DE1260659B - Polymerizable coating agent - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09d

German class: 10 p.m. - 3

Number: 1 260 659

File number: J 19749IV c / 22 h

Filing date: April 14, 1961

Open date: February 8, 1968

The present invention relates to a polymerizable coating agent, which consists of a / ^ - unsaturated ether, an unsaturated polyester resin and a polymerization catalyst.

The known solvent-free coatings or paints based on unsaturated polyesters contain peroxide catalysts which cause the final hardening of the coating. Such Peroxide catalysts are not contained in the coating composition according to the invention. As a result of special composition of the coating agents, these have the advantage that they are excellent Have drying properties and are completely polymerizable compared to the known paints are.

According to the invention, the polymerizable coating agent consists of a ^ -unsaturated ether, the aliphatic or aromatic one containing at least three unsaturated ether substituents is polyhydroxylic compound, and the polymerization catalyst consists of a metal salt dryer.

The viscosity of the coating compositions proposed by this invention depends to a large extent on the molecular weights of the polyester resin used in the composition of matter and the Polyether compound. The viscosity of these masses can be polymerizable or volatile by adding non-polymerizable solvents are lowered. Suitable solvents for degradation The viscosity of these compositions are styrene and vinyl toluene and aromatic hydrocarbons as well Ester solvents.

Preferably the polyether compound employed in this invention has a molecular weight between 200 and 5000.

The polyether compound can expediently be produced in a manner not claimed here by joint reaction of a / 5, y-alkene halide, such as allyl chloride, with a polyhydroxyl compound such as polyglycerin.

Other / ?, γ-unsaturated compounds, such as derivatives of 2- and 3-methallyl, ethallyl, chlorallyl, Crotyl and cinnamyl alcohols can be reacted with polyhydroxy compounds, which three or contain more hydroxyl groups per molecule, such as pentaerythritol or polyglycerol.

Polyether compounds suitable for use in the present invention are allylated polyglycerin, Mannitol allyl ether, sucrose allyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, Polymerizable coating agent

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr
and Dipl.-Ing. S. Staeger, patent attorneys,
8000 Munich 5, Müllerstr. 31

Named as inventor:

Alan James Backhouse, Windsor, Berkshire;

Leonard Louis Pearson,

Ronald Lambourne,

Slough, Buckinghamshire (UK)

Claimed priority:

Great Britain 14 April 1960 (13 443)

Glyceryl triallyl ether and pentaerythritol triallyl ether crosslinked with hexamethylene diisocyanate.

Allyl ethers formed by adding allyl alcohol to epoxy groups can also be used, provided that the number of allyloxy groups is not less than three per molecule. Esters of the reaction products of allyl alcohol and propylene or ethylene oxide can be used, such as tetra (allyloxyethyl) pyromellitate. Likewise suitable compounds are the phthalate or adipates of 3-allyloxy-4-hydroxy-butene-1 (from butadiene monoxide and allyl alcohol).

The polyester resins preferred for use in the present invention are made from maleic and Phthalic anhydrides and a glycol such as propylene glycol. Other unsaturated dibasic Acid anhydrides or acids such as fumaric or itaconic can be used in place of or together with Maleic acid can be used. Likewise, other unsaturated dibasic anhydrides or acids, such as isophthalic or adipic, can be used in place of or together with phthalic anhydride. Preferably the weight ratio of unsaturated to saturated acid in the polyester resin is between 1: 2 and 4: 1.

Suitable glycols are ethylene, propylene, butylene, diethylene glycol and monoglycerides of drying or non-drying oils.

