KR101405350B1 - Alkyd Resins Composition, Manufacturing Method of the same, and enamel paint including the same - Google Patents

Abstract

The present invention provides a process for producing a polyimide resin, comprising: a first polymerization step of polymerizing a first fatty acid having an iodine value in a range of 100 to 135, a second fatty acid having an iodine value in a range of 50 to 70, a polybasic acid, and a polyhydric alcohol at a first reaction temperature; And a second polymerization step of polymerizing the intermediate product after the first polymerization step at a second reaction temperature higher than the first reaction temperature.

Description

[0001] The present invention relates to a method for producing an alkyd resin, an alkyd resin prepared from the same, and an enamel paint containing the alkyd resin,

More particularly, the present invention relates to a method for producing an alkyd resin for enamel paints, an alkyd resin prepared therefrom, and an enamel paint containing the alkyd resin. will be.

Alkyd resins used in enamel paints used in general buildings can be classified into dry oil (iodine is 140 or more), semi-drying oil (iodine is 100 to 140), and non-drying oil (iodine is 100 or less) (Oil 55% or more), heavy oil (oil 45 ~ 55%) and short oil (less than 45% oil) according to whey.

Most of the enamel paints for architectural use are natural drying type, and iodine 100 or more drying oil is used, and whey is heavy oil type (oil 45 ~ 55%).

The following properties are required for the resin composition of the enamel coating for architectural use. First, after drying, it should be dry. Second, it should be excellent in gloss and ruler workability. The resins used for architectural enamel coatings are mainly composed of heavy oil alkyd resins using soybean fatty acid. Enamel paints made from heavy oil alkyd resin using soybean fatty acid have excellent coating film gloss and pigment miscibility after coating but have a problem of slow drying (drying in the inside of coating film) and poor spreadability in brush coating. Therefore, in a large-scale construction site, it is required not only to dry the surface but also to dry in the inside of the building. Since it is looking for a paint excellent in workability of a brush (roller) This excellent architectural enamel paint is required.

The present invention aims to provide a process for preparing an alkyd resin for an enamel paint which is capable of controlling the drying property and is improved in workability in roller working, and an alkyd resin produced therefrom.

A method for producing an alkyd resin according to one aspect of the present invention comprises

A first polymerization step of polymerizing a first fatty acid having an iodine value in a range of 100 to 135, a second fatty acid having a iodine value in a range of 50 to 70, a polybasic acid, and a polyhydric alcohol at a first reaction temperature; And

And a second polymerization step of polymerizing the intermediate product after the first polymerization step at a second reaction temperature higher than the first reaction temperature.

Preferably, the first fatty acid is 80 to 99 parts by weight, the second fatty acid is 1 to 20 parts by weight, the polybasic acid is 25 to 40 parts by weight, and the polyhydric alcohol is 20 to 30 parts by weight.

The polybasic acid is preferably contained in an amount of 25 to 35 parts by weight of a saturated base acid and 1 to 5 parts by weight of an unsaturated base acid.

At this time, it is preferable that the mixing ratio of the polyhydric alcohol and the sum of the fatty acid and the polybasic acid is in the range of 1.0 to 1.2: 1.0 as an equivalent ratio.

Also, the first reaction temperature may be 155 to 160 ° C, and the second reaction temperature may be 215 to 220 ° C.

The molecular weight of the alkyd resin is preferably in the range of 19,000 to 60,000. Another aspect of the present invention provides an alkyd resin having a molecular weight of 19,000 to 60,000, which is produced by the above-described method for producing an alkyd resin.

Another aspect of the present invention provides an enamel paint comprising the above-described alkyd resin.

In this case, the enamel paint is preferably contained in an amount of 30 to 70 parts by weight of the alkyd resin, 20 to 50 parts by weight of the pigment, and 1 to 20 parts by weight of the solvent.

The enamel coating preferably further comprises 0.1 to 1 part by weight of a dispersing agent, 0.1 to 1 part by weight of a drying agent, 0.1 to 1 part by weight of a defoaming agent and 0.1 to 1 part by weight of a leveling agent as an additive.

