JP2003510401A - Use of water-soluble zirconium compounds as drying accelerators for aqueous coatings - Google Patents

Abstract

  (57) [Summary] The present invention relates to the use of a water-soluble zirconium compound as a drying accelerator in an aqueous coating. In this case, the zirconium compound is preferably a compound such as ammonium zirconium carbonate, zirconium acetoacetate, zirconium hydroxychloride, zirconium orthosulfate, zirconium propionate and / or potassium zirconium phosphate. Preferably, the coating is a paint and stucco.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the use of water-soluble zirconium compounds as drying accelerators for aqueous coatings.

[0002]

[Prior art]

Conventional systems for fast-drying coatings generally contain a solvent. In the case of these solvent-based coatings, the drying rate can be adjusted by varying the solids content and / or the solvent. Aqueous coatings are harmless to the environment and, in contrast to solvent-based coatings, have become increasingly popular these days. Polymer dispersions are commonly used as binders for the production of water-based coatings.

A drawback of aqueous coatings is that the drying rate depends on temperature and humidity. At low humidity, the drying rate is generally faster, sometimes faster than with conventional coatings. Of course, in the case of high humidity and low temperature such as morning and evening, the evaporation rate of water is significantly hindered and the drying rate is very slow. Promoting the drying of aqueous coatings is especially for outdoor applications,
For example, it is desired for buildings, bridges, paints for ships and road markings and plasters for outdoor use. There are three different practically relevant principles for rapidly drying aqueous coatings.

According to the agglomeration principle, the agglomeration of ionically stabilized binders is by applying a coating containing polyamine and ammonia as a volatile base and then evaporating the ammonia (US Pat. 527,853, European Patent Application Publication (A) 0,594,321, 0,728,822, 0,409,459) or a coating agent. At the same time, by spraying an acid solution (International Patent No. 94 / 29,391) or a salt solution (
European Patent Application Publication (A) No. 0,200,249, US Pat. No. 4,
571,415 and 5,403,393).

Modification of the viscosity at the surface of the coating is described, for example, in European Patent Application Publication (A) No. 0,
Applying a thickening agent to the fresh coating as disclosed in 721,003,
It can be achieved by applying the base to a fresh coating containing the thickener which has not been activated thereby by increasing the viscosity or adjusting to a low pH value.

In the case of the water absorption method, water-absorbing substances such as silica gel, ion exchangers, polymer gels etc. are used during the application of the coating.

In the case of coatings whose drying is activated by evaporation of a volatile base such as ammonia, the range of applications is limited, for example, by the odor annoyance. The coatings which are contacted with the salt after application of the coating have the disadvantage that they are limited to using weakly stabilized dispersions. The salts used must be sprayed together as a solution or sprayed or sprayed later. If the salt in solid or solution form is subsequently applied, most of it is washed off, for example by rain. This significantly impairs the efficiency of this method. Most of the salt released by rain reaches groundwater. Therefore, this type of drying method is not desirable.

From EP-A-0,709,441 it is known to use zirconium compounds in paints and adhesives. In this case, the zirconium compound is used as a desiccant, a cross-linking agent, a thixotropic agent, a radical scavenger during the decomposition reaction of the coating film and generally as a complex chloride substance for the contents causing bleeding or discoloration of the surface. There is.

[0009]

[Constitution of the invention]

Surprisingly, the inventor has found that coatings containing one or more water-soluble zirconium compounds clearly accelerate drying. This is especially the case at low temperatures. In this case, surprisingly, no special requirements are placed on the binder contained in the coating.

In the case of the use according to the invention, the coating agent is preferably up to 50% by weight, in particular 0.5 to 10% by weight, particularly preferably 1 to 5% by weight, calculated as zirconium oxide based on the binder.
Containing a zirconium compound.

As the zirconium compound, it is preferable to use zirconium ammonium carbonate, zirconium acetoacetate, zirconium hydroxychloride, zirconium orthosulfate, zirconium propionate and / or potassium zirconium phosphate. It is particularly preferable to use ammonium zirconium carbonate.

The zirconium compound can be added to the coating as a solid and / or as an aqueous solution.

Zirconium-containing coatings are, in addition to binders, film-forming agents, pigments, fillers (eg titanium dioxide, talc, calcite, dolomite), thickeners (eg cellulose ether, acrylic acid, polyurethane thickeners). ), Dispersants, wetting agents, preservatives, emulsifiers and / or defoamers. Pigment volume concentration (PVK)
Is generally 15 to 90%. To improve the stability of the coating, the coating may optionally further comprise 0.1 to 5% by weight, preferably 0.5 to 5% by weight, based on the binder.
1% by weight of ionic and / or nonionic emulsifiers may be added.

