CN1074463A - Aqueous coating composition - Google Patents

Abstract

A kind of gel monochrome or polychrome aqueous coating composition are disclosed, showing as extremely, light, flash of light property, brightness change with the visual angle, have eye-catching effect and decorative effect especially, and surprising homogeneity and dispersiveness are arranged, its viscosity can apply the technology adjustment as requested.By the filmogen and the thickening material of adding appropriate amount in composition, and add specific metal-salt, and keep the ratio of Sodium hexametaphosphate 99 and Tai-Ace S 150 to obtain improved effect between 1: 2 to 2: 1.This new coating composition is suitable for spraying, brushing or roller coat.

Description

Aqueous coating composition

The present invention relates to a kind of moisture monochrome or polychrome coating composition that has specific flash of light and brightness flop and have unexpected eye-catching effect and decoration function and have special luminance brightness, dispersiveness, use properties and homogeneity with the visual angle difference.More specifically say, the present invention relates to be suitable for spraying, roller coat or the filmogen that except that containing typical additives and basic components, also contains suitable consumption of brushing and the water base monochrome or the polychrome coating composition of thickening material.The ratio that the viscosity of the coating composition that this is new can be passed through to change Sodium hexametaphosphate 99 and Tai-Ace S 150 is regulated arbitrarily in 100 to 50000 centipoise scopes a variation in 1: 2 to 2: 1.

At present, day by day obvious with water-based paints replace solvent-based lacquer, this is because the problem of the harmful steam volatilization causing of solvent environment and HUMAN HEALTH aspect.

For many years, so-called polychrome coating composition has caused very big concern, and this based composition is the composition that contains monochromatic drop or the immiscible each other different colours drop that closes, thereby it is applied to a certain when surface, the color effect that can obtain to be thoroughly satisfied.

By US-A-3,458,328 known a kind of compositions that mainly contain following ingredients:

(a) first form and aspect that can flow contain a kind of moisture hydrophilic colloid membrane-forming agent.

(b) the second free-flowing aqueous phase, color is mutually different with first, and incompatible substantially in the presence of (c);

(c) the not solvating agent of described hydrophilic colloid, initially be present among at least a above-mentioned phase, its consumption should make described first form and aspect that can flow free-flowing aqueous insoluble mutually basically mutually with second, wherein said composition is applied to desired when surface, and the decorative coveringn of many area limitings that a kind of each interval of the different outward appearances by this first and second phase obviously distinguishes can be provided thereon.

In this application, pointed out that also the consumption of solvating agent must not be not enough to form insoluble throw out, but should only form the suspension of viscid discrete or gluey drop.In this specification sheets, specially narrated insoluble sedimentary from eliminating.

At US-A-3, introduced a kind of composition in 725,089, said composition is a homogeneous by normally reading apart from its outward appearance of visual inspection, it mainly consists of:

(a) first form and aspect that can flow contain a kind of moisture hydrophilic colloid membrane-forming agent;

(b) the second free-flowing aqueous phase, color is mutually different with first;

(c) be present at least the first mutually with second the not solvating agent of hydrophilic colloid membrane-forming agent in one of mutually, consumption should make this first and second phase insoluble substantially each other, this first is many discrete little droplet-like mutually, size range is greater than the little drop of colloid, but less than 25 microns, thereby it is interior invisible normally to read distance at naked eyes, and said composition is applied to described when surface thus, and a kind of decorative coveringn with uniform outer appearance is provided thereon.

By GB-A-2,078,243 known a kind of multicolor paint comprises a kind ofly forming the aqueous dispersion of the resulting hydration drop of complexing salt by two kinds of polyelectrolyte with opposite charges and a kind of reaction reaction with one of polyelectrolyte.

In all above-mentioned three applications, the basic ingredient of composition also has Xylo-Mucine and Tai-Ace S 150 except pigment and typical additives, and this dispersion liquid only obtains with physical method, formation be colloidal dispersion.