809 507/640

3 4

The polyether compound and the polyester resin, B e i s ρ i e 1 1

which are used in this invention,

can with or without polymerizable or non-2 parts of an unsaturated polyester resin, which

mixed polymerizable solvents and the resulting from maleic anhydride (3 mol), phthalic acid Solidify the composition to form a 5 hydride (1 mole) and propylene glycol (4.4 moles) dry film after the addition of a suitable catalyst and up to an acid number of 35 mg KOH each are hardened. Grams condensed were allylated with 1 part

The weight ratio of the at least three un-polyglycerol (iodine number 220, 5.0% OH, viscosity saturated ether substituents per molecule containing 45 seconds in B. S. B. 3 cup at 25 ° C, molecular polyether compound The preferred weight for polyester resin is approximately 4000) and 1 part butyl acetate for wise between 1: 1 and 1: 4. These materials contain further diluted paints. Cobalt naphthenate usually no polymerizable solvents. solution (containing 6% cobalt metal) was in a If dilution is required, do not use an amount of 1.6% based on the total weight of the polymerizable solvents, such as esters and aromatic-reactive components, added as dryers matic hydrocarbons. 15 and spread the mass on a wooden panel. the

With these masses, the catalyst is a single mass, had a "dust-free" state after metal salt dryer or a mixture of metal 2 ¹ J ₂ hours and was dried over night (16 hours salt dryer. Furthermore, a compound or at 25 ⁰ C) was solid dried , compounds can be added, which on.

the effect of the metal dryer has a synergistic 20 Example 2

Have an effect; 1 part of the unsaturated described in Example 1 belongs to such compounds

Dibutyl hydrogen phosphate. Examples of such polyester resin was also 1 part of the im Dryer catalysts are cobalt salts, such as allylated polyglycerol naphthenate described in Example 1, a mixture of manganese and lead mixed with 1.0% of a cobalt naphthenate solution naphthenates and a combination of vanadium-25 (containing 6.0% cobalt metal). the naphthenate and dibutyl hydrogen phosphate. The amount of mass that has the appropriate viscosity for paint vanadium salt and phosphate ester ranges from 0.025 to purpose was painted on a wooden panel 0.1% (expressed as metal) and 0.15-0.5%, and went "dust free" in 4 hours and was over based on the total weight of polyester resin, dried overnight, and polyether compound. 30th

The metal salt catalyst dryer can be made to the compositions of Example 3

be added a few weeks before use. The 2 parts of an unsaturated polyester resin, which

Stability of the masses is further improved if they are made from maleic anhydride (3MoI), phthalic anhydride stabilizers are added, for example 4% hydride (1 mol) and propylene glycol (4,4MoI) her dipentene, 9% bornyl acetate or 10% nitropropane, 35 and up to an acid number of 35 mg KOH each expressed as percent by weight of the mass. Gram was condensed, 1 part mannitol

The technical progress of the mixed allyl ethers according to the invention (iodine number 277, 13% OH) and paint consists in the fact that these are immediately applied to a base with 1 part of butyl acetate for painting purposes, diluted with a brush. 1.4% cobalt naphthenate solution (containing can be applied, whereby coatings ins- 40 6% cobalt metal) were added, based on the particular reactive components obtained for decorative purposes, as a dryer, and can that very quickly get a dry surface Painted mass on a wooden panel. Give it and dry it out within a few hours. It was found that the mass was "dust-free". The painter can use these paints without hurry in 4 hours and work overnight (16 hours, and the paints obtained are the ones 45 at 25 ° C) had dried firmly. comparable to the known ones with peroxide “. · Λ λ

catalyzed masses are obtained, but in which B e 1 s ρ 1 e

the paints before processing the per- 4 parts of an unsaturated polyester resin, which

oxide catalyst must be added. These consist of maleic anhydride (0.95 mol), phthalic acid Paints must immediately after addition 50 anhydride (0.05 mol), propylene glycol (0.8 mol) and the catalyst can be processed by spraying. the monoglyceride of coconut oil fatty acid (0.3 mol)

In addition, the paints prepared in accordance with and have an acid number of up to 35 mg KOH of the invention had a better shelf life than per gram condensed were with 2 parts Paints to be catalyzed by the addition of peroxide, mixed allylated polyglycerine (molecular weight which gel a short time after the addition of peroxide, 55 approximately 4000, iodine number 220, 5% OH, viscosity so that they cannot be kept. Dem- 45 seconds in B. S. B. 3 cup at 25 ° C) and with 1 part on the other hand, as already mentioned, the paint xylene can be further diluted for paint purposes. 1.6% Keep masses according to the invention for a long time, especially cobalt naphthenate solution (containing 6% cobalt, especially if a stabilizer such as dipentene, metal) is added, based on the total weight of the compound will. 60 action components were added as a dryer.

