Oxidative drying the composition for coatings containing polythiol

 

(57) Abstract:

Composition for coating, comprising: (a) one or more thiol compounds; (b) one or more oxidative drying polyunsaturated condensation products of one or more fatty acids and/or esters, one or more polyols, and optionally one or more polycarboxylic acids and/or anhydrides of polycarboxylic acids and optionally other structural units; (C) one or more photoinitiators. The ratio between the number of unsaturated groups and the number of SH functional groups is preferably from 2:1 to 20:1. Preferably photoinitiator represents a mono-, bis - or triarylphosphine or mixtures thereof. 8 C.p. f-crystals, 6 PL.

The invention relates to compositions for coatings containing polyunsaturated polymer, thiol compound and photoinitiator.

U.S. patent 3729404 discloses a composition comprising political, Polian and a photosensitive component. The photosensitive component is used in combination with phosphine and positivum connection. In this known composition does not occur oxidative drying. Thiol compound is used for cross-linking. Specific polyene when Knymi groups. Such groups are education acrolein, which is a toxic compound. As there are only two terminal unsaturated fragment to a circuit that is similar to the composition hardens slowly and forms a soft covering film. A similar arrangement is disclosed in U.S. patent 4078118.

In the application GB-A, 2189499 disclosed composition for coatings containing unsaturated polyorganosiloxane, tifunctional organosiloxane and photoinitiator. Due to high content of siloxane groups the ability to re-coating and the pigment dispersion is very weak.

The objective of the invention is a composition for coating, which is free from the above disadvantages. In addition, the composition for coating should, on the one hand, show a rapid curing at low temperatures and, on the other hand, sufficiently long to ensure that their properties during storage, especially in the same container.

This object is achieved by a composition for coating, including:

a) one or more thiol compounds;

b) one or more oxidative drying polyunsaturated condensation products of one or more fatty acids and/or complex ehfironosakh acid and optional other structural units;

C) one or more photoinitiators.

Unexpectedly, it was shown that the addition of thiol compounds to oxidative drying polyunsaturated condensation products results in the presence of photoinitiator to more rapid curing at low temperatures compared with the conventional composition for coatings containing oxidative drying polyunsaturated condensation products and drying agents. The composition in accordance with the invention demonstrates quick drying, can be achieved and good conservation properties during storage even in the same container.

Preferably, the oxidative drying polyunsaturated condensation products have more than five double and/or triple bonds.

Unsaturated groups in oxidative drying the polyunsaturated condensation products preferably are introduced by means of fatty acids, but may, alternatively or additionally, be administered by one or more used polyols, carboxylic acids or anhydrides, or other structural blocks.

Suitable oxidative drying polyunsaturated condensation products are alkyd resins. At least frequent is x aliphatic compounds, at least part of which is polyunsaturated. Unsaturated aliphatic compounds are preferably unsaturated fatty acids, more specifically polyunsaturated fatty acids. Examples of monounsaturated fatty acids are Mirandolina acid, palmitoleic acid, oleic acid, gadolinia acid, erucic acid, ricinoleic acid and mixtures thereof. Examples of polyunsaturated fatty acids include linoleic acid, linolenic acid, eleostearic acid, Likhanova acid, arachidonic acid, clupanodons acid, cesinovo acid and mixtures thereof. You can also use fatty acids containing conjugated double bonds, such as fatty acid digidratirovannogo castor oil fatty acid, wood oil and/or fatty acid oil of calendula.

Examples of suitable divalent polianovich compounds are ethylene glycol, 1,3-propandiol, 1,6-hexanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,2-dimethyl-1,3-propandiol and 2-methyl-2-cyclohexyl-1,3-propandiol. Examples of suitable triolo are glycerin, trimethylated and trimethylolpropane. Suitable polyvinylidene, such as detromethorphan and di-, tri - and tetrapartite. It is preferable to use compounds having 3-12 carbon atoms, for example glycerol, pentaerythritol and/or dipentaerythritol.

