DE1943523C3 - Use of reaction products as thixotropic additives for coating agents - Google Patents

Description

HO- (CH ₂ CH ₂ O) _n -H

20th

in which η denotes a number from 1 to 30, have been produced as a thixotropic-producing additive for coating agents, in amounts of 0.05 to 10%.

3. Use of the reaction products according to claim 1 or 2 as an additive to coating agents based on oil paints.

35

The invention relates to a method for preventing the dripping of coating agents from underneath Use of certain reaction products.

The usual, air-drying, ready-mixed paints, such as resin paints, those with fatty acids are modified, have oil-modified paints made from synthetic resins, and other oil paints all have the disadvantage that they drip off or run down when applied to surfaces, regardless of whether they are brushed, dipped, coated in a flow process or by spraying are upset. The dripping or running off leads to an irregularity in the coating film and requires a double overcoat or special operation which makes it difficult to produce a to achieve a coating of sufficient effect.

The invention has set itself the task. links to find that, as an additive to coating agents, prevent dripping without the To affect the gloss significantly.

Polyamide resins have already been recommended as components of coating agents.

These materials are usually solid or semi-pasty at room temperature and generally show so poor compatibility with coating materials that they form blistering when mixed with them cause. To avoid this, an additional prior kneading process is necessary with subsequent treatment with the help of a grindstone or a sand rubbing surface, what the usefulness such a coating process is reduced.

According to the invention, the object set is achieved by using terminal carboxyl groups Reaction products with a constant hydroxyl value of less than 10 caused by reaction one mole of a dimeric fatty acid with 0.1 to 0.99 moles of a glycol having a molecular weight up to 1500 have been produced, as a thixotropic-producing additive for coating agents, in quantities from 0.05 to 10% solved. Preference is given to glycols of the general formula

HO- (CH ₂ CH ₂ O) _n -H

is used, in which / 1 means a number from 1 to 30. In particular, those used according to the invention are used Reaction products used as additives to coating agents based on oil paints.

The reaction is carried out until the hydroxyl value of the reaction mixture is constant Value not higher than 10 reached. The reaction products always consist essentially of Compounds of molecules that have a carboxyl group at both ends and some do not contain reacted hydroxyl groups. These compounds are oily at room temperature and can be easily painted with oil paints such as B. phthalic acid alkyd resins and urethane oils of the oil-modified type or mixed colors. They have a strong preventive effect against dripping or running-off without im to sacrifice some of the gloss of the coated surface.

Dimer acids that door the manufacture of that Drip or run-off preventing agents according to the invention are used, consist of long-chain, aliphatic, dibasic acids with about 36 carbon atoms in the molecule. you will be by polymerizing a natural or synthetic, polymerizable, unsaturated, monobasic Fatty acid having a hydrocarbon chain containing 8 to 24 carbon atoms, usually contains about 18 carbon atoms in the molecule. The polymerization takes place on thermal or catalytic route, using, for example, activated clay as a catalyst. Usually can dimer acids through polymerization of drying or semi-drying oils, free fatty acids or simple aliphatic, alcoholic esters of these acids can be obtained. For example you can use as starting materials those that have a high content of linoleic or linolenic acid exhibit. Suitable drying or semi-drying oils are, for example, soybean oil and linseed oil and cottonseed oil. Usable fatty acids are tall oil and the like In the manufacture of dimeric acids, most aliphatic acids have enough double bonds to to form mixtures of dibasic acids and higher polymerized fatty acids. this happens probably in terms of the Diels-Alder reaction. Examples of polymerization methods for production dimeric acids are described in U.S. Patents 2,793,219 and 2,793,222. In trade available dimer acids consist for the most part of a dimer acid with 36 carbon atoms, which is formed from long-chain, aliphatic, dibasic acids, and a small proportion trimeric acids, similar to a tribasic acid with 54 carbon atoms in the molecule, as well as some higher polymerized, aliphatic acids and something

leftover monomers. The polyethylene glycols, which are used as the coupling group of the dimeric acid molecules, can by polymerization can be obtained from ethylene oxide. These glycols include ethylene glycol, diethylene glycol, Triethylene glycol and higher polyethylene glycols.