The method for producing an alkyd resin according to an aspect of the present invention is a method for producing an alkyd resin by increasing the molecular weight of a resin by performing a one step reaction in which a fatty acid having an iodine value of 50 to 70 is used within 0 to 20% It is possible to accelerate the drying of the solidification in the roller, and to improve the workability of the roller.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout the description and claims, unless the context requires otherwise, the word "comprise" is intended to include the stated article, step or group of articles, and steps; It is not meant to exclude an object, step or group of objects or a group of steps.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. In particular, any feature that is indicated to be advantageous or advantageous may be combined with any other feature or feature that is indicated to be advantageous or advantageous.

Method for producing alkyd resin

The alkyd resin used in the present invention is reacted with a fatty acid, a polybasic acid and a polyhydric alcohol to obtain an alkyd resin having a weight average molecular weight ranging from 19,000 to 60,000.

1. Fatty acid

The fatty acid includes a first fatty acid having an iodine value in the range of 100 to 135, and a second fatty acid having an iodine value in the range of 50 to 70. The mixing ratio of the first fatty acid and the second fatty acid is in the range of 80 to 99: 1 to 20 by weight.

Within the above-mentioned range, the fatty acid containing an unsaturated covalent bond at the time of resin synthesis does not self-polymerize at a high temperature, and viscosity is not abruptly adhered, resulting in uniform polymerization stability. However, if the second fatty acid is used in a larger amount than the above range, natural drying may be slowed down after the paint is prepared

Therefore, in the present invention, the use of the second fatty acid within the range of 20 to 40% of the total fatty acid amount prevents the risk of gelation during the high temperature reaction and controls the rate of drying by oxidizing in air.

The first fatty acid may be soybean oil fatty acid, dehydrated castor oil fatty acid, rice bran fatty acid, linseed oil fatty acid, and the second fatty acid may be mono fatty acid.

2. Polybasic acid

As the polybasic acid, at least one of phthalic anhydride, isophthalic acid, unsaturated maleic anhydride, fumaric acid, etc., which is a saturated base acid, may be used, and it is preferable to use both a saturated base acid and an unsaturated base acid

In this case, it is preferable that 25 to 35 parts by weight of a saturated base acid and 1 to 5 parts by weight of an unsaturated base acid are used.

3. Polyhydric alcohol

As polyhydric alcohols, diethylene glycol, dipropylene glycol, glycerin, trimethyolpropane, 1,3-butylene glycol, pentaerythritol, dipentaerythritol, monopentaerythritol and the like can be used.

At this time, it is preferable that the above-mentioned total equivalents of fatty acids and polybasic acids and equivalents of polyhydric alcohols are in the range of 1.0: 1.0 to 1.2.

In the alkyd resin composition for architectural enamel paints of the present invention, the mixing ratio of the polyhydric alcohol, the fatty acid and the polybasic acid is preferably 1.0 to 1.2: 1.0, It is preferable to mix such that the polyhydric alcohol in the equivalent ratio of the fatty acid and the polybasic acid is included in the range of about 0 to 20%.

If the mixing ratio of the polyhydric alcohol and the fatty acid and the polybasic acid is designed to be less than 1: 1, that is, when the polyhydric alcohol content is less than the content of the polybasic acid, there is no hydroxyl group adhering to the steel sheet, .

The fatty acids, polybasic acids or acid anhydrides, and polyhydric alcohols described above are synthesized as an echidic resin through the following reaction.

First, it is a first polymerization step in which a fatty acid, a polybasic acid and a polyhydric alcohol are reacted. At this time, the second fatty acid is used within 0 to 20% of the total amount of fatty acids.

The first fatty acid may be contained in an amount of 80 to 99 parts by weight, the second fatty acid may be contained in an amount of 1 to 20 parts by weight, and the polybasic acid may be included in an amount of 25 to 40 parts by weight. And 1 to 5 parts by weight of a base acid. The polyhydric alcohol is reacted by adding 20 to 30 parts by weight.