All of the coating materials proposed according to the invention were painted onto a wooden panel. It with known non-reactive substances, it was found that they produce a "dust-free" Pigments are pigmented. State had reached and overnight (16 hours

The invention is solidly dried by the following at 25 ^° C.). games explained, parts are by weight. 65.

The term "dust-free" as used here, Example 5

relates to the earliest point in time when drying 2 parts of an unsaturated polyester resin, which

Film in which dust does not adhere to the surface. from fumaric acid (3 mol), phthalic anhydride (1 mol),

Propylene glycol (4.4 mol) was produced and condensed up to an acid number of 45 mg KOH per gram, 1 part allylated polyglycerine (iodine number 240, 3.0% OH, viscosity 30 seconds in 3 cup BOD at 25 ⁰ C) mixed and further diluted with 1 part 5 butyl acetate for painting purposes. Cobalt naphthenate solution (containing 6% cobalt metal) in an amount of 1.6%> based on the total weight of the reaction components, was added as a dryer, and the mass was spread onto a wooden panel. It turned out that it reached a "dust-free" state after 2 ¹ J ₂ hours and was solid dried overnight (16 hours at 25 ° C).

Examples

2 parts of an unsaturated polyester resin, which was prepared from maleic anhydride (3 mol), phthalic anhydride (1 mol) and propylene glycol (4.4 mol) and condensed to an acid number of 35 mm KOK per gram, were ally zo lated with 1 part Polyglycerin (iodine number 240, 3.0% OH, viscosity 30 seconds in 3 cup BOD at 25 ^° C.) and diluted further with 1 part of butyl acetate for painting purposes. Vanadium naphthenate solution (containing 6% vanadium metal) in an amount of 0.83% based on the total weight of the reaction components and dibutyl hydrogen phosphate in an amount of 0.25% based on the total weight of the reaction components were added. The mass was brushed onto a wooden panel and became "dust-free" after 5 hours and had dried firmly overnight.

Example 7

2 parts of an unsaturated polyester resin, which is made from fumaric acid (1 mol) and polyethylene glycol with the average molecular weight of 300 (1 mol) and up to an acid number of 19.2 mg COC per gram was condensed, were mixed with 1 part of allylated polyglycerin (iodine number 240, 3.0% OH, viscosity 30 seconds in a B. S. B. 3 cup at 25 ° C) and continue with 1 part butyl acetate for Diluted for painting purposes. Cobalt naphthenate solution (containing 6% cobalt metal) in an amount of 1.6%, based on the total weight of the reaction components, was added as a siccative and the Painted mass on a wooden panel. It was found that the mass produced a "dust-free" Reached state and dried firmly overnight.

Claims (5)

Patent claims: 1. Polymerizable coating agent, consisting of a ^, ^ - unsaturated ether, an unsaturated one Polyester resin and a polymerization catalyst and optionally a solvent, characterized in that that the ^, y-unsaturated ether at least aliphatic or aromatic polyhydroxylic ones containing three unsaturated ether substituents Compound and the polymerization catalyst consists of a metal salt dryer. 2. Coating agent according to claim 1, characterized in that the dryer consists of a Cobalt salt. 3. Coating agent according to claim 1 and 2, characterized in that it is a synergistic Contains agents such as dibutyl hydrogen phosphate for the metal salt dryer. 4. Coating agent according to one of the preceding claims, characterized in that that the unsaturated ether is that of polyglycerine. 5. Coating agent according to one of the preceding claims, characterized in that that the weight ratio of the unsaturated ether compound to the polyester resin is between 1: 1 and 1: 4. Considered publications:
German Auslegeschriften Nos. 1 019 421, 1 024 654, 1011551; Kunststoff-Rundschau, 1957, pp. 185 to 191;
Farbe und Lack, 1956, p. 105;
Wagner - Sar x, Lackkunstharze, 1959, p. 132. 809 507/640 1.68 © Bundesdruckerei Berlin