From the Japanese patent application 5 332/64 is a method for preventing dripping of Coating agents known, which by the use a polymerized fatty acid or its alkyl ester with 1 to 4 carbon atoms is. The product is obtained by the heat polymerization of an unsaturated fatty acid and consists mainly of a binary acid, which is the oil paint dissolved in petroleum small amounts should be added. In contrast, prevent the reaction products according to Invention, as the comparative experiments given below show, the coating agent drips off to a much better degree, without significantly damaging the gloss. This was door the professional not to be expected.

U.S. Patent 3,429,817 describes a synthetic ester lubricant. To increase the lubricating effect, 0.001 to 4.9 percent by weight of an ester are used here, that by reacting about 2 moles of a glycol having 2 to 5 carbon atoms in the molecule formed with about one mole of a binary unsaturated fatty acid having 18 carbon atoms in the molecule is. Obviously, this ester is one in which the binary acid with a Excess of glycol is implemented. The thixotropic agent of the present invention is however, it is a reaction product of a glycol with an excess of binary acid. Namely, if more than 1 mole of glycol reacts with 1 mole of the binary acid, Jas shows reaction product has a high degree of polymerization, and such an article is for the purposes of the present invention Invention not suitable.

The new agents according to the invention do not require any additional coating of the treated areas. They can be easily mixed with the coating agent without causing blistering and without a kneading process being necessary. The finished surface does not require any post-treatment with the help of a grindstone or the like.

The above-mentioned anti-drip agents according to the invention can be used in certain Quantities are added directly to the coating agent and easily mixed with it to achieve the intended Purpose to achieve. Moves the amount of anti-drip agent to be used usually on the order of 0.05 to 10 percent by weight, preferably 0.1 to 3%. calculated on the total weight of the paint. If a smaller amount of the the drip contraceptive agent as indicated above is the effect achieved in terms of contraception draining is not sufficient. When the amount of the anti-drip agent increases is high, is evident when the coating agent is stored to an undesirably high degree a secretion of the Pigment.

The present invention will be further explained with reference to the following examples.

example 1
1. Synthesis of the anti-drip agent

To 114.4 g (0.2 mol) of a dimer acid, which was prepared by thermal dimerization of linoleic and linolenic acids obtained from soybean oil to form dibasic acids having 36 carbon atoms in the molecule, diethylene glycol was added in various amounts, namely 20.1 g (0.19 mol), 19.1 g (0.18 mol), 17.0 g (0.16 mol), 14.8 g (0.14 mol), 12.7 g (0.12 mol ), 10.6 g (0.10 mol), 8.5 g (0.08 mol) and 4.25 g (0.04 mol) were added. In the presence of an acidic catalyst, each mixture was ^{reacted at 210 °} C. for 3 hours until the hydroxyl value of the reaction mixture assumed a constant value of not more than 10. In this way, eight kinds of test samples of an anti-drip agent according to the invention were synthesized.

2. Making the paint
A mix of

nu »1 ·· λ 11 Ji weight part

Phthalic acid alkyd resin

(calculated on a dry basis) 30.0

Titanium white 6.6

Zinc oxide 13.4

Calcium carbonate 20.0

Solvent 30.0

Desiccant 2.0

was kneaded in a ball mill for 4 hours to make a white color.

3. Try the drip prevention
Means

The white color produced according to 2. was adjusted to a viscosity of 30OcP at room temperature, then each of the above-mentioned eight test samples of the das Contraceptive drip, which was synthesized according to 1., the color in various amounts of 0.1, 0.35 and 0.70%, calculated on the weight of the color composition, were added. The mixes were made carefully stirred and left to stand overnight. Then they were taking education on a test paper of film coatings of various thicknesses, namely 75, 100, 150, 200 and 250 microns. Each test paper was held vertically, and the state of paint bleeding was observed. For the evaluation of the gloss, a coating film of 150 microns thick was placed on a glass plate were formed, and the reflectance values were below the first and seventh days after the film was made measured at an angle of 60 "with a gloss meter.

