JPS63235381A - Anti-sagging agent for use in non-aqueous paint - Google Patents

Abstract

PURPOSE:To form an anti-sagging agent for use in a non-aqueous paint, which provides excellent thixotropic properties, thickening properties, adhesiveness of a coating film, and storage stability, by mixing two kinds of specified fatty acid amides with each other. CONSTITUTION:This anti-sagging agent for use in a non-aqueous paint is prepared by mixing two fatty acid amides A and B in a weight ratio of A to B of 100:0-20:80. Said amide A is one obtained by reacting a mixture of one or more 3-4C straight-chain saturated fatty acids (a) and 12-hydroxystearic acid (b) [the molar ratio of (a) to (b) is 1:9-8:2] with ethylenediamine or hexamethylenediamine; and said amide B is one obtained by reacting a mixture of one or more 6-22C straight-chain saturated fatty acids (c) and 12- hydroxystearic acid (b) [the molar ratio of (c) to (b) is 0:10-8:2] with ethylenediamine, hexamethylenediamine or xylylenediamine.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applied to anti-sagging agents for non-aqueous paints, special Kotar epoxy paints, tar urethane paints, pure epoxy paints,
This invention relates to anti-sagging agents that are highly effective for 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]

Known anti-sagging agents conventionally used in non-aqueous paints include derivatives of montmo 17-iF-ite, hydrogenated castor oil, oxidized polyethylene wax, and metal soap, but all of these have various drawbacks. are doing. For example, montmorinite derivatives exhibit strong thickening when mixed with non-aqueous paints, but the viscosity and anti-sag effect decrease during storage. Hydrogenated castor oil exhibits an anti-sagging effect when swollen using an appropriate dispersion method, but temperature control, which is one of the dispersion conditions, is extremely difficult, and it tends to thicken heavily and generate seeds, especially during storage. There are things to do.

Although oxidized polyethylene wax has a certain degree of anti-sagging effect, the anti-sag effect is extremely weak in the area of heavy-duty anti-corrosion paints. The swelling properties of metal soaps such as aluminum stearate vary depending on the solvent and temperature, and they tend to form precipitates and seeds especially when mixed with polar solvents such as alcohol and water. Special Publication No. 51-58464 and Special Publication No. 60-4
N,N'-12-hydroxystearic acid ethylene di7mide, N,N'-12-hydroxystearic acid hexamethylene diamide and N, which are described in No. 4352.
, silylene diamide in N'-12-hydroxystearic acid has the property of being difficult to swell, and the swelling temperature is in a fairly high temperature range, for example, 70° C. or higher, in the organic vehicle of a commonly used paint. Therefore, since the necessary swelling cannot be obtained under normal usage conditions, it is difficult to obtain the indexability imparting effect. In addition, Japanese Patent Publication No. 60-44352 and Japanese Patent Publication No. 60-44352
- Hydrogenated castor oil fatty acid (12-hydroxystearic acid) described in No. 223876 and zo carbon number 6 to
Fatty acid amides obtained by reacting a mixture of 12 linear saturated fatty acids with ethylene diamine, butylene diamine, or xylylene diamine form a swelling tangent under normal usage conditions of about 50 to 70°C, and have a certain degree of indexability. Although a good effect can be obtained, the anti-sagging effect is not sufficient for heavy-duty anticorrosive paints that require thick coating such as tar evo medium paint, tar urethane paint, pure epoxy paint, and polyurethane paint. Furthermore, the above-mentioned fatty acid amide has an increased affinity with the solvent, and therefore, there is a risk that the fatty acid amide bleeds to the surface as the solvent evaporates during drying during the coating film formation process, causing delamination.

[Problem that the invention seeks to solve]

Recently, in the paint industry, there has been a trend toward thicker coatings for general non-aqueous paints, including heavy-duty anti-corrosion paints, and as a result, conventional anti-sag agents such as those mentioned above have not been able to provide sufficient anti-sag results. In addition, two problems have arisen, including high deterioration, strong viscosity, coating adhesion, and storage stability. Therefore, the object of the present invention is to conduct extensive research in order to solve these problems, and to provide an anti-sag agent for non-aqueous paints that exhibits an excellent anti-sag effect.