Alternative or additionally as structural units for oxidative drying polyunsaturated condensation products can be used polycarboxylic acid. Examples of suitable polycarboxylic acids include phthalic acid, citric acid, fumaric acid, metaconule acid, maleic acid, citraconate acid, isophthalic acid, terephthalic acid, 5-tert-utilizatorului acid, trimellitic acid, pyromellitic acid, succinic acid, adipic acid, 2,2,4-trimethyladipic acid, Aslanova acid, sabotinova acid, diarizonae fatty acid, cyclopentane-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, tetrahydrophthalic acid, endometrin-cyclohexane-1,2-dicarboxylic acid, butane-1,2,3,4-tetracarbonyl acid, antisapation-cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,2,4,5-tetracarbonyl acid and butane-1,2,3,4,-tetracarbonyl acid. EO ether, for example a complex ester of alcohol having from 1 to 4 carbon atoms.

If necessary oxidative drying polyunsaturated condensation products may include other structural units, which may, for example, be derived monocarboxylic acids, such as pavlikova acid, 2-ethylhexanoate acid, lauric acid, palmitic acid, stearic acid, 4-tert-butylbenzoic acid, cyclopentanecarbonyl acid, naphthenic acid, cyclohexanecarbonyl acid, 2,3-dimethylbenzoic acid, 2-methylbenzoic acid, benzoic acid, 2,2-dimethylolpropionic acid, tetrahydrobenzoic acid and gidrirovanny and not gidrirovanny abietic acid or its isomers. If necessary, upon receipt of an alkyd resin in question monocarboxylic acids can be used fully or partly in the form of triglycerides, such as vegetable oil. If necessary, you can use a mixture of two or more of such monocarboxylic acids or triglycerides.

If necessary as a structural blocks oxidative drying polyunsaturated condensation products can also be used isocyanates. Suitable from the cyanate, diphenyldiisocyanate and dicyclohexylmethane. You can also use triisocyanate.

A characteristic example of a suitable main part is the condensation product of soybean oil, phthalic anhydride and pentaerythritol.

Alkyd resins can be obtained by the esterification components of replacing part of these components have been converted into simple ether diols or diols transformed into a complex polyester. Alternatively, the unsaturated fatty acid can be added in the form of dried oils, such as sunflower, flax, fish oil tuna, digidrirovannoe castor oil, coconut oil and digidrirovannoe coconut oil. As a result of transesterification with polyols and optionally other structural units receive target alkyd resin. This transesterification usually occurs at a temperature 115-250°C, optionally in the presence of a solvent, such as toluene and/or xylene. The reaction is usually carried out in the presence of a catalyst for transesterification amount of catalyst. Examples suitable for use in the transesterification catalyst include acids such as n-toluensulfonate, the primary connection, this is and triphenylantimony chloride.

Preferably, the composition for coating includes more than 79 wt.% oxidative drying polyunsaturated condensation products relative to the total weight of the solid resin. Molecular weight of oxidative drying polyunsaturated condensation products may, for example, be from 50 to about 80,000, preferably from 500 to 10000.

Examples of suitable thiol compounds include, but are not limited to, esters of thioglycolic, thiosalicylic acid, mercaptoethanol acid, mercaptohexanol acid, 2-mercaptopropionic acid or 3-mercaptopropionic acids and polyols, such as glycols, pentaerythritol, dipentaerythritol and tetramethylchroman, and optionally a fatty acid such as oleic acid, stearic acid, isononanoic acid or fatty acid sunflower. Typical examples of suitable thiol compounds are etilenglikoli(thioglycolate), etilenglikoli(2-mercaptopropionate), etilenglikoli(3-mercaptopropionate), pentaerythritoltetranitrate(thioglycolate), pentaerythritoltetranitrate(2-mercaptoacetate), pentaerythritoltetranitrate(2-mercaptopropionate), pentaerythritoltetranitrate(3-mercaptopropionate), trimethylolpropane(2-mercapto is propionic acid, stearic acid and 3-mercaptopropionic acid.

Examples of suitable thiol compounds also include hyperbranched Paleologue kernel based on the original polyol, such as trimethylolpropane and dimethylolpropionic acid. This polyol consistently atrificial through 3-mercaptopropionic acid and isononanoic acid. These methods are described in European application EP-A 0448224 and International application WO 93/17060.

Thiol compound may be, for example, a structure corresponding to the formula R[(C6H6O)nCH2CHOHCH2SH]3where R is a triol, such as trimethylolpropane or glycerin. An example of such a compound is commercially available from Henkel under the trademark of Henkel CapcureŽ 3/800.