In the first polymerization step, it is preferable to proceed at a first reaction temperature of 150 ° C to 160 ° C and a reaction time of 1 hour. If the reaction temperature is lower than 150 ° C, there is a problem that initial dehydration does not occur. If the reaction temperature exceeds 160 ° C, a part of the polyalcohol raw material having a low boiling point is generated and a rapid dehydration reaction proceeds.

Next, the second polymerization step in which the temperature is gradually raised from 215 ° C to 220 ° C, which is the second reaction temperature, and the condensation reaction proceeds for 3 to 5 hours.

After the addition of the second fatty acid in the range of 50 to 70 iodine, the initial gelation (hardening) is prevented by the above two-step reaction, and the molecular weight can be increased to a desired level. The weight average molecular weight of the alkyd resin thus produced is in the range of 19,000 to 60,000, which is greatly increased than the conventional molecular weight. At this time, the molecular weight of the alkyd resin significantly increased with the reaction time.

Enamel paint composition

The enamel coating composition according to one aspect of the present invention is prepared using 30 to 70% of the alkyd resin, 20 to 50% of the pigment and 1 to 20% by weight of the solvent.

In the present invention, the kind of the pigment and the solvent are not limited, but 25 to 30 parts by weight of the white pigment R-706 may be used as the pigment, and 19 to 21 parts by weight of the mineral spirits may be used as the solvent. In this case, 0.1 to 1 part by weight of a dispersant, 0.1 to 1 part by weight of a desiccant, 0.1 to 1 part by weight of a defoaming agent and 0.1 to 1 part by weight of a leveling agent are preferably used.

The additive in the present invention may further be a common additive used in the production of an enamel paint. 0.1 to 1 part by weight of a dispersing agent, 0.1 to 1 part by weight of a drying agent, 0.1 to 1 part by weight of a defoaming agent and 0.1 to 1 part by weight of a leveling agent may be used as additives.

The additive in the present invention may further be a common additive used in the production of an enamel paint.

Example

Manufacture of alkyd resins

Example 1

A thermometer, a condenser, a stirrer, and a condenser for water removal were installed in a 2L four-necked flask, and a heating device was attached. 243 g of soybean fatty acid having 125 to 135 iodine, 27 g of 50 to 70 fatty acid of iodine, 162 g of phthalic anhydride as saturated base acid, 1 g of maleic anhydride as unsaturated base acid, 54 g of glycerin, 91 g of pentaerythritol, 26 g of xylene was added as a refluxing solvent, and the temperature was raised to 160 캜 with stirring. The condensation reaction was carried out for about 1 hour to prevent low boiling point alcohol and rapid dehydration. And the temperature was raised to 220 캜 while stirring. The condensation reaction was carried out for about 3 hours to obtain an alkyd resin having a viscosity of Z4 and a molecular weight of 19,000 as a condensation reaction product.

Example  2

A thermometer, a condenser, a stirrer, and a condenser for water removal were installed in a 2L four-necked flask, and a heating device was attached. 243 g of soybean fatty acid having 125 to 135 iodine, 27 g of 50 to 70 fatty acid of iodine, 162 g of phthalic anhydride as saturated base acid, 1 g of maleic anhydride as unsaturated base acid, 54 g of glycerin, 91 g of pentaerythritol, As the refluxing agent, 26 g of xylene was added and the temperature was raised to 160 캜 while being stirred slowly. The condensation reaction was carried out for about 1 hour to prevent low boiling point alcohol and rapid dehydration. And the temperature was raised to 220 캜 while stirring. The condensation reaction was carried out for about 4 hours to obtain an alkyd resin according to the present example having a viscosity of Z5 and a molecular weight of 28,000 as a condensation reaction product.