By BE-A-735,138, known a kind of system lacquer method especially prepares the method for multicolor paint, and wherein dyeing or painted aqueous solution or emulsion can be allowed and produced precipitation or gelling, and if desired, throw out or painted or stained gel can be processed and be obtained dispersion liquid.As if can pass through physical method, for example heating reaches sedimentation or gelling, but with aqueous solution or emulsion follows first solution with a kind of energy or reactant aqueous solution is precipitated or the water-soluble liquid-phase mixing of certain material of agglomerative or this material is more favourable.

At SU-A-1, in 045,906, introduced a kind of painted hard microcapsule, its method for making is emulsification dyestuff or a pigment in a polywater solution, adds aluminum salt solution, handles with latex and 50-80 ℃ of heating again.

By GB-A-1,224,390 a kind of as can be known methods that prepare aluminium one carboxymethyl cellulose complex compound (Al-CMC), this method can be used for preparing slurry coating and emulsion paint.According to this patent application, obtain product by for example Xylo-Mucine being mixed with aluminium salt, this material is dissolved in the alkaline water washing and dry this complex compound that obtains.

At EP-B-0,182, in 962, at least disclose a kind of method of preparing multicolor paint, one or more alkaline mediums that contain anionic cellulose thickening material (as Xylo-Mucine) and the reaction soln that contains the inorganic salt (being preferably Tai-Ace S 150) of heavy metal or trivalent metal are reacted.Obtain being with the insoluble throw out of color fibre shape by this reaction, thereby obtain a kind of polychrome particulate suspension at reaction end.Obtain a kind of random dispersion liquid of coloured particle thus, can be made into the thread facing of star-like, plate-like, pearl or other shape outward appearance.

Therefore, the difference of above-mentioned EP patented product and US patent and GB-A-2078243 patent is final coating of particles, in described known content, all obviously do not relate to or do not predict formation and do not dissolve sedimentary content, it can make japanning have this unarguable advantage of permanent stability.

At present appreciablely be, at United States Patent (USP) 3,458, in 328, in order not produce throw out, and just gel japanning then correspondingly adds 10% ammonia solution, with reacting aluminum sulfate, avoid the partial reaction with CMC, promptly form English Patent GB1, the complex compound described in 224,390.

Known, in the reaction of Xylo-Mucine and Tai-Ace S 150, generate acid, need be neutralized.As at EP0, form solid particulate described in 182,962 like that, also should be owing to adding lime carbonate and small amounts of sodium hydroxide.In fact known ammonia and sodium hydroxide and aluminium reactant salt generate gelatinous hydrate, otherwise lime carbonate then this reaction can not take place.At US-A-3, carried out in 458,328 add in the ammonia react energy and in about 50% the prescription used aluminium amount and in the long or short time, produce aluminum hydroxide precipitate.

The consumption of used sodium hydroxide can not provide enough alkaline degree to consume the aluminium of existing respective amount in the above-mentioned EP patent.But this prescription is owing to there being lime carbonate to have required alkali equivalent, and wherein said alkali equivalent passes through to have reacted neutralizing effect in heterogeneous.Therefore can conclude that the gluey outward appearance of above-mentioned United States Patent (USP) is because the reaction result of aluminium hydroxide rather than Xylo-Mucine and Tai-Ace S 150.At EP0, it also is possible forming complex compound in 182,962 the product, and this is not because there is calcium sulfate to exist, and just because Xylo-Mucine and reacting aluminum sulfate obtain known Al-CMC complex compound, it dissolves in the alkaline water liquid, and it is a solid granular.

But find out, use lime carbonate to increase and lump or condense, be unfavorable for spraying especially, because their meeting plug nozzles, grit usually breaks away from basic unit, causes uneven image, and product does not resemble that the client of many Application Areass is bright desired, dispersibility and ductility.The decoration function and eye-catching effect and the brightness change performance that also do not have in the market more and more strong request.