The following scheme of the synthesis involves reacting an aryl - or alkylhalogenide with NaHS for the introduction of the above mentioned groups of mercaptan in the alkyl or aryl compound, respectively. Another alternative is the interaction of the Grignard reagent with sulfur for introduction into the structure of these mercaptan. The reaction joining polymercaptan with polyolefin Michael is another example of the method of obtaining Polish is dinani, relative to the total weight of the solid resin, more preferably 3-20 wt.% thiol compounds. These thiols may have, for example, a molecular weight of from 50 to 20000.

Alternatively, oxidative drying polyunsaturated condensation product and a thiol compound may be included, if required, in the same copolymer.

The ratio between the number of unsaturated groups and a number SH-functional groups in the composition for coating is preferably at least 1.5:1. Best results are obtained if the ratio is from 2:1 to 20:1.

Photoinitiator required for use in accordance with the invention, generally are compounds that are activated by UV radiation and/or fluorescent light. Examples of suitable photoinitiators include, for example, ketones such as methyl ethyl ketone, 2,3-butandiol, 1-hydroxycyclohexyl, 2-hydroxy-2-methyl-1-phenylpropane-1-it, and aromatic ketones, such as acetophenone, benzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, valerophenone, hexanophenone, o-methoxybenzophenone-phenylbutyrate-phenylbutyrate, n-morpholinopropan, dibenzosuberone, 4-morpholinobutyrophenone, benzoylmethylene and antinational esters, 4-morfolinoetilrutin; quinone compounds and antrona, for example, hydroquinone, anthraquinone, naphthoquinone, acenaphthene and 3-methyl-1,3-diazo-1,9-benzanthrone; phenolic compounds such as 2,4-dinitrophenol; and phosphine compounds such as triphenylphosphine and tri-o-tolylphosphino; azo compounds, for example, azobisisobutyronitrile; connection dioxanone, including, for example, 2-isopropyl-thioxanthone, 1-chloro-4-propoxyimino, 2,4-deoxidization and 2 chlorothioxanthone; and various other compounds, for example, benzil, benzaldehyde, 1-naphthaldehyde-tetralone, 2-acetylphenanthrene, 3-acetylphenanthrene, 9-acetylphenanthrene, 10-thioxanthine, 3-acetylindole, 9-forenoon, 1-indanone, 9-xanthene, 9-thioxanthone, 7-H-Benz[de]anthracene-7-it, 1-acetonaphthone and 2-acetonaphthone. You can use a mixture of different photoinitiators.

Preferably photoinitiator is phosphinoxide connection, such as 2,4,6-trimethylbenzaldehyde-phosphine oxide (LucirinŽNPO manufactured by BASF) or bis(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-pentyl-phosphine oxide (DMBAPO, IrgacureŽ 403 manufactured by Ciba Specialty Chemicals). Especially preferred are acylpolyamines compounds such as mono-, bis - or triarylphosphine or mixtures thereof. Example BisI Ciba Specialty Chemicals).

Preferably the composition contains from 0.01 to 10 wt.% photoinitiator, more preferably 0.1 to 3 wt.%, calculated on the total weight of the solid resin.

Composition for coating in accordance with the invention can also contain various additives such as UV stabilizers, co-solvents, dispersing agents, surfactants, inhibitors, fillers, antistatic agents, lubricants, anti-foam agents, diluents, plasticizers, antioxidants, anti-freezing agents, waxes, thickeners, thixotropic agents, etc. of the Composition can be used in the form of transparent varnish or they may contain pigments. Examples suitable for use pigments are metal oxides, such as titanium dioxide or iron oxide, or other inorganic or organic pigments.

The characteristics of the drying composition for coating in accordance with the invention make it possible not to use a metal driers such as cobalt. However, these dehumidifiers can be used additionally, if needed.

Composition for coating in accordance with the present invention can be used in the form of a composition with a high solids content, including ocrite with a high content of solvents. Alternatively, the composition can be used in aqueous compositions for coating.

Composition for coating in accordance with the present invention can be applied in the usual ways, including drawing with a brush, roller, spray or dipping.

The composition can be stored in the form of one-component compositions, preferably in a light tight container. Alternatively, the composition for coating can be stored in the form of two or more components that are mixed before use.

Composition for coating in accordance with the invention is particularly suitable for use as decorative or household coverage, for example, for the coating of wooden surfaces, such as door and window frames, but can also be used in industry, in particular for the coating of wooden surfaces. The composition can also be used for coating surfaces made of metal, concrete, plastic and other materials.

