JPH0826257B2 - Anti-dripping agent for non-aqueous paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an anti-sagging agent for non-aqueous paints, particularly tar epoxy paint, tar urethane paint, pure epoxy paint,
The present invention relates to an anti-sagging agent which has excellent effects on heavy-duty anticorrosive paints such as polyurethane paints and chlorinated rubber paints and non-aqueous paints such as acrylic paints and alkyd (modified) resin paints.

[Conventional technology]

Conventionally known anti-sagging agents used for non-aqueous paints include montmorillonite derivatives, hydrogenated castor oil, polyethylene oxide wax, metal soaps and the like, all of which have various drawbacks. For example, a montmorillonite derivative exhibits strong thickening when mixed with a non-aqueous paint, but the viscosity and the sagging prevention effect are lowered during storage. Hydrogenated castor oil exerts a sagging prevention effect when swollen by an appropriate dispersion method, but temperature control, which is one of the dispersion conditions, is extremely difficult, and particularly, strong thickening easily occurs during storage and seeds are generated. Sometimes. Oxidized polyethylene wax has a dripping prevention effect to some extent, but the dripping prevention effect is extremely weak in the area of heavy anticorrosion paint.
Metal soaps such as aluminum stearate have different swelling properties depending on the solvent and temperature, and particularly when a polar solvent such as alcohol or water is mixed, they tend to cause precipitation or seeds. N, N'-12-hydroxystearic acid ethylenediamide, N, N'-12-hydroxystearic acid hexamethylenediamide and N, N'-described in Japanese Patent Publication No. 51-58464 and Japanese Patent Publication No. 60-44352. 12-Hydroxystearic acid xylylenediamide has a property that it is difficult to swell, and the swelling temperature is in a considerably high temperature range, for example, 70 ° C. or higher in an organic vehicle of a paint which is usually used. Therefore,
Since the required swelling cannot be obtained under normal use conditions, it is difficult to obtain the thixotropic effect. Further, hydrogenated castor oil fatty acid (12-hydroxystearic acid) and carbon number 6 described in JP-B-60-44352 and JP-A-60-223876.
~ 12 fatty acid amide obtained by reacting a mixture of linear saturated fatty acids with ethylenediamine, butylenediamine or xylylenediamine forms a swelling structure under normal use conditions of about 50 to 70 ° C and imparts some thixotropy. Although it is possible to obtain the effect, the sagging prevention effect is not sufficient for heavy anticorrosion paints such as tar epoxy paints, tar urethane paints, pure epoxy paints and polyurethane paints that require thick film coating. Further, the above fatty acid amide has an increased affinity with a solvent, so that the fatty acid amide may bleed to the surface due to solvent volatilization during drying in the process of forming a coating film, which may cause delamination.

[Problems to be solved by the invention]

In the recent paint industry, even general non-aqueous paints such as heavy-duty anticorrosion paints have a tendency to be thick film coating. Accordingly, the conventional anti-sagging agents as described above do not provide satisfactory sagging prevention results, and also have high There are problems with thixotropy, strong viscosity increase, coating adhesion, storage stability, etc. Therefore, the present invention has been eagerly studied in order to solve such problems, and it is an object of the present invention to provide an anti-sagging agent exhibiting an excellent anti-sagging effect on non-aqueous paints.

[Means for solving problems]

DISCLOSURE OF THE INVENTION In view of the above, the present invention has led to various studies, and as a result, fatty acids obtained by reacting ethylenediamine or hexamethylenediamine with a mixture of 12-hydroxystearic acid and one or more straight chain saturated fatty acids having 3 to 4 carbon atoms. We have found that amide is an anti-sagging agent with excellent thixotropy, strong viscosity increase, coating adhesion, and storage stability. Furthermore, by using it together with conventional fatty acid amides, The present invention has been found to improve synergistic effects by improving dispersibility, swelling property, thixotropy, adhesion of coating film, storage stability and the like, leading to the present invention.