Therefore an object of the present invention is to provide a kind of monochrome or polychrome aqueous coating composition that overcomes above-mentioned defective, more particularly will provide a kind of is not as insoluble sedimentary solid granular in the suspension, but be used to spray, the soft gel compositions of brushing or roller coat, the visual required administration form of its viscosity changes arbitrarily.A further object of the present invention is that a kind of aqueous coating composition will be provided, and wherein under the polychrome situation, observes this particle for bright and good distribution from the naked eyes visual range, and needn't use and effectively apply technology and just can apply.One object of the present invention is will provide a kind of to have or the composition of the storage tolerance performance of long or short period of time at least, said composition keeps its performance constant, for example do not occur being separated or deposition or sedimentation etc., and when being applied in it in basic unit, has satisfied flash of light with the visual angle difference, brightness flop and special eye-catching effect and decoration function.

Be surprised to find that thus, if in prescription, be to add special metal-salt to the anionic cellulose thickening material with in aluminium salt rather than add lime carbonate, and, can obtain the effect and the effect of all the invention described above by making final product have the consumption adding additive and the filmogen of absolute abnormal characteristic.

This discovery is unexpected, because based on known references, people are desired to be to be similar to the such solid particulate prescription of above-mentioned EP patent, rather than antipole is near the prescription of the gel of having introduced, but this prescription is more stable, has good visible colored particles and improved dispersiveness, homogeneity and the property used.

Therefore target of the present invention is the gluey aqueous coating composition of a kind of monochrome or polychrome, its viscosity finally applies technology and change arbitrarily according to required, it is characterized in that, except that usual component and additive, it also contains 2-80%(weight) filmogen, 0.8-10%(weight) thickening material and the metal-salt of selection.

Metal-salt all can use, its negatively charged ion should be enough a little less than, to show the improved action on the meaning of the present invention.The metal-salt of the metal (for example zirconium) of metal of the 1st and the 2nd subgroup (for example zinc) and the 4th and the 8th subgroup and alkaline-earth metal (for example barium and magnesium) most preferably but does not comprise calcium salt.

The salifiable group of the optional self energy of this negatively charged ion can be inorganic or organic.Therefore be preferably oxyhydroxide, muriate, carbonate, supercarbonate, acetate, oxalate, tartrate, lactic acid salt, maleate, fumarate etc. in the above-mentioned metal-salt.Should reach finally whether can select this salt according to economic condition owing to the change color influences said composition.Therefore wherein preferred salt is organic salt, carbonate, muriate and oxyhydroxide.With regard to practicality, cost and validity, magnesiumcarbonate is that override is selected.

The preferable amount of metal-salt is not harsh, and based on the composition total weight meter, its scope is generally 0.05-6%(weight).

For the viscosity that makes composition changes in the preferable range of 100-50000 centipoise, and then the ratio of change Sodium hexametaphosphate 99 and Tai-Ace S 150 suits.According to the present invention, preferred ratio range is 1: 2 to 2: 1.

And under the alkaline pH condition, be easy to make the particle dissolving, and therefore, in order to obtain more stable particle or spheroid, interpolation or use POLY ALUMINIUM CHLORIDE replace Sodium hexametaphosphate 99 to suit, and its amount ranges is 0.01-1.8%.

In a preferred specific embodiments, the present invention correspondingly relates to the aqueous coating composition that contains following component:

(a) 10-90%(weight) water;

(b) 0.1-2.5%(weight) mould inhibitor;

(c) 0.05-2%(weight) dispersion agent;

(d) 0.8-10%(weight) thickening material;

(e) 0.2-28%(weight) pigment;

(f) 2-80%(weight) membrane-forming agent;

(g) 0.1-8%(weight) ethylene glycol;

(h) 0.1-5%(weight) butyl phthalate;

(i) 0.05-3%(weight) defoamer;

(l) 0.05-6%(weight) Tai-Ace S 150;