[Means to solve the problem]

In view of the above, the present invention has been made after extensive research and is based on the combination of ethylene diamine or hexamethylene diamine, 12-hydroxystearic acid, and a linear saturated fatty acid having 3 to 4 carbon atoms. It has been discovered that the fatty acid amide obtained by reacting with a mixture of the above is a highly modified, strong thickening, coating film adhesion, storage stability (poor sagging prevention agent). The inventors have found that the dispersibility, swelling properties, indexability, adhesion of allH, storage stability, etc. of conventional fatty acid amides can be improved and a synergistic effect can be achieved by using them in combination with other fatty acid amides, leading to the present invention.

The present invention deals with 11i of straight chain saturated fatty acids having 3 to 4 carbon atoms.
A mixture of F1 or higher and 12-hydroxystearic acid (
The mixture ratio of this linear saturated fatty acid and 12-hydroxystearic acid is in the range of 1:9 to 8:2 molar ratio) and ethylenediamine or hexamethylenediamine to obtain fatty acid amide' (A) and Carbon number 6
A mixture of 12-hydroxystearic acid and one or more straight chain saturated fatty acids having 1 to 22
The mixing ratio of 2-hydroxystearic acid is 0:l0~8
:2 molar ratio range) and ethylenediamine, hexamethylenediamine or kyrelylenediamine [B], and the above (A)
and CB) in a weight ratio of 100:0 to 20:80.

Examples of straight chain saturated fatty acids having 3 to 4 carbon atoms used in 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.

Further, as the amine, ethylenediamine or hexamethylenediamine can be used. Common polyfulkylene polyamines such as propylene diamine, butylene diamine, octamethylene diamine, diethyl ethylene triamine, and triethylene tetramine can also be used, but all of these ingredients form better anti-sag agents than ethylene diamine or hexamethylene diamine. It was found that the mixing ratio of one or more straight chain saturated fatty acids having 3 to 4 carbon atoms and 12-hydroxystearic acid was 1:9.
A molar ratio of from 4:6 to 7:3 is particularly preferred. When the mixed amount of 12-hydroxystearic acid is increased from the above ratio, fatty acid amide (
The dispersibility and swelling properties of A) are reduced. On the other hand, if the amount of 12-hydroxystearic acid mixed is less than the above ratio, the dispersibility will improve, but the thixotropy will decrease and the effect of preventing dripping of non-aqueous paints will become weaker.

Straight chain saturated fatty acids (including animal and vegetable oils) having 6 to 22 carbon atoms that can be used to produce the fatty acid amide (B) of the present invention
Examples of the acid include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, etc., and each of these may be used alone or in a mixture. These straight chain saturated fatty acids and 1
The mixing ratio of 2-hydroxystearic acid is 0:10-8
:2 molar ratio, particularly preferred is a molar ratio of 0:10 to 6:4. If the amount of 12-hydroxystearic acid mixed is less than the above ratio, the thixotropy will be lowered and the effect of preventing the non-aqueous paint from dripping will be weakened.

As the amine that can be used to produce the fatty acid amide (B) of the present invention, in addition to ethylenediamine and hexamethylene diamine used in the production of the fatty acid amide (A), medium silylene diamine can also be used.

The anti-slip agent of the present invention is composed of the above-mentioned fatty acid amide (A) or a mixture of this and the fatty acid amide (B), and in the case of a mixture, the mixing ratio is in the range of less than 100:0 to 20:80 weight ratio, especially 80:0. :20 to 30 near 0@quantity ratio i range is preferable. If the fatty acid amide (B) is increased from the above ratio, the improvement effect of the fatty acid amide (A) in terms of dispersibility, swelling properties, thixotropy, and thickening properties cannot be obtained, and it is difficult to obtain a satisfactory anti-sagging agent.