The present invention is a mixture of one or more straight chain saturated fatty acids having 3 to 4 carbon atoms and 12-hydroxystearic acid (the mixing ratio of this straight chain saturated fatty acid and 12-hydroxystearic acid is 1: 9 to 8: 2). A mixture of 12-hydroxystearic acid and a fatty acid amide [A] obtained by reacting ethylenediamine or hexamethylenediamine with a molar ratio range) and one or more kinds of linear saturated fatty acids having 6 to 22 carbon atoms. (The mixing ratio of this linear saturated fatty acid and 12-hydroxystearic acid is in the range of 0:10 to 8: 2 molar ratio) and a fatty acid amide obtained by reacting ethylenediamine, hexamethylenediamine or xylylenediamine [ B]
And the weight ratio of [A] and [B] is from 100: 0 to 20:80.
The anti-dripping agent for non-aqueous paints in the range.

Examples of the linear saturated fatty acid having 3 to 4 carbon atoms which can be used for producing the fatty acid amide [A] of the present invention include propionic acid and butyric acid. These may be used alone or as a mixture. Moreover, ethylenediamine or hexamethylenediamine can be used as the amine. Although general polyalkylene polyamines such as propylene diamine, butylene diamine, octamethylene diamine, diethylene triamide, and triethylene tetramine can also be used, these are components that form a superior anti-sagging agent than ethylene diamine or hexamethylene diamine. It turns out that it can't be. The mixing ratio of one or more straight chain saturated fatty acids having 3 to 4 carbon atoms and 12-hydroxystearic acid is in the range of 1: 9 to 8: 2, and particularly, the molar ratio of 4: 6 to 7: 8. preferable. When the mixing amount of 12-hydroxystearic acid is more than the above-mentioned ratio, the dispersibility and swelling property of the fatty acid amide [A] formed are lowered. On the contrary 12-
When the mixing amount of hydroxystearic acid is less than the above ratio, the dispersibility is improved, but thixotropy is reduced and the effect of preventing the non-aqueous paint from sagging is weakened.

A straight chain saturated fatty acid having 6 to 22 carbon atoms (including animal and vegetable fats and oils) that can be used for producing the fatty acid amide [B] of the present invention
Examples thereof include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and the like, and these may be used alone or as a mixture. 12 with these straight chain saturated fatty acids
The mixing ratio of hydroxystearic acid is in the range of 0:10 to 8: 2, particularly preferably 0:10 to 6: 4. 1
When the mixing amount of 2-hydroxystearic acid is less than the above ratio, thixotropy is reduced and the effect of preventing the non-aqueous paint from sagging is weakened.

As the amine that can be used to produce the fatty acid amide [B] of the present invention, xylylenediamine can be used in addition to the ethylenediamine and hexamethylenediamine used to produce the fatty acid amide [A].

The anti-sagging agent of the present invention comprises the above fatty acid amide [A] or a mixture of the fatty acid amide [A] and the fatty acid amide [B]. In the case of the mixture, the mixing ratio is from less than 100: 0 to 20:80, particularly 80: A range of 20 to 30:70 weight ratio is preferred. When the amount of the fatty acid amide [B] is increased from the above range, the effect of improving the dispersibility, swelling property, thixotropy and viscosity increase by the fatty acid amide [A] cannot be obtained, and a satisfactory anti-sagging agent is difficult to obtain.

The reaction for producing the fatty acid amides [A] and [B] of the present invention may be carried out in accordance with ordinary production of fatty acid amides. For example, a mixture of 12-hydroxystearic acid and the straight chain saturated fatty acid used in each is mixed with diamine and 150
The dehydration reaction may be carried out at a reaction temperature of ℃ to 200 ℃ for about 5 to 6 hours, and the end point of the reaction may be controlled by the acid value and the amine value. Fatty acid amides [A] and [B] thus obtained
Is a light yellow to light tan solid with a melting point of 95 ° C to 150 ° C and has an acid value and amine value of 15 or less.

The anti-sagging agent of the present invention contains a fatty acid amide [A] alone or a fatty acid amide [A] and a fatty acid amide [B], and these are mixed with an aliphatic solvent, an aromatic solvent or a mixture thereof. After heating and dissolving in an organic solvent that is a solvent, cool it to make a swollen gel paste of fatty acid amide,
This may be added to a non-aqueous paint and kneaded and dispersed to be used, or the above fatty acid amide crushed to 45 μ or less by a crusher may be added to a paint and kneaded and used. .