(m) 0.1-4%(weight) Sodium hexametaphosphate 99;

(n) 0.02-4%(weight) methylated spirits;

(o) 0.01-3%(weight) wilkinite;

(p) 0.1-7%(weight) coalescing agent;

(q) 0.05-6%(weight) metal-salt;

(r) 0.01-2%(weight) sodium hydroxide; With

(s) 0.05-4%(weight) wetting agent;

And, also contain in order finally to obtain stable particle

(t) POLY ALUMINIUM CHLORIDE 0.01-8%(weight),

Wherein all wt per-cent all calculates by composition total weight.

Be prepared the technological process of the present composition according to well-known condition.

If desired is monochrome or polychrome composition, also should predict logical some variation.In order to obtain monochromatic composition, generally all must under stirring fast, mix the solution of preparation respectively, until reaching desired particle specification, generally rotating speed is 1000-2000 rev/min; And under the situation of polychrome composition, stir with slower speed, the particle until obtaining to require is preferably 10-900 rev/min.

The following example has been done more detailed description to the present invention, prepares basic solution at first respectively, and these solution are respectively:

Tai-Ace S 150;

Sodium hexametaphosphate 99;

Ethanol;

Membrane-forming agent;

Wilkinite;

Wetting agent;

Metal-salt.

According to desired product, different solution is poured in the reactor, and added other component, keep pH value, temperature and stirring velocity in preset value simultaneously.

The material of relevant purpose composition of the present invention should also be pointed out that following content.

In order to obtain the tone (mainly being the pearly-lustre tone) of light especially, select luminous glittering pigment for use, otherwise then only selected no delustering pigment, obtain " low key tone ".In most cases, pigment can be differentiation by its CAS value, for example 12001-26-0,1317-70-0,1317-80-2,18282-10-5,1309-37-1 or 544-63-8.Can further enumerate following pigment: 4792 Iriodin, 216 Rutile Red Pearl; 4209 Iriodin, 235 Rutile Green Pearl; 4288 Iriodin, 225 Rutile Blu Pearl; 6960 Iriodin, 163 Shimmer pearl; 4285 Iriodin Rutile Platinum Gold; 4287 Iriodin, 219 Rutile Lilac Pearl; All products all can be available from Merck AG.Other spendable pigment comprises pearlaceous white Superfine; Supersilk; Silkwhite; Superwhile; Pearlwhite; Sparkle; Supersparkle; Metallic color pigment such as Brass; Brillian Gold; Sparkle Gold; Golden Bronze; Copper; Nu-Antique Silver; Nu-Antique Gold; Nu-Antique Bronze; Nu-Antique Copper; Super Russet; Super Bronze; Super Copper; And high brightness colorant such as Gold; Blue Red; Green; Violet; Orange; All products all can be available from Mearlin.These pigment can be separately or are mixed mutually and use, and consumption is a 0.2-28%(weight).

Filmogen can be made of any known product that is usually used in the field of painting, for example styrene-propene acid resin, band branched paraffin carboxylic acid vinylester resin, acrylic resin, can be separately with or shared.Can enumerate following commercially available prod: the Repolem(Atochem product) or AC-33-X(Rohm and Haas product).Thickening material also is a kind of ionic commonly used or product of nonionisable substance of being selected from the japanning field, preferably is selected from known commercially available thickening material, as carboxymethyl cellulose " the Legacolor(Cesalpinia product), Walocel etc.

In order more to clearly reveal feature of the present invention, introduce below and specify embodiments of the invention.But should be understood that this only makes usefulness for example, rather than will limit the scope of the invention the scope with claim.

Embodiment

Solid-shade paint:

Prepare monochromatic composition base fluid, it is as follows to fill a prescription:

Ingredients weight parts

Water 76.63

Mould inhibitor 1.16

Dispersion agent 0.60

Pigment 7.00

Thickening material 2.15

Filmogen 9.30

Ethylene glycol 0.93

Butyl phthalate 1.86

Defoamer 0.37

They are stirred till evenly together.Store the base fluid of this preparation standby.