The reaction for producing the fatty acid amides (A) and (B) of the present invention may be carried out in accordance with the production of ordinary fatty acid amides. For example, a mixture of 12-hydroxystearic acid and the linear saturated fatty acid used in each case is mixed with diamine and 15-hydroxystearic acid.
The dehydration reaction may be carried out at a reaction temperature of 0° C. to 200° C. for about 5 to 6 hours, and the end point of the reaction may be controlled by the acid value and amine value. Fatty acid amides (A) and (B) thus obtained
Its properties are a light yellow to pale yellowish brown solid with a melting point of 95°C to 150°C, and its acid value and amine value are each 15 or less.

The anti-sagging agent of the present invention contains fatty acid amide (A) alone or fatty acid amide (A) and fatty acid amide (B), and these are combined with an aliphatic solvent, an aromatic solvent, or a mixture thereof. The fatty acid amide may be heated and dissolved in an organic solvent and then cooled to form a swollen gel paste of the fatty acid amide, which is added to a non-aqueous paint and used by kneading and dispersing. It may be ground to 45 μm or less using a grinder, added to the paint, and kneaded for use.

[For production]

The anti-sag characteristic 1 of the present invention is applied to heavy anticorrosive paints such as tar epoxy paints, tar urethane paints, pup epoxy paints, polyurethane paints, chlorinated rubber paints, and acrylic paints,
It can be applied as an anti-sagging agent for non-aqueous paints such as full-kid (modified) paints. The amount of the anti-sagging agent of the present invention added varies depending on the type of paint and the required performance, but it is usually the total amount of fatty acid amide (A) or fatty acid temide (A) and fatty acid amide (B). , 0.2 to 4.0% by weight, preferably 0.3 to 2.0ifi%. If the amount added is less than 0.2% by weight, the desired effect of preventing the paint from dripping during application will not be sufficient, which is undesirable. It is also possible to use a large amount exceeding 4.0% by weight, but in this case it is not preferable because the gloss retention of the coating film may be deteriorated. The anti-sagging agent of the present invention is preferably added during the pigment dispersion process of the paint, and the dispersing machine is preferably a machine that applies dispersion heat such as a ball mill, sand grinder, colorless digilver, etc.
Practical effects can be obtained over a wide range of kneading and dispersion temperatures from room temperature to as high as 80°C.

EXAMPLES The present invention will be explained below 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 2-hydroxystearic acid and 1 mol of butyric acid were added to 1 mole of fatty acid amide (A). After heating to 100℃ and uniformly dissolving it, 1 mol of ethylenediamine was added, the temperature was gradually raised in a stream of % Nt gas, and the reaction was carried out at 180℃ to 185℃ for 7 hours to reach an acid value of 5. .4, an amine value of 5.0, and a pale yellow fatty acid amide (A) having a melting point of 120°C was obtained.

Production Examples 2 to 4 and Comparative Production Examples 1 to 3 Below, Production Examples 2 to 4 were carried out in the same manner as Production Example 1 using the raw materials shown in Table 1.
Fatty acid amide (A) of No. 4 and comparative fatty acid amides of Comparative Production Examples 1 to 3 were prepared.

Production Example 5; Production Example 1 of Fatty Acid Amide (B) 1.2 mol of 2-hydroxystearic acid and 0.0 mol of patvmitic acid.
Pour 8 mol into a four-sided flanucco, heat to 100°C to dissolve uniformly, add 1 mol of hexamethylene diamine, gradually raise the temperature in a N gas stream, and heat to 190°C to 200°C.
After reacting at ℃ for 7 hours, the acid value was 5.8, the amine value was 5.2,
A pale yellow fatty acid 7mide (B) with a melting point of 125°C was obtained.

Production Examples 6 to 9 and Comparative Production Examples 4 to 7 Below, Production Examples 6 to 9 were carried out in the same manner as Production Example 5 using the raw materials shown in Table 2.
Fatty acid amide (B) of No. 9 and comparative fatty acid amides of Comparative Production Examples 4 to 7 were prepared.