[Work]

The anti-dripping agent of the present invention is applied as an anti-dripping agent for non-aqueous paints such as tar epoxy dyes, tar urethane paints, pure epoxy paints, polyurethane paints, chlorinated rubber paints and other heavy anticorrosion paints and acrylic paints and alkyd (modified) paints. it can. The addition amount of the anti-sagging agent of the present invention varies depending on the type of paint and the required performance, but is usually the amount of the fatty acid amide [A] or the total amount of the fatty acid amide [A] and the fatty acid amide [B] with respect to the paint. , 0.2 to 4.0% by weight, preferably 0.3 to 2.0% by weight. If the amount added is less than 0.2% by weight, the effect of preventing sagging of the target paint during coating is not sufficient, which is not preferable. Also
It is possible to use a large amount exceeding 4.0% by weight, but this is not preferred because it may deteriorate the gloss retention of the coating film. The addition time of the anti-sagging agent of the present invention is usually preferably added in the pigment dispersion step of the paint, and as a dispersion machine, a machine that requires heat of dispersion such as a ball mill, a sand grinder or a cowless dissolver is suitable. Practical effects can be obtained over a wide range of dispersion temperatures from room temperature to high temperatures of 80 ° C.

EXAMPLES Hereinafter, the present invention will be described with reference to Production Examples, Comparative Production Examples, Examples, Comparative Examples and Test Examples, but the present invention is not limited thereto. Parts and percentages are by weight.

Production Example 1; Production of fatty acid amide [A] 1-mol of 12-hydroxystearic acid and 1-mol of butyric acid were placed in a four-necked flask of 1 and heated to 100 ° C to uniformly dissolve, then 1 mol of ethylenediamine was added, and N ₂ was added. The temperature was gradually raised in a gas stream and the reaction was carried out at 180 ° C to 185 ° C for 7 hours to obtain a pale yellow fatty acid amide [A] having an acid value of 5.4, an amine value of 5.0 and a melting point of 120 ° C.

Production Examples 2 to 4 and Comparative Production Examples 1 to 2 The fatty acid amides [A] of Production Examples 2 to 4 and Comparative Production Examples 1 to 3 were prepared in the same manner as in Production Example 1 using the raw materials shown in Table 1. A comparative control fatty acid amide was prepared.

Production Example 5: Production Example of Fatty Acid Amide [B] 12-Hydroxystearic acid (1.2 mol) and palmitic acid (0.8 mol) were placed in a four-necked flask of 1 and heated to 100 ° C. to uniformly dissolve, and 1 mol of hexamethylenediamine was added. Then, the temperature was gradually raised in a N ₂ gas stream, and the reaction was carried out at 190 ° C to 200 ° C for 7 hours to obtain a pale yellow fatty acid amide [B] having an acid value of 5.8, an amine value of 5.2 and a melting point of 125 ° C. .

Production Examples 6 to 9 and Comparative Production Examples 4 to 7 The fatty acid amides [B] of Production Examples 6 to 9 and Comparative Production Examples 4 to 7 were prepared in the same manner as in Production Example 5 using the raw materials shown in Table 2. A comparative control fatty acid amide was prepared.

Example 1 20 parts of the fatty acid amide [A] of the above Production Example 1 was xylol
The mixture was heated and dissolved in 80 parts, and stirred and kneaded while gradually cooling to obtain a paste-like anti-dripping agent.

Example 2 10 parts of the fatty acid amide [A] of Production Example 1 and 10 parts of the fatty acid amide [B] of Production Example 5 were heated and dissolved in 80 parts of xylol, and the mixture was stirred and kneaded while gradually cooling to give a paste form. The anti-dripping agent was obtained.

Hereinafter, the fatty acid amides of Production Examples 1 to 9 and Comparative Production Examples 1 to 7 were used, and the composition ratios shown in Tables 3 and 4 were used for Example 1
Alternatively, the anti-dripping agents of Examples 3 to 13 and Comparative Examples 1 to 18 were prepared in the same manner as in Example 2.

Test Example 1 A test example when added to a tar epoxy paint is shown.

