.0: 1.1 to 1.2, the equivalent of the total fatty acid and polyacid and the polyhydric alcohol of the second reaction It is preferable that the equivalent is in the range of 1.0: 1.0 to 1.1.

Hereinafter, the present invention will be described in detail.

The enamel resin used in the present invention was prepared according to a conventional method using semi-drying oil fatty acid, dry oil fatty acid and polybasic acid or acid anhydride, polyhydric alcohol and the like.

At this time, the fatty acids that can be used in the production of the enamel resin may be selected from fatty acids such as soybean oil, dehydrated castor oil, rice bran fatty oil, linseed oil, copper oil, etc., and as a polybasic acid, saturated base acid, phthalic anhydride, isophthalic acid, terephthalic acid, adidi. It is selected from pixic acid and the like, and unsaturated dibasic acid may be selected from maleic anhydride, fumaric acid and the like. As polyhydric alcohols, those selected from diethylene glycol, dipropylene glycol, propylene glycol, ethylene glycol, 1.3 butylene glycol, methyl propanediol, neopentyl glycol, glycerin, trimethol propane, monopentaerythritol, dipentaerythritol, etc. Can be used.

When iodine uses a large amount of fatty acids of 140 or more, natural drying can be accelerated after paint production.However, in the synthesis of resins, fatty acids containing unsaturated covalent bonds self-polymerize at high temperatures and rapidly adhere to a gel. There is a risk of this. That is, it is preferable to use the fatty acid amount of 140 or more fatty acids within 20-40% of the total fatty acid content, that is, when the amount of fatty acids having an iodine of 140 or more is inserted more than 40%, an excessive reaction with polyhydric alcohol This is because there is a risk of gel due to excessive viscosity due to self polymerization (Heat Polymerization or Oil Bodying).

In addition, when iodine uses less than 100 fatty acids, the time of oxidizing in air and drying naturally is delayed. Therefore, in the present invention, iodine limits the amount of fatty acids of 140 or more, and iodine limits the use of fatty acids of 100 or less.

Accordingly, the mixing ratio of the fatty acid having an iodine in the range of 100 to 135 and the fatty acid having the iodine at 140 or more is 60 to 99: 1 to 40 in an equivalent ratio, and more preferably the fatty acid having the iodine in the range of 100 to 135 and the iodine The mixing ratio of fatty acids having 140 or more is in the range of 80 to 99: 1 to 20 in equivalent ratio.

Therefore, in the present invention, the fatty acid with iodine 140 or more is used within 20 to 40% of the total fatty acid content to prevent the risk of gel during high temperature reaction and to accelerate the rate of oxidation and drying in the air.

In addition, in the alkyd resin composition for architectural enamel paint of the present invention, as described above, the mixing ratio of the polyhydric alcohol compound and the fatty acid and the polyacid compound is preferably 1.0 to 1.1: 1.0 as an equivalent ratio, that is, to the polyhydric alcohol, It is meant that it is desirable to mix the polyhydric alcohols in an equivalent ratio of fatty acids and polyacids in an increased proportion within the range of about 0-10%.

In the alkyd resin composition for architectural enamel of the present invention, as described above, the equivalence ratio of the polyhydric alcohol, the fatty acid and the polyacid compound was designed so that the equivalence ratio was 1.0 to 1.1: 1.0. If the mixing ratio of polyhydric alcohol, fatty acid and polyacid is less than 1: 1 as the equivalent ratio, that is, if the polyhydric alcohol content is less than the polyhydric acid content, the adhesion with the material (mainly iron) will not be satisfactory. .

Hereinafter, the manufacturing method of the alkyd resin composition according to the present invention will be described in more detail.

In the present invention, there is a big feature in that the fatty acid is divided into two stages and reacted. The problem of the existing enamel resin is that the iodine uses less than 140 fatty acids by the one-step reaction method, so that the conjugated double bond is insufficient, and the rate of forming a dried coating film by combining with oxygen in the air is low. It is assumed that the poor workability is caused by insufficient molecular weight in synthesizing the resin and not compatible with aliphatic solvents.

Therefore, the present invention is to provide an enamel resin composition and a method of working with iodine which is excellent in brush workability by increasing the molecular weight of the resin by a two-stage reaction method using a small amount of fatty acids of 140 or more to improve the drying speed.

If the fatty acid with iodine of 140 or more is initially inserted in the two-step method, the viscosity may be too high due to the rapid reaction with the polyhydric alcohol, which may cause problems in the process. Therefore, the iodine is cooled at the point where the fatty acid of 125 to 135 is initially inserted to obtain a theoretical solid dispersion of 30 or less and the theoretically generated water. After cooling, iodine has a fatty acid of 140 or more at less than 20 ~ 40% of the total fatty acid content. After the fatty acid is added, the solution is gradually heated to the highest temperature, undergoes a dehydration condensation reaction for 4 to 6 hours, and cooled to obtain a resin product when the required viscosity and acid value are obtained. It is possible to prepare a resin composition for producing an enamel paint for building to promote the solidification drying and excellent brush workability.