Multicolor paint:

Preparation multicolor paint base fluid, it is as follows to fill a prescription:

Ingredients weight parts

Water 76.64

Mould inhibitor 1.16

Dispersion agent 0.60

Pigment 7.00

Thickening material 2.14

Filmogen 9.30

Ethylene glycol 0.93

Butyl phthalate 1.86

Defoamer 0.37

Mix all components under the room temperature till evenly, store this solution for standby.

Prepare following solution respectively:

Solution A:

Ingredients weight parts

Water 89.45

Tai-Ace S 150 9.94

Cellulose thickener 0.61

Solution B:

Ingredients weight parts

Water 94.89

Sodium hexametaphosphate 99 5.11

Solution C:

Ingredients weight parts

Water 80.05

Mould inhibitor 1.21

Dispersion agent 0.63

Titanium dioxide 3.23

This mixture was stirred 10-15 minute, adds following material then:

Ingredients weight parts

Thickening material 2.25

Filmogen 9.72

Ethylene glycol 0.97

Butyl phthalate 1.95

Defoamer 0.39

Solution D:

Ingredients weight parts

Methylated spirits 41.72

Thickening material 58.28

Solution E:

Ingredients weight parts

Water 89.70

Mould inhibitor 0.30

Wilkinite 10.00

Solution F:

Ingredients weight parts

Water 92.50

Sodium hydroxide 7.50

Solution G:

Ingredients weight parts

Water 75.00

Wetting agent 25.00

Solution H:

Ingredients weight parts

Water 22.16

Solution D 1.14

Solution E 3.30

Mould inhibitor 0.79

Filmogen 67.92

Coalescing agent 4.30

Defoamer 0.39

When preparing straight-shade coating compositions of the present invention, at first mix mutually with the base fluid of 51.83 parts of above-mentioned preparations with 14.65 parts of water.Then 1.03 parts of magnesiumcarbonate are dissolved in 6.00 parts of water and obtain magnesium salt solution.

In a reactor with 4.49 parts of above-mentioned solution A and 2.06 parts of water and 6.023 parts as mentioned above the solution B of preparation put together.Add 66.48 parts of above-mentioned base fluid+water, 7.03 parts of magnesiumcarbonate solution, 12.90 parts of Solution H, 0.17 part of solution F, 0.36 part of solution G and 0.86 part of defoamer under the room temperature in this mixture, the while vigorous stirring also keeps the pH value to be 6.8-7.3.According to used pigment, when applying on base material, this coating composition provides a kind of bright color of the outward appearance that the light reflection is arranged and be thoroughly satisfied.

During preparation polychrome composition, 1.25 parts of magnesiumcarbonate are sneaked in 6.28 parts of water, prepare magnesiumcarbonate solution separately.In a reactor, pour 6.28 parts of above-mentioned solution A, 2.51 parts of water into, 5.24 the base fluid of part solution B, 62.88 parts of above-mentioned independent preparations, and under stirring at a slow speed, add 7.54 parts of magnesiumcarbonate solution, 13.84 parts of Solution H, 0.20 part of solution F, 0.44 part of solution G and 1.04 parts of defoamers again.When applying on base material, this japanning shows satisfied contrast effect between the little color dot of the background colour of homogeneous and different colours, have special decoration and eye-catching effect.

According to the present invention, if the list of 1-5 part or polychrome composition and 9-5 part film forming medium-comprise 10-50 part water, 0.65-3 part mould inhibitor, 0.2-6 part thickening material, 0.5-12 part talcum, 10-28 part filmogen, 0.2-6 part coalescing agent, 0.05-4 part defoamer, 0.01-3 part dispersion agent and 0.05-3 part wetting agent are put together, can obtain to spray, the japanning product of brushing or roller coat.