Example  3

A thermometer, a condenser, a stirrer, and a condenser for water removal were installed in a 2L four-necked flask, and a heating device was attached. 243 g of soybean oil having an iodine value of 125 to 135, 27 g of 50 to 70 fatty acids of iodine, 162 g of phthalic anhydride as a saturated base acid, 1 g of maleic anhydride as an unsaturated basic acid, 54 g of glycerin as a polyhydric alcohol, As the refluxing agent, 26 g of xylene was added and the temperature was raised to 160 캜 while being stirred slowly. The condensation reaction was carried out for about 1 hour to prevent low boiling point alcohol and rapid dehydration. And the temperature was raised to 220 캜 while stirring. Condensation reaction was carried out for about 5 hours to obtain an alkyd resin according to the present example having a viscosity of Z6 and a molecular weight of 58,000 as a condensation reaction product

Comparative Example 1

A thermometer, a condenser, a stirrer, and a condenser for water removal were installed in a 2L four-necked flask, and a heating device was attached. Thereto, 270 g of soybean fatty acid having 125 to 135 iodine, 162 g of phthalic anhydride, 123 g of pentaerythritol and 26 g of xylene as a refluxing solvent were added and the mixture was heated to 220 캜 while being stirred slowly. Condensation reaction was carried out for about 5 hours to obtain an alkyd resin composition for architectural enamel having a viscosity of Z3 and a molecular weight of 1,9000 as a condensation reaction product.

Example 1 Example 2 Example 3 Comparative Example 1 Remarks Soybean fatty acids with 125 to 135 iodine 243 g 243 g 243 g 270 Secondary fatty acid
Iodine is 50 to 70 fatty acids 27g 27g 27g Phthalic anhydride 162g 162g 162g 162 g Pentaerythritol 91g 91g 91g 123 g glycerin 54g 54g 54g - Xylene 26g 26g 26g 26g Maleic anhydride 1 g Molecular Weight 19,000 28,000 58,000 1,9000

In the embodiments, the second fatty acid having iodine value of 50 to 70 is applied, so that the reaction time can be maintained for a long time to increase the molecular weight. On the other hand, the molecular weight was the same as that of Comparative Example 1 and Example 1, but the workability was improved as described later due to differences in composition

At this time, it is preferable that the first fatty acid is included in 45 to 55 parts by weight and the second fatty acid is included in 1 to 10 parts by weight. The polybasic acid may be contained in an amount of 25 to 40 parts by weight, preferably 25 to 35 parts by weight of a saturated base acid saturated base acid and 1 to 5 parts by weight of an unsaturated base acid. The polyhydric alcohol is reacted by adding 20 to 30 parts by weight.

Experimental Example

Experimental Example 1

As shown in the following Table 2, using the alkyd resin for paints obtained in each of the above Examples and Comparative Examples to evaluate the properties of the alkyd resin after painting, the alkyd resin paint for architectural enamel according to the present invention .

Raw material name  Amount of blending The resins of the Examples and Comparative Examples 55 White pigment 25 Dispersant 0.3 drier 0.1 Defoamer 0.1 drier 0.25 Solvent 19.6 Sum 100

At this time, each component used in the experiment is as follows. White pigment: Titanium oxide (R-706 from DuPont) Dispersing agent: Polyamine amide of unsaturated polycarboxylic acid (NUOSPERSE657 from Elraments Specialties Inc., Defoamer: Polysiloxane BYK-066N from Biwa) (Mixed Drier / MD 1000 from Jin Yang Chemical Co., Ltd.), leveling agent: polyether-modified polymethylsiloxane (BYK-320 from Biwa K.K.), solvent: mineral spirits

Then, in order to examine the properties of the paints shown in Table 2, an applicator using an alkaline resin for enamel prepared in the test steel was applied with a thickness of 40 to 60 microns. Here, the film thickness means the thickness of the dried film. After drying at room temperature to obtain a test coat, the coating performance was investigated. The properties of the irradiated coating films are shown in Table 2. In Table 2, each characteristic was measured in the following manner.

1. The viscosity of the coating was measured with a Crevs-Stormer viscometer.

2. Set-to-touch was judged to be tack-free when the fingertip was lightly tacked but tacky, but the paint did not stick to the fingertip.

3. Dry-Hard (dry-hard), the test plate between the thumb and the thumb, close to the thumb side of the test, press hard (not twist), remove and gently rub a soft cloth. At this time, if there is no fingerprints on the coated film, it is assumed that it is solidified.