For comparison purposes, commercially available anti-drip agents, namely a polyethylene wax (comparative 1) and a metal soap (comparative 2) of the same white color were added in amounts of 0.5% based on the weight of the color mass. In addition, the dimer acid alone was added to the paint in an amount of 0.7 percent by weight. The color mixtures obtained in this way were tested in exactly the same way as described above with regard to their dripping effect and their gloss value.

The results are shown in Table 1.

The following measurement system was used as the criterion for evaluating the run-off properties of the test paints applied:

0 = no draining could be determined at all;

1 = the degree of sagging is sr> low that the

Color does not reach the top of the lower step of the test strip;

=

=

=

the dripping or bleeding of the paint reaches the lower level of the test strip to some extent;
dripping is moderate or severe bleeding is evident;
the dripping occurs to a large extent.

As can be seen from Table 1, the anti-dripping agents according to the invention are very effective and do not cause any noticeable decrease in the gloss of the coating film.

table

Test samples of the draining
contraceptive agent

Binding attempt

Test agent 1

Test agent 2

Test agent 3

Test means 4

Test agent 5

Test means 6

Test means 7

Test means 8

Dimer acid ....

Comparison means 1
Comparison means 2

Molar ratio

from dimer

Acid to glycol

1: 0.95 1: 0.9

1: 0.8 1: 0.7 1: 0.6 1: 0.5

.0.4

: 0.2

Added 75 µ crowd 2 1%) 0 _ 0 0.7 0 0.35 0 0.7 0 0.35 0 0.7 0 0.35 0 0.7 0 0.35 0 0.7 0 0.1 0 0.35 0 0.7 0 0.1 0 0.35 0 0.7 0 0.1 0 0.7 0 0.1 1 0.7 2 0.5 0.5

Extent of dripping

2 (X) ■

KX) μ I 50 µ 2 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 1 3 4th 3 3

4th
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1

0
2
1

4th
4th

250;

4th
0
0
0
0
0
0
0
0
0
ί

0
0
1

0
0
1

0
2
1

4th
4th

shine

I. Tau

92.2
91.4
91.5
90.5
90.8
90.0
90.5
89.5
90.2
89.7

91.3
91.2
90.8
91.5
91.4
90.4

91.0
91.0

91.5
90.7
92.5
93.3

7. Taj. 85.2

84.0 84.6 82.5 83.3 80.7 81.6 78.1 80.9 77.3 81.0 80.7 76.7 81.0 80.4 75.5 75.0 74.0 70.3 65.0 87.8 88.6

Example 2

To 114.4 g (0.2 mol) of a dimer acid obtained by thermal dimerization of soybean oil obtained linoleic and linolenic acids was 0.1 mol of polyethylene glycol with a molecular weight of 200, 400, 600, 1000 and 1500 added. There were test samples from the drainage contraceptive agents according to the invention, namely samples Nos. 9 to 13 in the same way as in Example 1 described, synthesized.

Any of the drip-preventing thus prepared Agent was added to a white paint, the viscosity of which was adjusted to 30OcP at room temperature was. The paint was mixed well and left overnight. Then the Paint for its anti-drip effect and gloss in the same way as in Example 1 checked.

For comparison purposes, a commercially available anti-drip agent, namely a polyethylene wax, was used (Comparative agent 1) and a metal soap (Comparative agent 2) each time in amounts of 0.5% the weight of the paint added. The color mixtures thus obtained were exactly the same Way as tested above with regard to their drainage properties and their gloss values.

The results are in TnbcUr- ? rforoMioiii

Tubelle

Test samples close the drainage
contraceptive agent

Blind test ....

Test means 9

Test means 10

Test means 11

Test medium 12

TeslmiUcl 13
Comparative means 1
Comparison means 2

Molckuhir

(! cwk-hl des

Polyalethylene

glycol

200

400

600

1000

1500

Molvcrliältiiis /ι,.- by dimerir sct / lc Acid / n (ilycol crowd 1: 0.5 0.7 1: 0.5 0.7 1: 0.5 0.7 1: 0.5 0.7 1: 0.5 0.7 0.5 0.5

Coloring the drip off

2
0
0
0
0

ItH) μ 15 »:» 2 (K) u 2 3 4th 0 0 0 0 0 0 0 1 I. 1 2 3 2 3 3 3 4th 4th 3 3 4th

dian /

(I] I I. Tap 7th day 4th 92.2 85.2 0 92.0 79.7 0 88.9 76.1 1 89.5 79.5 3 88.4 78.7 3 84.7 74.0 4th 92.5 87.8 4th 93.3 88.6

As can be seen from Table 2, show the anti-drip agents according to the invention extraordinary effects without noticeable loss of shine.