Hereinafter the invention is described and illustrated by the following examples. These examples are also the manufacturers of the following substances (see table a).

The dal and thiol compounds, present in the present compositions.

The drying time is measured as follows. Composition for coating is applied using a plate for application to the glass plate. Drying takes place in a room with constant temperature of 10°C and relative humidity 80% for lighting TL-055. Drying is checked with the help of VK-Registrar drying. Thus obtained results can be classified as follows:

phase 1: a line drawn by a pin closes again ("open time");

phase 2: pin leaves a trace in the form of rough line ("dust free");

phase 3: the pin leaves a straight line on the paint, which is no longer closed ("tack-free time").

Examples 1-6, comparative examples a and b

In examples 1-6 composition for coatings are produced with increase in the content of pentaerythritol-tetrakis(3-mercaptopropionate) (RTSM) from 1 to 20 wt.%. Comparative examples a and b refer to compositions that do not contain thiol compounds. In examples 1-6 and comparative example 0.5 wt.% besatisfied (IrgacureŽ) is used as photoinitiator. The composition of comparative example And does not contain photoinitiators, but instead contains 7.5 wt.% the calcium. Containing pentaerythritol-tetrakis(3-mercapto-propionate) and Alcide in comparative example A, the composition includes 0.06 wt.% cobalt, 0.38 wt.% zirconium, 0.23 wt.% of calcium. In addition, it contains an agent that prevents the formation of a surface film comprising 0.54 wt.% 2-butanonoxime.

All compositions of examples 1 to 6 and comparative examples a and b contain Alcide with high solids content, based on the fatty acid podsolnechnika, when the concentration of the oil 74% and the solids content of 90 wt.% in white-spirit with a viscosity of 6.3 Pas at 23°C. Bulk pigment concentration (PVC) in all compositions is 15%.

The results of the tests on drying using VK-Registrar drying are presented in table 1.

As can be seen from table 1, changes in the number of thiol resins lead to reduced drying time by increasing the concentration of the thiol. The absence of thiol resin composition of comparative example leads to long-term desiccation, and the presence of only 1 wt.% pentaerythritol-tetrakis(3-mercaptopropionate) leads to a real increase in the speed of drying. In the presence of 3 wt.% pentaerythritol-tetrakis(3-mercaptopropionate) is achieved Bolo in comparative example A.

Examples 7-11

In examples 7-11 get a composition for coating, which includes the same compounds as the composition in example 3. All compositions of examples 7-11 include pentaerythritol-tetrakis (3-mercaptopropionate) in an amount of 5 wt.%, calculated on the total weight thiol and alkyd compounds. The content of besatisfied different. We have conducted several tests on the hardening, as in examples 1-6. The results are presented in table 2, where the number of besatisfied specified in weight percent based on the total weight of the alkyd and thiol compounds.

As shown in table 2, increasing the number of photoinitiator up to 2 wt.% leads to decrease drying time. However, further increase in the number of besatisfied to 3 wt.% does not affect the reaction rate.

Example 8 is similar to example 3. Although the results are somewhat different, these differences are not significant.

Examples 12-14

In examples 12-14 are white pigmented product with 15% PVC containing 1.0 wt.% IrgacureŽ 819, thiol compound and Alcide with high solids content, based on the fatty acids of sunflower oil content of 74% and a solids content of 90% is about the amount of binding of the product of condensation of detromethorphan, 2,2-dimethylolpropionic acid, stearic acid and 3-mercaptopropionic acid. This product is produced in the following way: 118,6 g of di(trimethylolpropane) and 508,2 g of 2,2-dimethylolpropionic acid loaded into a reaction flask equipped with stirrer, input for nitrogen, thermocouple, cooling Vigreux and the office of the Dean-stark. The mixture atrificial at 140°C using a 14.4 g of n-toluenesulfonic acid as a catalyst. After the cessation of hydrodistillation the use of vacuum to remove water. When the amount of acid becomes less than 10, add 698,4 g of stearic acid, maintaining the temperature of the mixture above 110°C. Then add 5 wt.% xylene and 289 g of 3-mercaptopropionic acid in doses within one hour, while the temperature rises from 120 to 140°C. Add 5 wt.% of xylene and the mixture is refluxed under reduced pressure. After a few hours, add another 7.2 g of n-toluenesulfonic acid and the mixture is boiled until the volume of acid below 10. Then added 4.6 g of lithium carbonate and after stirring for 30 minutes 233 g of white spirit. The resin is boiled and filtered under pressure using a nozzle to filter ClarcelŽ, supplied by Elf Atochem. The solids content in the received cm is at 23°C, is 1,42 Pas.