According to the two-step reaction method of the present invention, the experiment is carried out in a two-step reaction, not a method of blending the whole amount at the initial reaction. Specifically, 70 to 80% of the amount of fatty acids was added to the initial blending, so that the equivalent ratio of the polyhydric alcohol, the fatty acid and the polyacid compound was 1.1 to 1.2: 1.0. This was to increase the molecular weight as possible by minimizing the loss of some polyhydric alcohol raw materials with low boiling point by rapidly producing the main chain ester by smoothly reacting the polyhydric alcohol and the polyacid.

In the one-step reaction, it is preferable to proceed the maximum reaction temperature within 200 ℃ or less, within 2 hours of the reaction time. The reaction temperature is set at 200 ° C. or less to prevent the loss of some polyhydric alcohol raw materials having a low boiling point and to control the progress of the rapid dehydration reaction. Theoretically, the end point of the one-step reaction should be determined by the amount of polyacid produced by the reaction of some polyalcohol equivalents having a low boiling point.

When the reaction proceeds above the theoretical production amount in the one-step reaction (more than 110%), the polyhydric alcohol to participate in the reaction in the two-stage reaction is over or under, and the equivalence ratio of the polyhydric alcohol and the polyacid is less than 1: 1 and reaches the end of the high temperature reaction. Be careful because there is a risk of gel.

In the two-stage reaction, 20 to 30% of the remaining fatty acid content is added at 100 ° C. or lower, and the temperature is gradually raised to the highest temperature of 220 ° C. to carry out the condensation reaction for 3 to 5 hours.

In general, the method of advancing the reaction by mixing the initial total amount is convenient in the synthesis of resin for enamel due to convenient workability and easy reaction control. However, in terms of increasing the molecular weight of the resin is not greatly improved, the solidification drying (internal drying) is not pulled. Therefore, in the present invention, by performing a two-step reaction using fatty acids having an iodine of 140 or more within 20 to 40% of the total amount of fatty acids, the molecular weight of the resin can be increased, and the solidification of the paint can be accelerated and the brush workability can be improved.

Hereinafter, the present invention will be described in detail through specific examples. However, it is a matter of course that the present invention is not limited only to the following examples.

<Example 1>

A 2 L four-necked flask was equipped with a thermometer, a condenser, a stirrer, and a condenser for removing water, and a temperature raising device was attached. 200 g of iodine 125-135 soybean fatty acid, 190 g of phthalic anhydride, 50 g of ethylene glycol, and 100 g of pentaerythritol were added thereto, and the temperature was raised to 180 ° C while gradually stirring. After condensation reaction was performed for about 2 hours to obtain theoretical water, the fruit was blocked and cooled. At 100 degrees C or less, 52 g of soybean fatty acids with 125-135 iodine and 8 g of fatty acids with iodine 140 were added, and it heated up at 220 degreeC, stirring gradually. The condensation reaction was carried out for about 5 hours to obtain an alkyd resin composition for building enamel according to this embodiment having a viscosity of Z6 and a molecular weight of 8,600 as a condensation reaction product.

<Example 2>

A 2 L four-necked flask was equipped with a thermometer, a condenser, a stirrer, and a condenser for removing water, and a temperature raising device was attached. 200 g of iodine 125-135 soybean fatty acid, 190 g of phthalic anhydride, 50 g of ethylene glycol, and 100 g of pentaerythritol were added thereto, and the temperature was raised to 180 ° C while gradually stirring. After condensation reaction was performed for about 2 hours to obtain theoretical water, the fruit was blocked and cooled. At 100 degrees C or less, 52g of soybean fatty acids with 125-135 iodine and 14g of fatty acids with iodine 140 were added, and it heated up at 220 degreeC, stirring gradually. The condensation reaction was carried out for about 5 hours to obtain an alkyd resin composition for building enamel according to this embodiment having a viscosity of Z 6+ and a molecular weight of 10,500 as a condensation reaction product.

<Example 3>

A 2 L four-necked flask was equipped with a thermometer, a condenser, a stirrer, and a condenser for removing water, and a temperature raising device was attached. 200 g of iodine 125-135 soybean fatty acid, 190 g of phthalic anhydride, 50 g of ethylene glycol, and 100 g of pentaerythritol were added thereto, and the temperature was raised to 180 ° C while gradually stirring. After condensation reaction was performed for about 2 hours to obtain theoretical water, the fruit was blocked and cooled. At 100 degrees C or less, 52g of soybean fatty acids with 125-135 iodine and 22g of fatty acids with iodine 140 were added, and it heated up at 220 degreeC, stirring gradually. The condensation reaction was carried out for about 5 hours to obtain an alkyd resin composition for building enamel according to this embodiment having a viscosity of Z 6+ and a molecular weight of 11,200 as a condensation reaction product.