(1) Paint composition: (a) Main agent Turklon 180 (manufactured by Yoshida Refinery) 20 parts Epicoat 834 (manufactured by Yuka Shell Epoxy) 20 Talc (manufactured by Nippon Talc) 30 Precipitating barium sulfate (manufactured by Sakai Chemical) 10 Thinner ^* 20 Total 100 parts * Thinner composition 40% toluene, 30% xylene, 20% ethyl cellosolve,
Methyl isobutyl ketone 10% 5 volume round tin can (diameter 170mm, depth 240mm), weigh the above main ingredient material, put 1/3 weight glass beads (diameter 1.5-2.0mm) into it, paint A blank paint is obtained by roughly dispersing with a shaker and then removing the glass beads.

(B) Hardener Versamide 115 (made by Henkel Hakusui) 70 parts Thinner 30 total 100 parts The above hardener raw materials are weighed and stirred with a lab disper to obtain a uniform transparent solution, which is used as the hardener.

(2) Addition method of anti-sagging agent: 500 g of blank paint and glass beads (diameter 1.5-2.0 mm)
400 g is weighed in one container, and an anti-sagging agent is added to the blank paint in an amount equivalent to 1% in terms of solid content, and dispersed using a test six-cylinder batch type sand grinder (Igarashi Kikai). The dispersion conditions are as follows: rotation speed 2080 rpm, dispersion time 35 minutes, dispersion temperature 50 ° C., then pass to remove glass beads and make test base paint.

(3) Preparation of test paint: As the test paint, use a mixture of 105 parts of the above-mentioned test base paint and 26.6 parts of the above curing agent.

With regard to the coating composition of (3) above, the viscosity was measured, and then a constant viscosity was measured using a thinner (20 ° C. using a B-type viscometer,
After adjusting the viscosity at 60 rpm to 20 ± 2 poises), tests were carried out on the anti-dripping property and the interlayer adhesion of the coating film.

(4) Test item measurement method: The test item measurement method is shown below. Unless otherwise specified, the same measurement method is used.

a. Thickening: Measured at 20 ° C. using a Stormer viscometer. The viscosity value indicates KU.

b. Anti-sagging property: Using a sag tester (manufactured by Taiko Equipment Co., Ltd.), the paint viscosity was adjusted to the viscosity of each test paint with a thinner, and measured using a glass plate at room temperature (20 ± 1 ° C). The sagging prevention property is indicated by the film thickness (μ) in which sagging occurs in almost half of the blank portion of the sag tester.

c. Granularity: In accordance with JIS K-5400 4.4 "Measurement method", measurement is performed using a crushing gauge (manufactured by Taikyu Equipment Co., Ltd.) and the judgment is A method.

d. Interlayer adhesion: Paint 60 on a glass plate (100 x 200 mm) with an applicator
Apply it to a film thickness of 0μ, leave it for 16 hours in a closed container (diameter of round tin can of 170 mm, depth of 240 mm), take out the glass plate from the closed container, and coat the paint again (film thickness 600
μ) and dried again in a closed vessel for 24 hours, then removed,
The coating film was knife-cut at an angle of 45 and the state of the boundary between the first layer and the second layer was observed. The judgment criteria are as follows.

◯: No boundary line is seen (no interlaminar peeling), Δ: There is a boundary line (no interlaminar peeling), ×: There is a boundary surface (there is a risk of interlaminar peeling), XX: There is interlaminar peeling.

e. Gloss retention; Paint is applied to a glass plate (100 x 200 mm) with an applicator 12
It is applied with a film thickness of 5μ, and after 24 hours, it is measured with a gloss meter (Murakami Color Research Institute). The gloss retention is indicated by a value of 60 ° gloss.

f. Accelerated storage stability test: The main coating material for test was hermetically sealed and allowed to stand at 50 ° C for 1 month, and then the viscosity increase, sag prevention property, interlayer adhesion, gloss retention and particle size were measured.

(5) Results: Table 5 shows the experimental results.

Test Example 2 A test example when added to the tar urethane paint is shown.