Example 1 20 parts of the fatty acid amide (A) of Production Example 1 was heated and dissolved in 80 parts of Kijiroll, and stirred and kneaded while gradually cooling to obtain a paste-like anti-sagging 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 Kijiroll, and mixed with stirring while gradually cooling to form a paste. An anti-sagging agent was obtained.

Hereinafter, using the fatty acid amides of Production Examples 1 to 9 and Comparative Production Examples 1 to 7, Examples 3 to 13 and Comparative Examples Anti-sag agents Nos. 1 to 18 were prepared.

Test example l Tar epoxy coating (Test example when this is added is shown.

(1) Paint composition: (a) Main agent Turclone 180 (Kaida TsuΔ!Oilsho (5) 2
Part 0 Talc (Japanese Taru Rian D 3
0 precipitated barium sulfate (Sakai Chemical fID10 thinner)
20 total
100 parts Hata Thinner composition Toluene 40%, Xylene 30%, Ethyl cellosolve 2
0%, methyl isobutyl ketone lO% 5] capacity round tin can (diameter 17ONL, depth 240m
), weigh out the base material, add it, coarsely disperse it in a paint shaker, filter it, remove the glass beads, and use it as a blank paint.

(b) Hardening agent persamide 115 (Henkel white water%'l) 70
Total parts: 100 parts The above curing agent raw material was weighed out and stirred with a lab body spar to form a homogeneous transparent solution, which was used as a curing agent.

(2) How to add anti-sag agent
2.0m) Weighed 400 g into a 1-inch container, added an amount of anti-sagging agent equivalent to 1% of the solid content of the blank paint, and used a test water bottle batch type sand grinder (manufactured by Igarashi Kikai). and disperse. Dispersion condition is rotation speed 20
8 Orpm.

The dispersion was carried out for 35 minutes at a dispersion temperature of 50° C., and then filtered to remove the glass beads to prepare a test base paint.

(3) Preparation of paint for test: The paint for test used is a mixture of 105 parts of the above main paint for test and 26.6 parts of the above curing agent.

The viscosity of the paint in (3) above was measured, and then thinner was used to maintain a constant viscosity (at 20°C using a B-type viscometer).
After adjusting the viscosity at 60 rpm to 20 ± 2 voids, tests were conducted for anti-sagging properties and interlayer adhesion of the coating film.

(4) Methods for measuring test items: The methods for measuring test items are shown below, but unless otherwise specified, the same measurement methods will be used.

a. Thickening property: Measured at 20°C using a Stormer viscometer. Viscosity values indicate KU.

b. Anti-sag properties; Using a sag tester (manufactured by Taiyu Kikai), the viscosity of the paint was adjusted with thinner to the viscosity of each test paint, and measured using a glass plate at room temperature (20±1°C). The anti-sagging property is indicated by the film thickness (μ) at which sag occurs in approximately half of the blank area of the sag tester.

C1 particle size; JISK-54004, <Measurement was carried out using a grain gauge (manufactured by Tenyu-samazai) according to the "grain measurement method", and the judgment was A.
Make it law.

d. Glabella adhesion: Paint was applied to a glass plate (100 x 200 m) with a G-coat applicator to a film thickness of 600 μm, left in an airtight container (51 round tin can diameter 170 m, depth 240 m) for 16 hours, and then placed in an airtight container. Take out the glass plate from inside, apply another layer of paint (film thickness 600μ), dry again in a sealed container for 24 hours, take it out, cut the paint film with a knife at a 45 angle, and apply the first and second layers. The condition of the eye border was observed. The judgment criteria are as follows.

○: Boundary cannot be seen (no peeling between layers), △:: Boundary is present (no peeling between layers), ×: Boundary is present (there is a risk of peeling between layers), xx: Peeling between fi.

e. Gloss retention: The paint is applied to a glass plate (100 x 200 m) with an ablator to a film thickness of 125 μm, and measured after 24 hours using a gloss meter (manufactured by Murakami Color Co., Ltd.).

Gloss retention is expressed as a 60° gloss value.

f. Accelerated Storage Stability Ratio Test; After the base paint for the test was sealed and left at 50° C. for one month, its thickening properties, anti-sag properties, interlayer adhesion, gloss retention, and particle size were measured.