In example 13 composition comprises a thiol compound 15 wt.% the product of condensation of dipentaerythritol, oleic acid and 3-mercaptopropionic acid.

In example 14 thiol compound formed by the condensation products of di-trimethylolpropane, 2,2-dimethylolpropionic acid, isononanoic acid and 3-mercaptopropionic acid.

In examples 12-14 SH functional group when calculating about $ 4. The number of thiol functional groups of about 10 EQ.% equivalent to the number of thiol functional groups in the composition of example 9, in which the number of counted SH functional groups is also equal to 4. The results of EK test for drying, also obtained at 10° C, are shown in table 3.

Example 15. Comparative examples C and D

In example 15 receive the same thiol compound as in example 12. This thiol compound used for the formation of a transparent coating without pigment. This transparent coating consists of 14 wt.% thiol compounds and 86 wt.% Setal Ž 270, conventional main part, commercially available from Akzo Nobel Resins, and 1.0 wt.% IrgacureŽ 819 (besatisfied) calculated on the total amount of binder.

In vacuume consists of 100 wt.% SetalŽ 270. In comparative example instead of photoinitiator using a metal drier. Used metal drier is a 7.5 wt.% Nuodex CombiŽ APB, resulting cobalt is 0.06 wt.% cobalt, zirconium, 0.38 wt.% and calcium 0.23 wt.%, all percentages calculated on the total weight of the binder. The composition of comparative example D contains no metal drier, but contains 1 wt.% IrgacureŽ 819 (besatisfied) .

Drying of the compositions of example 15 and comparative examples C and D were tested as described above. The results are presented in table 4.

Examples 16 and 17. Comparative examples E-N

Thiol compound, analogous to example 15, is used to produce a transparent composition for the coating of example 16 and 17. In example 16 transparent composition for coating contains 14 wt.% thiol compounds and 86 wt.% SetalŽ 293, alkyd resin with high solids content. In example 17 transparent composition for coating contains 14 wt.% thiol compounds and 86 wt.% SynolacŽ 6094, also alkyd resin with high solids content.

Comparative examples E and F were carried out with a transparent composition for coating, with the 6094. In comparative examples E and G to 7.7 wt.% Nuodex CombiŽAPB used instead of photoinitiator. In comparative examples F and H, which uses a metal drier, transparent composition for coating containing 1 wt.% IrgacureŽ 819 (besatisfied).

The results of the tests on the drying carried out in accordance with the foregoing, are presented in table 5.

1. Composition for coating, containing a) one or more thiol compounds; (b) one or more oxidative drying polyunsaturated condensation products of one or more fatty acids and/or esters, one or more polyols, and optionally one or more polycarboxylic acids and/or anhydrides of polycarboxylic acids and optionally other structural units and (C) one or more photoinitiators.

2. Composition for coating under item 1, characterized in that the ratio between the number of unsaturated groups and a number SH-functional groups is at least 1.5:1, preferably from 2:1 to 20:1.

3. Composition for coating according to any one of the preceding paragraphs, characterized in that the composition comprises 1-30 wt.%, preferably 3-20 wt.% thiol compounds relative to the total weight of the solid fuel is more isocyanates used as structural building blocks for oxidative drying polyunsaturated condensation product.

5. Composition for coating according to any one of the preceding paragraphs, characterized in that the composition is a composition for coating high solids content, containing 0-40 wt.%, preferably 0-30 wt.% the solvents.

6. Composition for coating according to any one of paragraphs.1-4, characterized in that the composition is an aqueous composition for coating.

7. Composition for coating according to any one of the preceding paragraphs, characterized in that photoinitiator is active under visible light.

8. Composition for coating according to any one of the preceding paragraphs, characterized in that photoinitiator is acylpolyamines connection, preferably mono-, bis - or triarylphosphine or mixtures thereof.

9. Composition for coating according to any one of the preceding paragraphs, characterized in that at least one oxidative drying polyunsaturated condensation product is a thiol compound or is one of the thiol compounds.

 

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4 cl, 2 tbl, 5 ex

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