Claims (11)

1, a kind of monochrome or polychrome coating composition, when said composition is applied on the base material, show unexpected flash of light, with brightness flop and the special eye-catching effect and the decorative effect at visual angle, it is characterized in that, it is except that containing filmogen commonly used, thickening material and additives known, the metal-salt that also contains 0.05-6% (weight), and its viscosity can change according to desired purposes.

2,, it is characterized in that metal-salt is selected from the oxyhydroxide of barium, magnesium, zinc and zirconium, muriate, carbonate, supercarbonate, acetate, oxalate, tartrate, lactic acid salt, maleate and fumarate according to the coating composition of claim 1.

3,, it is characterized in that metal-salt is a magnesiumcarbonate according to the coating composition of claim 2.

4,, it is characterized in that its viscosity is 100 to 50000 centipoises according to each described coating composition of claim 1-3.

5, according to each described coating composition of claim 1-4, the consumption that it is characterized in that filmogen is a 2-90%(weight).

6, according to each coating composition of claim 1-5, the consumption that it is characterized in that thickening material is a 0.8-10%(weight).

7, according to the described coating composition of above each claim, it is characterized in that the ratio of Sodium hexametaphosphate 99 and Tai-Ace S 150 remains between 1: 2 to 2: 1,, change viscosity so that according to desired purposes.

8,, it is characterized in that using consumption to be 0.01-8%(weight according to the described coating composition of above each claim) POLY ALUMINIUM CHLORIDE replace Sodium hexametaphosphate 99, to obtain stable particle.

9,, it is characterized in that it comprises component according to the described coating composition of claim 1-8:

(a) water 10-90%(weight);

(b) mould inhibitor 0.1-2.5%(weight);

(c) dispersion agent 0.05-2%(weight);

(d) thickening material 0.8-10%(weight);

(e) pigment 0.2-28%(weight);

(f) filmogen 2-80%(weight);

(g) ethylene glycol 0.1-8%(weight);

(h) butyl phthalate 0.1-5%(weight);

(i) defoamer 0.05-3%(weight);

(l) Tai-Ace S 150 0.05-6%(weight);

(m) Sodium hexametaphosphate 99 0.1-4%(weight);

(n) metal-salt 0.05-6%(weight);

(o) coalescing agent 0.1-7%(weight);

(p) sodium hydroxide 0.01-2%(weight);

(q) wetting agent 0.05-4%(weight);

(r) wilkinite 0.01-3%(weight);

(s) methylated spirits 0.02-4%(weight); With

For the final stable particle that obtains also comprises

(t) POLY ALUMINIUM CHLORIDE 0.01-8%(weight),

Wherein all wt per-cent is all represented the per-cent based on composition total weight.

10, according to the described aqueous coating composition of above-mentioned each claim, be specially adapted to spraying, brushing or roller coat, it is characterized in that the medium that contain following material with 1-5 part list or polychrome composition and 9-5 part mix: 10-50 part water, 0.65 to 3 part of mould inhibitor, 0.2 to 6 part of thickening material, 0.5 to 12 part of talcum, 10 to 28 parts of filmogens, 0.2 to 6 part of coalescing agent, 0.05 to 4 part of defoamer, 0.1 to 3 part of dispersion agent and 0.05 to 3 part of wetting agent.

11, the method for above described monochrome of each claim of preparation or polychrome aqueous coating composition, wherein the base fluid of these two kinds of compositions, so that the solution of Tai-Ace S 150, Sodium hexametaphosphate 99, filmogen, wilkinite, sodium hydroxide, wetting agent and metal-salt etc. prepare in advance, it is characterized in that, when preparing monochromatic composition, different solution and base fluid are separately placed a reactor jointly, stirring velocity remains on 1000 to 2000 rev/mins, till meeting the requirements of specification; And during preparation polychrome composition, stirring velocity remains on 10-900 rev/min, decides according to desired particle specification.