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

Table 5 (Part 1) Table 5 (Part 2) Test example 2 A test example when added to tar urethane paint is shown.

(1) Composition of the paint: (a) Main agent Turclone 180 (Yoshikawa Refinery I!RI 23 parts Talc (manufactured by Nippon Talc) 23 xylene The above main agent ingredients are placed in an 85-capacity round pre-medium can (diameter 170w 1 depth 240m) Weigh and add the weight of the glass beads (
Diameter 1.5~2. ows) and remove the coarsely dispersed L1 filtration L1 glass beads using a paint shaker, and use it as a blank paint.

(b) Use the curing agent Sumi Joule N-75 (manufactured by Sumitomo Bayer Urethane).

(2) How to add anti-sagging agent 500g of blank paint and glass peas (diameter 1.5-2
．． Weigh 400g of 0vx) into a container No. 11, add anti-sagging agent equivalent to 1% solid content of the blank paint, and disperse using a test water bottle batch type sand grinder (manufactured by Igarashi Kikai) ◇Dispersion conditions are Rotation speed 208Or
The pm1 dispersion time is 35 minutes and the dispersion temperature is 50° C., and then the glass beads are removed by filtration to prepare a test base paint.

(3) Preparation of test paint: The test paint consists of 100 parts of the above test base paint and 2 parts of curing agent.
Use a mixture of 5 parts.

For the paint in (3) above, measure the viscosity, then use thinner (xylene/MIBK = -) to maintain a constant viscosity (using a B-type viscometer, set the viscosity at 20°C and 60 rpm to 20 ± 1 poise). ), the anti-sagging coating was tested for glabellar adhesion.

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

Table 6 (Part 1) Table 6 (Part 2) Test example 3 A test example when added to chlorinated rubber paint is shown.

(1) Composition of paint: Titanium oxide R-820 (Ishihara Sangyo 25g)
Weigh out the above raw materials into a round tin can (diameter 1701 g, depth 240 m) with a total capacity of 100 parts5), and add -weight glass pieces (diameter 1.5
~2r+v) Roughly disperse the mixture in a paint shaker, filter it, and remove the glass beads to obtain a blank paint.

(2) Addition method of anti-sagging agent: Add 500g of the above blank paint and a glass piece (diameter 1.5
~2.0) Weigh 400g into 11 containers, add anti-sagging agent to the blank paint in an amount equivalent to 0.6% solids, and disperse using a test water bottle batch type sand grinder (manufactured by Igarashi Kikai). do. Dispersion conditions are rotation speed 208 Orp.
The m1 dispersion time was 35 minutes and the dispersion temperature was 50°C, and then the glass beads were removed by filtration to obtain a base paint for test 1.

(3) Test method: The above test paints were tested for viscosity, firstly adjusted to a constant viscosity (0.20° C. at 70°C) using xylene, and then tested for anti-sag properties and gloss.

(4) Results: Table 7 (Part 1) Table 7 (Part 2) [Effects of the Invention] As is clear from the data of the above-mentioned test examples, the anti-sagging agent according to the present invention has an excellent effect on increasing the amount of paint used in non-aqueous paints. viscosity,
1! It can be seen that it exhibits an anti-sagging effect that exhibits inter-lI adhesion, gloss retention, and paint stability.

Claims (1)

[Claims] 1. 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 the straight chain saturated fatty acids and 12-hydroxystearic acid is 1: 9 to 8:2 molar ratio) and ethylenediamine or hexamethylene diamine [A], and one or more straight chain saturated fatty acids having 6 to 22 carbon atoms and 12- A mixture of hydroxystearic acid (the mixing ratio of linear saturated fatty acid and 12-hydroxystearic acid is in the range of 0:10 to 8:2 molar ratio) and ethylenediamine, hexamethylenediamine or xylylenediamine are reacted. An anti-sagging agent for non-aqueous paints, comprising the obtained fatty acid amide [B], characterized in that the weight ratio of the above [A] and [B] is in the range of 100:0 to 20:80.