The binder included in the coating is generally a homo- and / or copolymer-based polymer dispersion. Suitable homo- and / or copolymers here are all known homo- and copolymers obtained in the form of dispersions.

In a particularly preferred embodiment, the copolymer is 7% based on the total amount of monomers.
Of 0 to 99.7 _{wt%, (C 1 ~C 12)} - monohydric alcohols, preferably (C ₁ ~
C ₈₎ - monoalcohols, such as methanol, ethanol, isopropanol,
Isobutanol, n- butanol and 2-ethylhexyl alcohol acrylic acid - and methacrylic acid esters; vinyl aromatic monomer; (C ₁ ~C ₁₂₎ -
Vinyl esters of alkane monocarboxylic acids such as vinyl acetate, vinyl propionate, vinyl-n-butyrate, vinyl laurate, ^(R) VeoVa 9 and ^(R) VeoVa 10 (Shell-Chemie: α, α-dialkyl branched Vinyl esters of monocarboxylic acids); vinyl halides such as vinyl chloride and vinylidene chloride; α, β-monoolefinically unsaturated nitriles such as acrylonitrile and methacrylonitrile; and alkyl esters of monoolefinically unsaturated dicarboxylic acids such as maleic acid. And a fumaric acid-di-n-butyl ester containing a radically polymerizable olefinically unsaturated compound selected from the group consisting of:

Furthermore, the copolymer is preferably 0.3 to 10% by weight, particularly preferably 0.5 to 5% by weight, based on the total weight of the monomers, of α, β-monoolefinically unsaturated mono- and dicarboxylic acids, For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, and their amides optionally substituted at the nitrogen atom, such as acrylamide, methacrylamide, N-methylolacrylamide and N-butoxymethacrylamide. .

Furthermore, 0 to 20% by weight, preferably 0.5 to 5% by weight, based on the total weight of monomers, of functional monomers, for example hydroxyl-containing monomers such as hydroxyalkyl acrylates and -methacrylates, particularly preferably hydroxyethyl. Methacrylate and hydroxypropyl methacrylate; and / or acetylacetoxy group-containing monomers, especially allyl acetoacetate, acetylacetoxyethyl methacrylate and acetylacetoxybutyl methacrylate; and / or crosslinking monomers, such as epoxy group-containing monomers, which improve wet adhesion. Monomers containing silane groups, especially glycidyl acrylate, glycidyl methacrylate, vinyltrimethoxysilane and methacryloxypropyltrimethoxysilane And / or nitrogen-containing monomers of the group of polymerizable monomers containing amino groups, uretdio groups or N-heterocyclic groups, such as dimethylaminoethyl acrylate and -methacrylate, N- (2-methacryloylethyl) -ethyleneurea; and / or It may contain keto group-containing monomers such as diacetoacrylamide, diacetomethacrylamide, acrolein and 2-butanomethacrylic acid ester.

In the self-crosslinking dispersion, the keto group-containing polymer is 5% based on the total weight of the monomers.
Up to% by weight of difunctional or polyfunctional carboxylic acid hydrazides, eg adipic acid hydrazide, may be included.

The binder may optionally contain emulsifiers, protective colloids, additives, auxiliaries and / or non-copolymerizable crosslinkers.

Suitable nonionic emulsifiers are, for example, alkyl polyglycol ethers or ethoxylated products of polypropylene oxide. Suitable ionic emulsifiers are first of all anionic emulsifiers, such as the alkali metal or ammonium salts of alkyl-, aryl- or alkylaryl sulfonates, -sulfates, -phosphates or -phosphonates.

Suitable protective colloids are natural substances such as gum arabic, starch and alginates, or modified natural substances such as cellulose derivatives, or synthetic polymers such as polyvinyl alcohol and polyvinylpyrrolidone, or mixtures thereof.

Coating agents include, among others, outdoor stucco, indoor stucco, outdoor paints, indoor paints, undercoat paints, woodworking paints or traffic paints.

The coatings of the invention in a broad sense also have adhesives, pastes, putties, sealants or pressure equalizing layers for outdoor insulation and finishing systems.

Zirconium-containing coatings also include additive-free binders which can be used for all purposes known as fast-drying binders.

The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples.

[0026]

【Example】

A) Manufacture of Synthetic Resin Stucco The synthetic resin stucco described in Examples and Comparative Examples has the basic formulation shown in Table 1.

