HU196620B - Process for producing alkyd resins with modified surface coating and their solutions - Google Patents

Abstract

The process according to the invention is characterized in that from 1 to 17 parts by weight of a modifying mixture of 1-17 parts by weight of an alkyd resin having a viscosity of 50% by weight of xylene in a 50% by weight xylol solution of 10 to 30 mg KOH / g is added at a temperature of 130150 ° C. 13 parts by weight of a mixture of 230260 epoxy equivalent epoxidized oil, 0.2 to 2 parts by weight of dimeric acid such as C 36 unsaturated dicarboxylic acid and 0.2 to 2 parts of alpha or beta-branched monocarboxylic acid, 350-400 mg KOH / g, 0-0 Addition of 1 part by weight catalyst, such as para-toluenesulfonic acid, the mixture is reacted at 150-180 ° C for 3-25 mg KOH / g acid and 50% xylene solution for a viscosity value of 400 to 1600 mPas, and optionally 130 100 parts by weight of resin melt at -160 ° C are diluted with 40-100 parts by weight of solvent. -1-

Description

FIELD OF THE INVENTION The present invention relates to the preparation of alkyd resins having a surface-modifying surface layer and their solutions which, when used in combination with a polyisocyanate or an aminoporaldinic acid resin, provide a coating having a particularly good chemical resistance.

Alkyd resins, unmodified, which are polyesters of polycarboxylic acids, polyalcohols and monounsaturated fatty acids, are not chemically resistant. This is because of the easy saponification of the ester bonds in the molecule structure and the presence of unreacted hydroxyl and carboxyl groups, which are considered defective sites.

In order to increase the chemical resistance there is, on the one hand, the stabilization of ester bonds, e.g. spatial shading and, on the other hand, reducing the number of defects by subsequent reaction, which can occur in the extreme case of coating formation.

There are many examples in the literature of improving quality for this purpose.

Thus, a known method for protecting ester bonds is the incorporation of branched chain carboxylic acids into the molecule. Just as these branching blocks prevent the formation of ester linkages as well as prevent their formation, the preparation of such alkyd resins requires a special procedure.

The usual method is the incorporation of verzatika acid as a glycid ester.

Such a process is described in Hungarian Patent No. 156,603.

Hungarian Patent No. 162,217 discloses the use of a catalyst for the incorporation of a branched carboxylic acid, whereas the process disclosed in Hungarian Patent No. 170,793 solves the above problem by preferentially reacting these difficult-to-integrate components. A common disadvantage of the described processes is the use of expensive starting materials and their use in relatively large amounts, but the technological process is also quite complicated.

Elimination of another group of defective sites - unreacted hydroxyl and carboxyl groups - is another way to improve chemical resistance. Possible reaction partners are primarily epoxy and isocyanate compounds.

In principle, the reaction can take place during the coating formulation, when the added polyepoxy or polyisocyanate compound acts as a crosslinking component.

In practice, this latter method is used and the resulting coating is considered to be polyurethane.

In particular, it is a particular embodiment where blocked polyisocyanate is used (Japanese Patent Application Laid-Open No. 7411278, Hungarian Patent Application No. 181,174).

A well-known way of modifying alkyd resins is to produce epoxy-modified alkyd resins and urethane alkyds. (Pocket Book of Varnish and Paint 1982 Bp. Technical Publisher), we can conclude that there are several ways to improve the chemical resistance of alkyd resins and coatings made with them, but de g

these solutions do not always give satisfactory results.

In our experimental work we have aimed to improve the properties of the coating formed by alkyd resins by reacting f with its free hydroxyl group. |

In our procedure, a three-member modifier com. | ponens combination: the presence of epoxidized oil, branched t-monocarboxylic acid and dimerized fatty acid - provides the unexpected effect. í

In our work we sought a solution which, compared to the methods known so far:

- more economical, ~ more reproducible, using simple technology.