<Example 4>

A 2 L four-necked flask was equipped with a thermometer, a condenser, a stirrer, and a condenser for removing water, and a temperature raising device was attached. 200 g of iodine 125-135 soybean fatty acid, 190 g of phthalic anhydride, 50 g of ethylene glycol, and 100 g of pentaerythritol were added thereto, and the temperature was raised to 180 ° C while gradually stirring. After condensation reaction was performed for about 2 hours to obtain theoretical water, the fruit was blocked and cooled. At 100 degrees C or less, 52g of soybean fatty acids with 125-135 iodine and 27g of fatty acids with iodine 140 were added, and it heated up at 220 degreeC, stirring gradually. The condensation reaction was carried out for about 5 hours to obtain an alkyd resin composition for building enamel according to this embodiment having a viscosity of Z7 and a molecular weight of 11,700 as a condensation reaction product.

Comparative Example 1

A 2 L four-necked flask was equipped with a thermometer, a condenser, a stirrer, and a condenser for removing water, and a temperature raising device was attached. 252 g of soybean fatty acid with iodine 125-135, 8 g of fatty acid with iodine 140, 190 g of phthalic anhydride, 50 g of ethylene glycol, and 100 g of pentaerythritol were added thereto, and the temperature was raised to 220 ° C while gradually stirring. The condensation reaction was carried out for about 7 hours to obtain an alkyd resin composition for architectural enamel having a viscosity of Z6 and a molecular weight of 7,500 as a condensation reaction product.

Comparative Example 2

A 2 L four-necked flask was equipped with a thermometer, a condenser, a stirrer, and a condenser for removing water, and a temperature raising device was attached. 260 g of soybean fatty acid having an iodine of 125 to 135 and an equivalent weight of 280 was added thereto, 190 g of phthalic anhydride, 50 g of ethylene glycol, and 100 g of pentaerythritol were heated to 220 ° C. with slow stirring. The condensation reaction was carried out for about 7 hours to obtain an alkyd resin composition for architectural enamel having a viscosity of Z 5 and a molecular weight of 6,800 as a condensation reaction product.

The alkyd resin coating composition for building enamel according to the present invention was prepared by using the alkyd resin composition for coating after the coating of the alkyd resin obtained in each of Examples and Comparative Examples, as shown in Table 1 below. Each was prepared. The composition ratio of the produced alkyd resin and each component is shown in Table 1.

Table 1 shows the content of each component used to prepare a conventional architectural enamel paint for comparison. As a solvent, a mixed liquid of mineral spirit and xylene was used.

 Raw material name Compounding amount Resin of Examples and Comparative Examples  60 Titanium oxide (TiO2)  15 Dispersant  0.25 Anti-cretter  0.1 Pinhole inhibitor  0.1 Flow inhibitor  0.1 Antifoam  0.3 Mixing dryer  2.75 Solvent  21.4  Sum  100

First, in order to find out the characteristics of each coating composition shown in Table 1, a quick-drying anti-corrosive primer paint on a test iron [dipai product; Metaron DNU-3000 reddish brown] was applied to a thickness of 30 to 40 micron and dried naturally, followed by airless spraying of a paint using an alkyd resin for enamel prepared above to a thickness of 40 to 60 micron. The coating film thickness here means the thickness of the dried coating film. After drying at room temperature, the test film was obtained and the film performance was investigated. The irradiated coating film characteristics are shown in Table 2. Each characteristic in Table 2 was measured by the following method.

1. Viscosity measured the viscosity of the paint with a Crebes-Stormer viscometer.

2. Set-to-Touch was tacky when the fingertips were lightly touched, but it was judged to be dry when the paint did not adhere to the fingertips.

3. Dry-Hard is to bite the test plate between thumb and cognitive, push the film to the thumb, press hard (do not twist), and lightly rub with a soft cloth. At this time, if there is no fingerprint mark on the coating film, it shall be solidified.

4. Glossiness of the coating film was measured by a BYK-Gardner Haze Gloss measuring instrument.

5. The concealment rate is 30 centimeters wide and the vertical surface is divided into 10 centimeters of black and white. Each paint was applied to the cover paper, and the degree of cover was visually determined.

6. The coating hardness shows the pencil hardness two days after the coating on the specimen. Use a pencil to show the hardness of the scratches or scratches on the coating.

7. Laura workability is indicated by checking whether the roll is pushed out or pushed by rubbing the steel plate several times so as to bury the manufactured paint on the roll. (A: Very good B: Normal, C: Under)

8. The appearance of the dry film was determined by comprehensively determining the observation results of the tee, leveling property, color separation, pinhole, cretaring, etc. of the surface of the completely dried film.