Comparative Example 1: The composition of the comparative plaster 1 corresponds to the basic formulation listed in Table 1. In this case a solids content of 50% as a binder, synthetic resin dispersions having a viscosity of pH values and 400mPas of 6 Mowilith ^(R) DM2452 ^{(manufacturer:} Clariant GmbH: Table 1, the component number 8) are used. The monomer base of this dispersion is composed of vinyl acetate, vinyl esters of Versatic acid ^(R) and acrylic acid esters.

To prepare the plaster, water is first prepared and the remaining ingredients are added under mixing in the order listed. After the raw materials have been metered in, the plaster is mixed until completely homogenized.

Table 1: Synthetic Resin Stucco Basic Formula ────────────────────────────┬─────── Ingredients | Parts by weight ────────────────────────────┼─────── 1. Water │ 56.9 2. Cellulose ester (MC type , Medium viscosity) │ 1.5 3. Dispersant (polyacrylate) │ 3.0 4. Preservative (isothiazolinone) │ 2.0 5. Wetting agent (polyphosphate) │ 0.6 6. Caustic soda solution (10% concentration) │ 2.0 7. Foaming agent (mineral oil base) │ 2.0 8. Synthetic resin dispersion │ 140.0 9. Pigment (titanium dioxide) │ 20.0 10. Filler (kaolin; 3 μm) │ 20.0 11. Filler (calcite; particle size 40 μm) │ 150.0 12. Filler (Calcite; particle size 130 μm) │ 170.0 13.Filler (calcite; particle size 130-500 μm) │ 100.0 14.Structural particles (calcite; particle size 1.5-2.0 mm) │ 300.0 15. Film forming aid (aliphatic hydrocarbon) │ 4.0 16. Build Membrane aid (glycol ether) │ 6.0 17. Fiber (polyethylene) │ 2.0 ────────────────────────────┼───── ─── │ 980.0 ────────────────────────────┴─────── Example 1: Zirconium-containing synthetic resin plaster Production of 1 The composition of the synthetic resin stucco 1 differs from the basic formulation shown in Table 1 only in that it further contains 20 parts by weight of a zirconium compound Bosefix PAS5200 (manufacturer: Clariant GmbH). As the binder, the same synthetic resin dispersion as in Comparative Example 1 is used.

To prepare the plaster, water is first prepared and the remaining ingredients are added under mixing in the order listed. In this case, the zirconium compound is added last. After the addition of the raw materials is completed, the plaster is mixed until completely homogenized.

Comparative Example 2: Manufacture of a comparative plaster 2 containing no zirconium compound: The composition of the comparative plaster 2 corresponds to the basic formulation given in Table 1, in this case 55% solids content as binder. content, synthetic resin dispersion having a viscosity of pH values and 2000mPas of 5 Mowilith ^(R) LDM1880 ^{(manufacturer:} Clariant GmbH)
(Table 1, component No. 8) is used. The monomer base of this dispersion consists of vinyl acetate and ethylene. The comparative stucco 2 is manufactured in the same manner as the comparative stucco 1 as described in Comparative Example 1.

Example 2 Production of Zirconium-Containing Synthetic Resin Stucco 2 The composition of the synthetic resin stucco 2 contains the basic formulation shown in Table 1 and additionally 20 parts by weight of the zirconium compound Bosefix PAS 5200 (manufacturer: Clariant GmbH). Only the points differ. As the binder, the same synthetic resin dispersion as in Comparative Example 2 is used.

To prepare the plaster, water is first prepared and the remaining ingredients are added under mixing in the order listed. In this case, the zirconium compound is added last. After the addition of the raw materials is completed, the plaster is mixed until completely homogenized.

B) Use test of comparative plasters 1 and 2 and zirconium-containing synthetic resin plasters 1 and 2 a) Production of test body Substrate, comparative plasters 1 and 2, synthetic resin plasters 1 and 2 and necessary members at constant temperature Temperature control the test body temperature to 5 ° C in the chamber. Stucco 10 cm x 15 cm at this temperature
Plaster plaster with a trowel on a cemented board with fibers of the following dimensions, then strip and texture to the grain thickness.

B) Testing of Specimens Specimens are tested for dryness after various drying times at a test temperature of 5 ° C. For this purpose the test bodies are each sprayed with 60 g of water. In this case, a water mist is generated by a commercially available atomizer. Place the specimen vertically while spraying. Collect the runoff liquid quantitatively. While the coating is still dry, the test solution rinses the particles, which causes the test solution to develop a white color. The dryness of the coating can be estimated from the color strength.

[0036]   The dryness of the stucco is evaluated according to the 6 ratings shown in Table 2.