The alkyd gum useful in the process of the present invention is prepared by 25-36 parts by weight of fatty acid or triglyceride, preferably sunflower oil fatty acid, tall oil fatty acid and / or ricinoleic triglyceride, and 22-29 parts by weight of polyalcohol such as ethylene glycol, diethylene glycol, pentaerythritol and 33-38 parts by weight of dicarbolic acid anhydride, such as phthalic anhydride, at 180-220 ° C with xylene azeotropic water removal, 10-30 mg KOH / g acid and 50% w / w xylene solution at 20 ° C. —Activity is achieved up to a viscosity of 1200 mPas. Then, the alkyd resin melt thus obtained is cooled to 130-150 ° C and 1 to 13 parts by weight of an epoxidized oil having a molecular weight of 230 to 260 and a molecular weight of 940 to 950, preferably epoxidized soybean oil and 0.2 to 2 parts by weight of dimeric acid. aliphatic dicarboxylic acid containing at least four double bonds and from 0.2 to 2 parts by weight of a monocarboxylic acid having an acid number of 350 to 400 mg KOH / g, preferably alpha-ethylhexanoic acid or beta-beta-dimethyl octanoic acid and 0-0.1 of a catalyst such as paratoluene sulfonic acid and 150-180 ° C at 325 mg KOH / g acid and 50% xylene solution at 20 ° C to a viscosity of 400-1600 mPas, then 130-160 After cooling to 100C, 100 parts by weight of the resin melt is diluted with 40-100 parts by weight of solvent, preferably xylene, butyl alcohol, ethylene glycol, monobutyl ether and A solution of an alkyd resin in combination with a polyisocyanate or aminophonaldehyde resin is used as a binder in the preparation of a paint coating agent.

The resulting coating has a significantly better chemical resistance than the unmodified base resin coating and improves the coating's flexibility and resistance to temperature changes.

All of this improvement is believed to be due to the incorporation of the three-membered modification system, epoxidized oil, branched monocarboxylic acid and dimerized fatty acid.

It is believed that the presence of epoxiesopoft provides a better bond between the carboxylic acids and the base resin.

The dimerized fatty acid tube monocarboxylic acid to each other and the ratio of the total amount thereof to the epoxidized oil controls the viscosity value.

-2196,620

The incorporation of branched monocarboxylic acid and epoxidized oil increases chemical resistance and the presence of dinerified fatty acid increases elasticity.

When the modifying components are incorporated into the resin, an additive reaction occurs and a protective layer is formed on the surface of the alkyd resin.

This explains why the modifiers (1-17% by weight), despite their amount, surprisingly greatly increase the resistance of the final product and the change in temperature as well as its elasticity.

The dimeric acid used in the resin is a C 36 unsaturated dipharboxylic acid prepared by dimerization of unsaturated C 18 fatty acids.

The process according to the invention is economical and easy to carry out precisely because of the small amount of modifying components.

Thus, according to the invention, 8399 parts by weight of a 10 to 30 mg KOH / g acidic acid solution having a viscosity of 400 to 1200 mPas in 50% by weight with 1 to 17 parts by weight of a modifying mixture are cpoxidized oil, dimeric acid and alpha or beta. with a mixture of branched fatty acids at 150-180 ° C, optionally in the presence of a catalyst, to give an acid number of 3-25 mg KOH / g. Then dilute.

However, the advantageous effect of the present invention is achieved only if the above-mentioned step of the procedure is followed and the modifying agent is added to the finished resin. .

The following examples illustrate the process of the invention.

Quality characteristics of the resin solution:

non-volatile (MSZ 9650/8) viscosity, acid number at 20 ° C (on a Höppler's reo viscometer)

50.4% by weight

1310 mPas 3.8 mg KOH / g

Example 1 (b)

Preparation of unmodified alkyd resin solution

In the reactor described in Example 1 (a), an alkyd resin solution is prepared as described therein without the addition of the modifying components used in Example 1 (a):

101.9 parts by weight

180.2 parts by weight

179.9 parts by weight 40.0 parts by weight

336.2 parts by weight 740.0 parts by weight castor oil, tall oil fatty acid, glycerol dictylene glycol, phthalic anhydride, xylene

Quality characteristics of the resin solution: (non-volatile (MSZ 9650/8) at 120 ° C, viscosity at 20 ° C for 2 hours (Höppler's reo-osmosis)

50.2% by weight

1190mPas

10.2 mg KOH / g

Example 1 (a)

Preparation of the modified alkyd resin solution of the invention

Weigh into a heated reactor equipped with a stirrer, inert gas inlet, thermometer and azeotropic water separator

10.19 parts by weight of castor oil,

18.02 parts by weight of tall oil fatty acid,

17.99 parts by weight of glycerin,

4.00 parts by weight of diethylene glycol and

33.62 parts by weight of phthalic anhydride.