Example 3

.1 °

To 114.4 g (0.2 mol) of a dimeric acid, which by thermal dimerization of linoleic and linolenic acids derived from soybean oil was obtained. 6.2 g (0.1 mol) of ethylene glycol were added and thus a drip preventing agent (experimental agent 14) in the same way as in the example! 1 indicated synthesized.

The agent obtained in this way was added to a white paint which had a viscosity of 30OcP Room temperature was set in an amount of 0.35% based on the weight of the paint. To Mixing it carefully and leaving it to stand overnight, the paint was drained and drained off Gloss tested in the same way as in Example 1. For comparison purposes, commercially available that Dripping preventive agents, namely a polyethylene wax (comparative agent 1) and a metal soap (comparative agent 2) each time added in an amount of 0.5% based on the weight of the paint. The so obtained Samples were tested for drainage in exactly the same manner as described above their gloss values checked. The results are shown in Table 3.

table

Test samples of the draining
contraceptive agent

Blind test
Test means 14
Comparison means 1
Center of comparison] 2

Mole ratio

by dimcrer

Acid to glycol

. : 0.5

Amount added

0.35

0.5

0.5

As is clear from Table 3, the anti-drip agent according to the present invention has Invention has a very significant effect and yet does not cause a noticeable decrease in gloss of the coating film.

Example 4

A crowd out

Part of the weight of phthalic acid alkyd resin (on

Dry matter calculated) 30

Lead yellow ⁸

75.

Extent of dripping

3
3

1 50 µ

3
0
4th
3

200 ι

4th
0

4th
4th

250 µ

4th
0

4th
4th

Glan /

I. day

92.2
92.0
92.5
93.3

7th day

85.2
86.2
87.8
88.6

Parts by weight

Prussian blue 1.3

Calcium carbonate 30.7

Solvent 30

Desiccant 2

was mixed in a ball mill for 4 hours to make a green color. She was in her Viscosity adjusted with a diluent to 30OcP at room temperature. A draining contraceptive agent (experimental agent 6), which is obtained by reacting one mole of a dimeric acid with 0.5 mole

609 616/121

Diethylene glycol was obtained, the paint was in an amount of 0.35% based on the weight of the paint added. After mixing thoroughly, the mixture was allowed to stand overnight. then their drip effect and gloss on the coating film were determined in the same manner as in Example I. described, checked.

For comparison purposes, commercially available anti-drip agents, namely a polyethylene wax (Comparative agent I) and a metal soap (

Equalizer 2) each time in amounts of 0.5%, calculated on the weight of the paint, added. then the mixtures in exactly the same way, as described above, for their drainage and their gloss values checked.

The results are shown in Table 4.

As can be seen from Table 4, the anti-dripping agent according to the invention has an excellent one Effect and causes almost no loss of gloss.

Table 4

Test samples of the draining
contraceptive agent

Blind test

Test means 6

Comparison means I
Comparison means 2

Moivcrhiiltnis

by dimcrer

Acid /.u cilvkol

/ ugcscl / tc amount

0.35

0.5

0.5

Color in the dropper

75;, H) II. 150., 2 (N) ι I. ■) 3 3 0 0 1 2 I. 1 T 3 I. 2 3 3

250:

3
3

(iliin /

I. day

93.7
92.7
86.2
77.2

7 day

86.8
90.8
85.0
73.8

Example 5 A mass of

r- »i- * i_ ι ■ - Ail JL Gewichistoile

Phthalic acid alkyd resin

(Dry weight) 30

Titanium white 16.0

Zinc oxide 16.0

Carbon black 2.0

Calcium carbonate 6.0

Solvent 30

Desiccant 2

was mixed in a ball mill for 4 hours to make a gray color. Your viscosity was adjusted to 30OcP at room temperature with a diluent. A draining agent (Test formula 6), which is obtained by reacting one mole of a dine acid with 0.5 mole of diethylene glycol

"ηΊ ο ^{Cn Was} ' ^{WUrdc the color in cincr Men} S ^{e of} 0 35%, calculated on the weight of the color, added.