9. Color separation stability was shown by visually observing whether the color separation phenomenon is indicated by rubbing the prepared paint on the iron plate and rubbing the same paint again with a finger.

Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 KU viscosity 91 92 91 94 90 90 Drying time (touch) 31 minutes 27 minutes 22 minutes 20 minutes 39 minutes 36 minutes Drying time (solidification) 6 hours 20 minutes 6 hours 4 hours 45 minutes 4 hours 20 minutes 7 hours 9 hours Gloss (glass plate / 60。) 92 91.8 91.1 92.3 91.4 90.5 Concealment 0.9633 0.9650 0.9674 0.9613 0.9675 0.9616 Coating hardness (2 days) 4B 4B 4B 4B 4B 4B Laura workability C B B A C C Dry coating appearance Good Good Good Good Good Good Color separation stability Stable Stable Stable Stable Stable Stable

As shown in Table 2, using the alkyd resin composition for building enamel according to the two-step reaction method of the present invention to prepare a coating composition for building enamel has the following distinct advantages.

Paints made of resin synthesized by two-step reaction method gradually increasing fatty acids with more than 140 iodine were excellent in solidification drying and brush workability. In terms of resin workability, the viscosity rise time was shortened at the end of the reaction when sufficient molecular weight was formed. In addition, the presence of a large amount of conjugated double bonds at the fatty acid terminals increased the speed of forming a dried coating film by combining with oxygen in the air. In addition, the brushability is improved because the resin is manufactured in a direction in which the whey is increased and the molecular weight is increased, thereby ensuring compatibility with the aliphatic solvent.

Although the present invention has been described above according to an embodiment of the present invention, it will be apparent to those skilled in the art that various modifications may be made without departing from the spirit of the present invention.

Claims (13)

Fatty acid having at least one iodine selected from the group consisting of soybean oil fatty acid, linseed oil fatty acid and rice bran fatty acid at least one iodine selected from the group consisting of 100-135 fatty acids, dehydrated castor oil fatty acid and paulownia oil artificial fatty acid Polyacids and ethylene glycols, propylene glycols, diethylene glycols, dipropylene glycols comprising 50-100% by weight of total polyacid equivalents of phthalic anhydride and 0-30% by weight of maleic anhydride of total polyacid equivalents. Obtained by condensation of a polyhydric alcohol, which is at least one glycol compound selected from among glycerin, trimethol propane, 1,3-butylene glycol, methyl propanediol, neopentyl glycol and pentaerythritol, and has a weight average molecular weight of 5,000 to 15,000. Alkyd resin composition for building enamel which is a range. The alkyd resin composition for architectural enamels according to claim 1, wherein the mixing ratio of the fatty acid having the iodine in the range of 100 to 135 and the fatty acid having the iodine at the range of 140 or more is in the range of 60 to 99: 1 to 40 in equivalent ratio. The alkyd resin composition for building enamel according to claim 1, wherein the mixing ratio of the fatty acid having an iodine in the range of 100 to 135 and the fatty acid having the iodine at 140 or more is in the range of 80 to 99: 1 to 20 in equivalent ratio. The artificial tablet according to claim 1, wherein the fatty acid having an iodine of 140 or more has a conjugated linoleic acid content of 50 to 60%, a saponification value of 200 to 220, a degree of neutralization of 195 to 200, and a hydroxy equivalent of 40 to 80. Alkyd resin composition for architectural enamels, characterized in that The alkyd resin composition for architectural enamels according to claim 1, wherein the total equivalents of the fatty acids and the polyacids and the equivalents of the polyhydric alcohols are in the range of 1.0: 1.0 to 1.1. Firstly reacting 50 to 80% of the total amount of fatty acids, polyacid and polyhydric alcohol; And A method for producing an alkyd resin composition for building enamel, comprising the step of adding the remaining amount of fatty acid 20 to 50% in a temperature range of 100 ℃ or less and secondary reaction. The method for producing an alkyd resin composition for building enamel according to claim 6, wherein the fatty acid having an iodine of 140 or more is added during the secondary reaction. The method for producing an alkyd resin composition for building enamel according to claim 6, wherein the equivalent of the fatty acid and the polyhydric acid and the equivalent of the polyhydric alcohol in the first reaction range from 1.0: 1.1 to 1.2. 7. The method for producing an alkyd resin composition for building enamel according to claim 6, wherein the equivalent of total fatty acid and polyacid and the equivalent of polyhydric alcohol in the second reaction range from 1.0: 1.0 to 1.1. The method for producing an alkyd resin composition for architectural enamels according to claim 6, wherein the reaction temperature is controlled not to exceed 200 ° C. during the first reaction. delete delete delete