An alkyd resin having an acid number of 15 mg KOH / g was prepared at 180-190 ° C with xylene azeotropic degreasing. The resin melt was cooled to 150 ° C and added

12.22 parts by weight of epoxidized soybean oil (epoxy equivalent: 260)

2.16 parts by weight of dimeric acid (C 36 unsaturated dicarboxylic acid from U-E Chemicals GmbH, DE)

1.80 parts by weight of beta-beta dimethyl octanoic acid.

The temperature is raised to 180 ° C and the reaction is continued until an acid value of about 4 mg KOH / g is reached and then cooled to 180 ° C.

94.00 parts by weight of xylene are prepared in a 50% solution.

Example 1 (c)

Preparation of alkyd resin solution prepared with modifying components

In the reactor described in Example 1 a), an alkyd resin solution was prepared at 180-190 ° C as described therein, except that all of the components of Example 1a were reacted in one step.

Quality characteristics of the resin solution: non-volatile (MSZ 9650/8) 120 ° C, 2 hours viscosity at 20 ° C (Höppler's reoviscometer) acid number

50.2% by weight

1200 mPas 12 mg (KOH / g

For the comparison of resin solutions, a two-component polyurethane dye coating material is prepared according to the following composition:

The component resin solution is titanium dioxide, rutile xylene

70.0 parts by weight 22.0 parts by weight

5.0 parts by weight

100.0 parts by weight

196,620

Component B is an aromatic polyisocyanate (75% w / w in ethyl acetate) toluene

50.0 parts by weight

50.0 parts by weight 100.00 parts by weight 5

Mixing ratio: 2 parts by weight Component A: 1 part by weight component B.

The comparative quality characteristics of the developed paint coatings are summarized in the following table:

1. (a) The invention comprises a synthetic resin solution 1. with reference resin solution (b) 1. c) comparative gynata solution Drying time at 20 ° C, MSZ 9640/23) 1st grade 20 minutes 20 minutes 20 minutes 7th grade 24 hours 24 hours 24 hours hardness, after 7 days (MSZ 9640/2, pencil) 3 H 3 II 3H elasticity, mm (MSZ 9640/6) Erichsen 8.7 mm 6.1 mm 6.2 mm elasticity (MSZ 9640/5) 2 mm 5 mm 5 mm bending Grip with grid cutter (MSZ 9640/25) grade on ungrounded sheet steel I 5 5 on a primed plate 0 2 1 chemical resistance (MSZ 9640/28) drop method, after 2 hours isobutyl acetate H 10 H'7 H5 immersed after 8 hours unchanged small blisters small, dense blisters toluene F 10 F6 F5 unchanged lemattul lemattul

Comparing the results, it can be seen that the material prepared by the process of the invention is more advantageous in terms of adhesion, flexibility and chemical resistance.

It can be stated that if the modifying components are not added in the order according to the process of the invention but are used as starting material 45, virtually no positive change is obtained.

Preferably, the binder coating material of the present invention is useful for protecting metal and wood surfaces, particularly chemical equipment.

They can be used advantageously in all cases where the use of heat-curing enamel paints would be desirable, but the size and material of the object or equipment do not allow the firing.

Example 2 a), 60 Preparation of the modified alkyd resin solution of the invention

The production apparatus described in Example 1 is weighed: 65

25.59 parts by weight of tall oil fatty acid,

6.50 parts by weight of ethylene glycol,

8:50 dietilénglikoh parts 13.93 parts 38.00 parts of phthalic anhydride, pentaerythritol, and a temperature of 200-210 ° C with xylene azeotropically removing water from 18 mg KOH / g acid number is reached the reaction components were added after cooling to 140 ^e C:

5.94 parts by weight of epoxidized soybean oil,

0.74 parts by weight of dimeric acid (Example 1)

1.10 parts by weight of alpha-ctylhexanoic acid.

