CN1241200A - Water-based alcohol hydroxycarboxylic peroxide compositions, preparation, and uses thereof - Google Patents
Water-based alcohol hydroxycarboxylic peroxide compositions, preparation, and uses thereof Download PDFInfo
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- CN1241200A CN1241200A CN 97180811 CN97180811A CN1241200A CN 1241200 A CN1241200 A CN 1241200A CN 97180811 CN97180811 CN 97180811 CN 97180811 A CN97180811 A CN 97180811A CN 1241200 A CN1241200 A CN 1241200A
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Abstract
A method of preparing an environmentally safe composition free of chlorinated solvents which is non-flammable, fully biodegradable, and low odor and the use of such composition for the removal of various coatings from metal substrates. The composition comprises a water-based mixture of one or more high boiling, high flash aromatic solvents (benzyl alcohol, benzyl ether, 1-phenoxy-2-propanol), a peroxide generating agent (hydrogen peroxide), and a hydroxycarboxylic acid (glycolic acid). It can be prepared as a liquid and used as such for immersion/dipping operations or as a thick paste ''cling-type'' material when optimal application requires a thin film. These can be applied by spraying or brushing.
Description
In decades, strong acid and halocarbon solvent-based compositions are used to peel off various supercoat from metal and other substrate.In recent years, owing to the disadvantageous effect of these paint removers of growing interest to healthy and environment, so whole world legislative bodies of national governments all limit and/or ban use of these materials.
In United States Patent (USP) 5215675, people such as Wilkins propose a kind of based on ethyl lactate and so on soluble ester and the moisture paint removing composition of the superoxide of hydrogen peroxide and so on.
In United States Patent (USP) 5405548 and United States Patent (USP) 5542986, Distaso has described the application at the aqueous based systems that is used for peeling off various supercoat of formic acid xylyl ester or formic acid benzyl ester and formic acid.
But there are several shortcomings in these prior art compositions, that is, low solvency power (poor efficiency), expensive, corrodibility, stability boundary be narrow, especially intensive, pungent odour beastly.
The present invention relates to a kind of can be effectively from the metallic surface, as removing the new paint removing composition of various supercoat, especially Resins, epoxy, cross-linked polyurethane and Synolac paint on the aluminum base alloy.
This paint remover comprises three kinds of basal components in deionized water or distilled water,, be with or without the solvent system based on one or more high boiling points, high flash point, aromatic alcohol of aromatic oxide that is; Hydroxycarboxylic acid; Generate agent with superoxide.
Put it briefly, comprise the 5-50 weight part in the product formula, the solvent system of preferred 25-35 weight part; The 3-20 weight part, the hydroxycarboxylic acid of preferred 3.5-7 weight part; With the 3-30 weight part, the superoxide of preferred 5-10 weight part generates agent.15-60 weight part in the paint remover, preferred 40-50 weight part is deionized water or distilled water.Can use other additive according to concrete purposes, as solubilizing agent, tensio-active agent, coupling agent, rheology modifiers, inhibiter, stablizer and evaporation suppressor.
In the present invention, weight part and weight percentage are meant active weight part and the weight percentage of forming.For example,, and in final product composition having, preferably contain the peroxidation hydrogen generating agent of 10 weight parts, so just should use the aqueous hydrogen peroxide of 20 weight parts if use 50% aqueous hydrogen peroxide.
The invention provides a kind of effective paint removing composition, it does not have chlorinated solvent, environmental sound and to user's gentleness.It is noncorrosive or only non-combustible, nontoxic, low smell of burn into and totally biodegradable a little to substrate.The present invention also provides and has been used to prepare liquid or cream (thickness) type prescription, to peel off material, technology and the technology of the substrate that the non-level that applies by spraying method or spread coating applies.
Paint removing composition of the present invention is preferably made by the premix following substances: (1) comprises the polar phase of hydroxycarboxylic acid, peroxidation hydrogen generating agent, deionized water or distilled water and selected additive; (2) comprise the nonpolar phase of organic solvent system.In order to prepare the liquid paint remover, under continuous mixing condition, nonpolar phase is slowly added in the polar phase, can form stable microemulsion liquid like this.Cream type paint remover just slowly is dispersed in polar phase in the nonpolar phase if desired.