Table 2: Classification of degree of dryness ┌───┬──────────┬────────────┐ │ Rating │ Dryness │ Coloring degree of test solution │ ├───┼──────────┼────────────┤ │ 1 │ Dry │ No coloring │ │ 2 │ Almost dry │ Slightly colored │ │ 3 │ Slightly dry │ Cloudy │ │ 4 │ Humid condition │ Significant turbidity │ │ 5 │ Wet condition │ White │ │ 6 │ Significant wet condition │ White │ └─── ──────────┴────────────┘ 4 of the comparative plasters 1 and 2 and synthetic resin plasters 1 and 2 at a drying temperature of 5 ° C
Alternatively, the degree of dryness according to the six ratings in Table 5 after a drying time of 7 hours is shown in Table 3.

Table 3: Dryness of plaster tested ┌────────┬────────────┬────────────┐ │ coating Agent │ Dryness after 4 hours of drying │ Dryness after drying of 7 hours │ ├────────┼────────────┼─────── ─────┤ │Comparative plaster 1 │ 4 │ 2 ~ 3 │ │ Synthetic resin plaster 1 │ 2 │ 1-2 │ │ Comparative plaster 2 │ 3 │ 2 │ │ Synthetic resin plaster 2 │ 2 │ 1 │ └────────┴────────────┴────────────┘ As can be seen from Table 3, zirconium-containing synthetic resin plasters 1 and 2 Always shows a higher degree of dryness than the comparative plasters 1 and 2 independent of the binder (synthetic resin plasters 1 and 2 contain different synthetic resin dispersions as binder) and independent of the drying time.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] September 19, 2001 (2001.19)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J038 CC011 CD001 CF011 CG141                       CG161 CH011 HA296 HA376                       HA416 JA43 KA08 KA09                       PB05                 4J040 DB011 DC001 DE011 DF021                       DG031 HA196 HA256 HA286                       HB22 KA35 KA38 KA42

Claims (13)

[Claims] 1. Use of one or more water-soluble zirconium compounds as a drying accelerator for aqueous coatings. 2. Use according to claim 1, wherein the total content of zirconium compounds is up to 50% by weight, calculated as zirconium oxide and based on the binder contained in the coating. 3. Use according to claim 2, wherein the total content of zirconium compounds is 0.5 to 10% by weight. 4. A zirconium ammonium carbonate as a zirconium compound,
Use according to any one of claims 1 to 3, wherein zirconium acetoacetate, zirconium hydroxychloride, zirconium orthosulfate, zirconium propionate and / or potassium zirconium phosphate is used. 5. Use according to claim 4, wherein ammonium zirconium carbonate is used as zirconium compound. 6. Use according to claim 1, wherein the zirconium compound is added to the coating as a solid and / or as an aqueous solution. 7. The coating material contains a film-forming agent, a pigment, a filler, a thickener, a dispersant, a wetting agent, a preservative, an emulsifier and / or an antifoaming agent in addition to the binder.
Use according to any one of 6. 8. Use according to claim 1, wherein the binder contained in the coating is a polymer dispersion based on one or more homo- and / or copolymers. 9. The copolymer comprises a) 70 to 99.7% by weight, based on the total amount of monomers, of (C ₁ -C ₁₂ ) -acrylic acid and methacrylic acid esters of monoalcohols, vinyl aromatic monomers, (C). _1- C ₁₂ ) -Alkane monocarboxylic acid vinyl ester, vinyl halogenide, α, β-monoolefinic unsaturated nitrile and / or monoolefinic unsaturated dicarboxylic acid alkyl ester selected from the group consisting of Radical-polymerizable olefinic unsaturated compounds, b) 0.3-10% by weight of α, β-monoolefinically unsaturated mono- and dicarboxylic acids and / or their amides or N-substituted amides One or more compounds selected from the group, and c) 0-20% by weight of hydroxyl-containing monomers, acetylacetoxy Use according to claim 8 containing a compound selected from the group consisting of group-containing monomers, epoxy group-containing monomers, silane group-containing monomers, nitrogen-containing monomers and / or keto group-containing monomers. 10. Use according to claim 8 or 9, wherein the binder contains emulsifiers, protective colloids, additives, auxiliaries and / or non-copolymerizable crosslinkers. 11. The coating material is an outdoor paint, an indoor paint, a traffic paint, an undercoat paint, a woodworking paint, an outdoor plaster or an indoor plaster.
Use according to any one of. 12. Use according to claim 1, wherein the coating is an adhesive, a paste, a putty, a sealant or a pressure equalizing layer for outdoor insulation and finishing systems. 13. Use according to claim 1, wherein the coating agent is an additive-free binder which is used as such.