The reaction was then continued at 150 ° C until a viscosity of 15-18 mg KOH / g acid and a viscosity of 1500-1600 mPas in 50% xylene solution was achieved, and the resin melt was dissolved in 92.0 parts by weight of xylene.

Quality characteristics of the resin solution Non-volatile material (MSZ 9650/8/120 ° C, 2 hours) Viscosity, acid number at 20 ° C (Höppler's reoviscometer)

50.3% by weight

1580 mPas

15.6 mg KOH / g

-4ί

196,620

'.0

Example 2 (b)

Preparation of a solution of unmodified alkyd resin

In the production apparatus described in Example 1 a), θ is prepared as described therein, but without the modifying components described in Example 2 a).

The composition is as follows:

25.59 parts by weight of tall oil

6.50 parts by weight of ethylene glycol,

8.50 parts by weight of diethylene glycol,

13.93 parts by weight of pentaerythritol,

38.00 parts by weight of phthalic anhydride, ¹⁵

82.00 parts by weight of xylene

Comparing the results, it can be concluded that the coating material made with the alkyd resin binder of the present invention exhibits improved chemical resistance and flexibility.

The coating is well suited for painting hospital equipment.

Example 3

3. (a)

Preparation of a modified alkyd resin solution of the invention

The manufacturing apparatus described in Example 1 is weighed:

Quality characteristics of the resin solution: non-volatile material 50.1% by weight (MSZ 9650/8) at 120 ° C, viscosity for 2 hours, 1430 mPas (Höppler's reoviscometer) at 20 ° C acid value 16.3 mg KOH / g

For comparison of the two resin solutions, an alkydamine combination heat-curing paint coating composition is prepared with the following composition:

resin solution 65 parts by weight of etheric niclamine-fornialdehyde resin 13 parts by weight of iron oxide-red pingment 10 parts by weight of iron oxide-yellow pigment 12 parts by weight of iron oxide-black pigment 3 parts by weight of isobutanol 7 parts by weight

100 parts by weight

The ink coating is formed by firing at 120 ° C for 30 minutes.

The comparative quality characteristics of the paint coatings are summarized in the following table:

1.55 parts by weight 35.94 parts by weight 16.06 parts 9.45 parts by weight 35.32 parts by weight castor oil, distilled sunflower fatty acid glycerol pentaerythritol and phthalic anhydride and polycondensation at 210-220 ° C until 28 mg KOH / g acid.

Cool the resin melt to 130 ° C and add:

1.26 parts 0.21 parts 0.21 parts 0.10 parts cpoxidised soybean oil, dimeric acid (Example 1), alpha-eralhexanoic acid and para-toluenesulfonic acid

The mixture was reacted at 160 ° C for 12 minutes and then cooled to 120 ° C.

15.5 parts by weight of ethylene glycol monobutyl ether and

25.5 parts by weight in a solvent mixture of n-butanol.

2. a) The alkyd resin of the present invention is a binder 2. (b) a binder made by conventional means of alkyd resin Hardness with pencil (MSZ 9640/2) 4H. 4H Flexibility. Erichsen (MSZ 9640/6) 6.2 mm 4.4 min Grip with grid cutter (MSZ 9640/25), grade 0 1 chemical with swabs of benzine, Rubbed with a load of 500 g ten times unchanged the cotton wool was slightly discolored Immersed in 100 ° C water for 1 hour versions H 9 small blisters

196,620

Example 3 (b)

Example 3 (d)

Preparation of the modified alkyd resin solution of the invention

Example 3 a) was carried out, but the amount of paratoluenesulfonic acid added was 0.05 parts by weight.

Preparation of unmodified alkyd resin solution

In the production apparatus described in Example 1a, an alkyd resin solution is prepared as described therein. such that the modifying components of Example 2 a) are not added.

Composition:

Example 3 (c)

Preparation of the modified alkyd resin solution of the invention

Example 3 a) was carried out but paratoluenesulfonic acid was not added.