Polar phase is made by the hydroxycarboxylic acid that adds the 3-20 weight part under continuous mixing condition, the superoxide generation agent of 5-30 weight part and the deionized water or the distilled water of 15-60 weight part.
Usually, nonpolar phase accounts for the 5-50 weight part of prescription, preferred 25-35 weight part.The mixture of the mixture of benzylalcohol, benzylalcohol and benzylic ether, phenoxypropanol and phenoxyethyl alcohol and benzylic ether is very suitable.The weight ratio of aromatic alcohol and ether is preferably 2.5: 1.
In order to form the liquid paint remover, under mixing condition continuously, nonpolar phase is slowly added in the polar phase, stable microemulsion liquid type composition transparent up to forming.
In order to obtain cream (thickness) type paint remover, utilize controlled scatter operation, polar phase is slowly added in the nonpolar phase.
Hydroxycarboxylic acid can be described by following general formula:
HOOC-(CH
2)
n-(CH
2)
m-OH formula I
Wherein n and m are the integer of 0-3, and n and m sum are at least 1; N and m sum preferably equal 1.Preferred hydroxycarboxylic acid is oxyacetic acid (oxyacetic acid), but also can use described other hydroxycarboxylic acid of following formula, as hydroxy-propionic acid.Usually, the consumption of oxyacetic acid is the 3-20 weight part, preferred 3.5-7 weight part.
Superoxide generates agent and is preferably hydrogen peroxide.Comprising on most of metallic surfaces of aluminium and alloy thereof that hydrogen peroxide generation decomposition reaction generates a kind of can producing oxygen immediately and the juvenile oxygen intermediate of water.Oxygen can be by at first with remollescent supercoat protuberance, allows a large amount of paint removing compositions infiltrate metal-coating interfaces then and quickens the depainting step.Although available concentration is up to the hydrogen peroxide of 70% weight, preferred working concentration is 30-35%.This can obtain by the hydrogen peroxide with deionized water dilution higher concentration.
Contain the overall paint removing effect that deionized water can improve final depainting prescription in the polar phase.If supercoat is a polar, as urethane, the solvent of high-k so just can produce positive influence when the separating charged zone as water (ε=80.2 are in 20 ℃), and other solvent in being convenient to like this fill a prescription is softening with film.
Deionized water the most advantageously comprises and is no more than about 1% weight, preferably is lower than the dissolve inorganic salts of about 200ppm.Preferred especially electric conductivity is lower than distilled water or the deionized water of about 400mho/cm.If can not satisfy above-mentioned water parameter, will cause peroxide breakdown, therefore suppressed paint removing effect.
Can in final composition, add other additive, as: coupling agent (aklylene glycol, DMSO); Stablizer (monoacetylaniline); Sequestrant (phosphonic acids, citric acid, EDTA); Inhibiter (benzotriazole, borate); And rheology modifiers (hydroxypropylcellulose, Natvosol, various natural gum, smog silicon-dioxide or precipitated silica).These additives are well known in the art.In general, their consumption is a 0.1-5.0% weight, preferred 0.2-3.0% weight.
Also can use evaporation suppressor, as silicone liquid (polysiloxane), water based wax emulsion or paraffin oil.In final product composition having, use the 0.1-3.0 weight part usually, preferred 0.2-2.5 weight part.Also can add solubilizing agent-emulsifying agent, as the polyethoxylated Isosorbide Dinitrate, especially polyethoxylated Arlacel-20, monopalmitate, monostearate, tristearate, monoleate or three oleic acid polysorbates.Usually use the 0.5-5.0 weight part.Use is based on the rheology modifiers of about 0.4-1.0 weight part of final product composition having.