(1) Composition of paint: (a) Main agent Turcron 180 (manufactured by Yoshida Refinery) 23 parts Epicron H-201-60 (manufactured by Dainippon Ink and Chemicals) 38 Talc (manufactured by Nippon Talc) 23 Xylene 8 MIBK 8 Total 100 parts Weigh the above main ingredient material into a 5 volume round tin can (diameter 170 mm, depth 240 mm), put 1/3 weight glass beads (diameter 1.5 to 2.0 mm) into it, and roughly disperse with a paint shaker, And remove the glass beads to make a blank paint.

(B) Hardener Use Sumidjuur N-75 (Sumitomo Bayer Urethane).

(2) Addition method of anti-sagging agent: 500 g of blank paint and glass beads (diameter 1.5-2.0 mm)
400 g is weighed in one container, and an anti-sagging agent is added to the blank paint in an amount equivalent to 1% in terms of solid content, and dispersed using a test six-cylinder batch type sand grinder (manufactured by Igarashi Kikai). The dispersion conditions are as follows: rotation speed 2080 rpm, dispersion time 35 minutes, dispersion temperature 50 ° C., then pass to remove glass beads and make test base paint.

(3) Preparation of test paint: The test paint consisted of 100 parts of the above-mentioned test base paint and 25 curing agents.
Use a mixture of parts.

For the paint of (3) above, the viscosity increase was measured, and then a constant viscosity (B) was measured using thinner (xylene / MIBK = 1/1).
The viscosity was adjusted to 20 ± 1 poise at 20 ° C. and 60 rpm using a type viscometer, and then the intercoat adhesion of the anti-dripping coating film was tested.

(4) Results: Table 6 shows the experimental results.

Test Example 3 A test example when added to a chlorinated rubber paint is shown.

(1) Paint composition: Super Klon 106H (Sanyo Kokusaku Pulp) 10 parts Super Klon 510 (Sanyo Kokusaku Pulp) 10 Paraffin chloride 50 (Toyo Soda Kogyo) 9 Titanium oxide R-820 (Ishihara Sangyo) 25 Epicoat 828 (Oilized Shell Epoxy) 1 xylene 45 total 100 parts 5 volume round tin can (diameter 170mm, depth 240mm), weigh the above raw material, and 1/3 weight of glass beads (diameter 1.5 ~ 2mm), and roughly disperse with a paint shaker, and then pass through to remove the glass beads to make a blank paint.

(2) Method of adding anti-sagging agent: 500 g of the above blank paint and glass beads (diameter 1.5 to 2.0
mm) 400 g is weighed into one container, and a dripping inhibitor is added to the blank paint by using a six-cylinder batch type sand grinder (made by Igarashi Machinery Co., Ltd.) for testing, in which a solid content of 0.6% is added. Dispersion conditions are rotation speed 2080 rpm, dispersion time 35 minutes,
The dispersion is carried out at a temperature of 50 ° C., and then the glass beads are removed by passing to obtain a test main component paint.

(3) Test method: The viscosity of the above test paint was measured, and then adjusted to a constant viscosity (70KU, 20 ° C) using xylene.
Tests were carried out for sagging prevention and gloss.

(4) Results: Table 7 shows the test results.

[Effects of the Invention] As is clear from the data of each of the above-mentioned test examples, the anti-dripping agent according to the present invention is used in a non-aqueous paint and exhibits excellent thickening properties, interlayer adhesion, gloss retention, and paint stability. It turns out to be effective.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoichi Iya 7 of 87, Imadabori Terada, Joyo City, Kyoto Prefecture

Claims (1)

[Claims] 1. A straight-chain saturated fatty acid having 3 to 4 carbon atoms.
Reacting a mixture of 12 or more kinds of 12-hydroxystearic acid (the mixing ratio of this linear saturated fatty acid and 12-hydroxystearic acid is in the range of 1: 9 to 8: 2 molar ratio) with ethylenediamine or hexamethylenediamine A mixture of 12-hydroxystearic acid and a fatty acid amide [A] thus obtained, and one or more linear saturated fatty acids having 6 to 22 carbon atoms (mixing ratio of this linear saturated fatty acid and 12-fudroxystearic acid). Is in the range of 0:10 to 8: 2) and fatty acid amide [B] obtained by reacting ethylenediamine, hexamethylenediamine or xylylenediamine with the weight of [A] and [B] above. Ratio is 100: 0
The anti-dripping agent for non-aqueous paints, which is in the range of up to 20:80.