1.55 parts by weight 35.94 parts by weight 16.06 parts by weight 9.45 parts by weight J5.00 parts by weight castor oil distilled sunflower oil fatty acid glycerol pentaerythritol phthalic anhydride ethylglycol monobutyl ester, n-butanol

Quality characteristics of resin solutions 3 (a) to (d)

3. (a) 3b) made according to the invention 3. c) 3, d) made in the traditional way Not a volatile substance 120 ° C, 2 hours, t% (MSZ 9650/8) 69.3 69.2 69.3 69.3

Viscosity at ° C, mPas (Höppler's reoviscometer

reoviszkoziméter) 690 780 850 670 Acid number, mg KOH / g 24.3 26.1 27.8 27

For comparison of the resin solutions, an alkydamine combination acid hardening paint coating composition is prepared with the following composition:

Lacquer:

resin solution 38.5 parts by weight of esterified melamine-formaldehyde resin 10.5 parts by weight of ethyl alcohol 8.5 parts by weight of xylene 20.0 parts by weight of ethylene glycol monoethyl ether 6.5 parts by weight of n-butyl alcohol 6.0 parts by weight

100.0 parts by weight

Coach:

para-toluenesulfonic acid 26.0 parts by weight n-butyl alcohol 40.0 parts by weight ethylene glycol monoethyl ester 34.0 parts by weight

100.0 parts by weight

Mix ratio:

part by weight varnish: 1 part by weight hardener

The comparative quality characteristics of hardened lacquer and finished lacquer coatings are summarized in the following table:

-611

196,620 f:

3. (a) 3. b) 3. c) an alkyd resin of the invention bonded 3. d) alkyd resin binder prepared in conventional manner Pot time, 20 ° C, hour 96 96 96 72 Drying speed at 20 ° C, hardness (pendulum) (MSZ 9640/4)% After 2 hours 37 39 40 42 after 4 o'clock 57 58 58 60 After 24 hours 71 71 72 72

Chemical resistance drip method,

After 2 hours (MSZ 9640/28) 50% Ethyl Alcohol ' F 10 F 10 F 10 F8-9 petrol F 10 F 10 F 10 F9 5% soda solution F 10 - H 10 F 10 -H 10 F 10 -H 10 F9 II9 The temperature has changed. durability (MSZ 9640/23) 26 cycles 24 cycles 24 cycles Article 16

Comparing the results, it can be concluded that the chemical resistance, the temperature change resistance is improved and the useful life increases with the modification according to the invention.

The role of the use of para-toluenesulfonic acid catalyst is surprising. With the same reaction parameters, increasing the amount of the catalyst simultaneously decreases the viscosity and the acid number, but there is no difference in the coating properties with the change of the volume ratio.

Claims (4)

Claims A process for preparing an alkyd resin having a modified surface layer or, if desired, a solution thereof, wherein the alkyd resin has a viscosity of from 400 to 1200 mPas in an amount of from 10 to 30 mg KOH / g in an acidic solution of 50% w / w xylene. 1 to 17 parts by weight of a modifier mixture which is 1 to 13 parts by weight of 230 to 260 epoxy equivalents of epixidized oil is added at temperature C, 0.2 to 2 parts by weight of a mixture of aliphatic dicarboxylic acid containing at least one unsaturated bond of 36 carbon atoms and 0.2 to 2 parts by weight of alpha or beta branched monocarboxylic acid having an acid number of 350 to 400 mg KOH / g, and 0 to 0.1 parts by weight with the addition of a catalyst such as p-toluenesulfonic acid, the mixture is reacted at 150-180 ° C in a solution of 3-25 mg KOH / g acid and 50% w / w xylene to a viscosity of 400-1600 mPas. 100 parts by weight of the resin melt at 130-160 ° C are diluted with 40-100 parts by weight of solvent. 2. The process of claim 1 wherein the epoxidized oil is epoxidized soybean oil. ⁴⁰ The process according to claim 1 or 2, wherein the branched monocarboxylic acid is alpha-ethylhexanoic acid or beta-beta-dimethyl octanoic acid. 4. Process according to any one of claims 1 to ⁴ , characterized in that the solvent is xylene, butyl alcohol, ethylene glycol, monobutyl ether.