After mixing thoroughly, the mixture was allowed to stand overnight. She was then drained on her and their gloss on the coating film in the

- »in the same way as in the example! I described, checked. For comparison purposes, commercially available anti-drip agents, namely a polyethylene wax (Comparative agent 1) and a metal soap (comparative agent 1) 2) m amounts of 0.5%, by weight

added to the color, and these mixtures were tested for their drainage and gloss values in exactly the same way as described above checked. The results are shown in Table 5.

Table 5

Test samples of the draining
contraceptive agent

Blind test

Test means 6

Comparison means 1
Comparison means 2

Molar ratio

by dimcrer

Acid to glycol

1: 0.5

Amount added

0.35

0.5

0.5

Extent of dripping

75; x 1 I 5 (1 _: i 2 (K); j 0 0 2 3 0 1 0 1 0 1 3 3 0 3 3

250 ,

Cilan /

I.Tiig

88.6
88.1
83.9
73.1

7th day

85.7
83.8
78.0
66.8

11 12

As can be seen from Table 5, the drip-off preventive agent (test agent 6),

Contraceptive agents according to the present invention that by reacting one mole of a dimer acid

an excellent effect and caused practically obtained with 0.5 mol of diethylene glycol, became the

no decrease in the gloss of the coating film. Color in an amount of 0.35%, on the color

5 calculated weight, added. After careful

Example ο mixture, the mixture was left to stand overnight.

Fine mixture of (iewiLhisieik · She was then drained on her and her

. _{,,, y <l} ,,,. Gloss on the oil coating film in the same way,

with urethane converted oil 350 _{wje jm Bcispje,, describedi tested}

Λ itanweilJ -. _{(Q For} comparison purposes, commercially available, das

Zinc oxide _3 anti-drip agent, namely a polyethylene

Calcium carbonate wax (comparative agent 1), a metal soap (comparative

Losungsmittc l U _{MUI, 2) and ejn po} i _y merisiertes oil (comparison means 3)

⁷ rocking agent ö each time in amounts of 0.5%, based on the weight of the paint

was added in a ball mill for a good 15 hours for 4 hours. Then the mixes were made

mixed to obtain a urethane color. on their draining effect and their gloss values in exactly

It was checked for viscosity with a thinner in the same manner as described above.

medium adjusted to 300 cP at room temperature. The results are shown in Table 6.

Table 6

Disproportion
from dimer Added 75 µ Coloring. of draining 2 (K) μ 250 µ shine 1st day 7th day Acid to Glycol crowd 1 4th 4th 64.9 62.4 <%> 0 100;. 1 50; i 0 0 44.1 42.7 0 1 3 4th 4th 41.6 38.7 1: 0.5 0.35 0 0 0 3 3 37.0 35.2 - 0.5 0 1 3 3 3 25.7 23.2 - 0.5 1 I. 0.5 I. 1

Test samples of the draining
contraceptive agent

Blind test

Test means 6

Comparison means I

Comparison means 2

Comparison means 3

As can be seen from Table 6, the anti-drip agent according to the present invention exercises has an excellent effect and causes a relatively small loss of gloss compared with the decrease in gloss that results from the addition of the other anti-dripping agents.

Claims (2)

Patent claims: 1. Use of terminal carboxyl groups having reaction products with a constant hydroxyl value of less than 10 obtained by converting one mole of a dimeric fatty acid with 0.1 to 0.99 mol of a glycol having a molecular weight up to 1500 have been used as a thixotropic additive for coating agents, in amounts of 0.05 to 10%. 2. Use of terminal carboxyl group-containing reaction products with a constant hydroxyl value of less than 10 obtained by reacting one mole of a dimeric fatty acid with 0.1 to 0.99 mol of a glycol of the general formula