4. The gloss of the coating was measured with a BYK-Gardner haze gloss meter.

5. Covering rate is 30 centimeters by 30 centimeters and length is 10 centimeters black and white, respectively. Each paint was applied to a cover paper, and the degree of concealment thereof was visually determined.

6. The hardness of the coating film showed the pencil hardness after 2 days from the coating on the specimen. The pencil shows the hardness to the extent that there is no scratches or scratches on the film.

7. The workability of Laura was checked by rubbing it on the iron plate several times so that the manufactured paint was sufficiently adhered to Laura, and checking whether Laura was good or not. (A: Very good B: Good, C: Not good)

8. Appearance of the dried coating film was determined by observing the results of coating, leveling, color separation, pinhole, creta ring, etc. on the surface of the completely dried coating film.

9. Color separation stability was measured by rubbing the prepared paint on an iron plate and then measuring the color separation when the same paint was re-rubbed and rubbed with a finger to indicate color separation

Item Example 1 Example 2 Example 3 Comparative Example 1 KU viscosity 95 97 100 95 Drying time (touch) 25 minutes 24 minutes 22 minutes 30 minutes Drying time (solidification) 6 hours 20 minutes 6 hours 5 hours and 30 minutes 7 hours Glossy (glass plate / 60.) 95.2 95.1 95.7 95.4 Concealment rate 0.9812 0.982 0.99 0.985 Film hardness (2 days) 4B 4B 4B 4B Laura workability B B A C Dry film appearance Good Good Good Good Color separation stability DE: 0.2 DE: 0.15 DE: 0.1 DE: 0.25

As shown in Table 3, in the case of producing the enamel paint using the alkyd resin according to the production method of the present invention, the solidification dry composition and the ruler workability were excellent. That is, by increasing the molecular weight of the resin, the conjugated double bond is present at a large amount at the end of the fatty acid, so that the rate of forming the dried film by binding with oxygen in the air becomes faster. In addition, the improvement in the workability of the ruler is presumed to be due to the increase in the molecular weight of the whey while the whey is increased.

While the present invention has been described in connection with what is presently considered to be practical and exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And such variations are within the scope of the present invention.

The scope of the present invention is defined by the following claims, and is not limited to the description of the specification, and all variations and modifications falling within the scope of the claims are included in the scope of the present invention.

Claims (10)

A first polymerization step of polymerizing a first fatty acid having an iodine value in a range of 100 to 135, a second fatty acid having a iodine value in a range of 50 to 70, a polybasic acid, and a polyhydric alcohol at a first reaction temperature; And
And a second polymerization step of polymerizing the intermediate product after the first polymerization step at a second reaction temperature higher than the first reaction temperature. The method according to claim 1,
Wherein the first fatty acid is 80 to 99 parts by weight, the second fatty acid is 1 to 20 parts by weight, the polybasic acid is 25 to 40 parts by weight, and the polyhydric alcohol is 20 to 30 parts by weight. 3. The method of claim 2,
Wherein the polybasic acid comprises 25 to 35 parts by weight of a saturated base acid and 1 to 5 parts by weight of an unsaturated base acid. The method according to claim 1,
Wherein the molar ratio of the polyhydric alcohol to the sum of the fatty acid and the polybasic acid is in the range of 1.0 to 1.2: 1.0. The method according to claim 1,
Wherein the first reaction temperature is 155 to 160 ° C, and the second reaction temperature is 215 to 220 ° C. The method according to claim 1,
Wherein the alkyd resin has a molecular weight of 19,000 to 60,000. delete delete An enamel paint comprising an alkyd resin produced according to the process for producing an alkyd resin as claimed in any one of claims 1 to 6,
Wherein the enamel paint comprises 30 to 70 parts by weight of the alkyd resin, 20 to 50 parts by weight of the pigment, and 1 to 20 parts by weight of the solvent.
10. The method of claim 9,
Wherein the enamel coating further comprises 0.1 to 1 part by weight of a dispersing agent, 0.1 to 1 part by weight of a drying agent, 0.1 to 1 part by weight of a defoaming agent and 0.1 to 1 part by weight of a leveling agent as an additive.