Nonpolar phase comprises the alcohol of one or more formulas II and III, and choosing contains the ether of a kind of formula IV arbitrarily:
R
1-CH
2-O-CH
2-R
2
Formula II formula III formula IV
Wherein X, Y and Z are hydrogen atom or two hydrogen atoms and a methyl.R can be ethyl, propyl group or sec.-propyl; And R
1And R
2For hydrogen atom and benzyl or all be benzyl.
In order more intactly to describe the present invention, can pay close attention to following examples:
Usually in manufacturing process, use stainless cylinder of steel and the industrial decollator that can under speed, operate up to 2000rpm.At first, all metallic interior surface are all handled (passivation) by contacting 2-3 hour with nitric acid (40% concentration), will be drawn in the stainless cylinder of steel by the nonpolar mixture that alcohol or alcohol mixture are formed then.
By under 300-400rpm, mixing 30-45 minute, will slowly be dispersed in the nonpolar phase as the silicone liquid of evaporation suppressor.In the mixture of gained, add solubilizing agent-emulsifying agent, rheology modifiers and inhibiter then.Solubilizing agent-emulsifying agent is the polyethoxylated polyoxyethylene-sorbitan mono-oleate.Rheology modifiers is a hydroxypropylcellulose.Inhibiter is a benzotriazole.
Again above-mentioned system was slowly disperseed 15-30 minute.Prepare the polar phase that comprises hydroxycarboxylic acid, superoxide generation agent and distilled water or deionized water separately, slowly add in the dispersion tank then.Hydroxycarboxylic acid is an oxyacetic acid.It is hydrogen peroxide that superoxide generates agent.The viscosity of composition takes place obviously to raise.In next stage, the speed of decollator is risen to 1000-1200rpm, at this moment all solid matters are uniformly emulsify all, stablely then generates a kind of cream type composition that will be described in more detail in Table A.
If the preparation liquid composition under continuous mixing condition, slowly adds nonpolar phase in the polar phase.The composition of polar phase and nonpolar phase as mentioned above.Add propylene glycol (coupling agent) and benzotriazole (inhibiter) then.Table A has provided a series of composite cream.
Table A
| Composition | (weight part) |
| Benzylalcohol benzylic ether 1-phenoxy group-2-propyl alcohol glycolic hydrogen peroxide (50% weight) polysorbate hydroxypropyl cellulose 2-sulfydryl benzotriazole silicone liquid propane diols monoacetylaniline deionized water | ???P-1??????P-2???P-3????P-4?????P-5???P-6?????P-7????P-8 ???35.0?????20.0??----???----????35.0??----????35.00??---- ???----?????15.0??----???15.0????---???----????----???---- ???----?????----??35.0???20.0????----??35.0????----???35.0 ???10.0?????10.0??10.0???10.0????10.0??10.0????----???---- ???9.0??????9.0???9.0????9.0?????---???----????9.0????9.0 ? ???1.4??????1.4???1.4????1.4?????1.4???1.4?????1.4????1.4 ???0.4??????0.4???0.4????0.4?????0.4???0.4?????0.4????0.4 ???0.2??????0.2???0.2????0.2?????0.2???0.2?????0.2????0.2 ???0.3??????0.3???0.3????0.3?????0.3???0.3?????0.3????0.3 ???----?????----??----???----????----??----????----???---- ???0.03?????0.03??0.03???0.03????0.03??0.03????0.03???0.03 ???43.67????43.67?43.67??43.67???52.67?52.67???53.67??53.67 |
Table B has provided a series of liquid composition.
Table B
| Composition | (weight part) |
| Benzylalcohol benzylic ether 1-phenoxy group-2-propyl alcohol glycolic hydrogen peroxide (50% weight) polysorbate hydroxypropyl cellulose 2-sulfydryl benzotriazole silicone liquid propane diols monoacetylaniline deionized water | ?L-1??????L-2?????L-3????L-4????L-5????L-6????L-7?????L-8 ?35.0?????20.0????----???----???35.0???----???35.0????---- ?----?????15.0????----???15.0???----???----???----????---- ?----?????----????35.0???20.0???----???35.0???----????35.0 ?10.0?????10.0????10.0???10.0???10.0???10.0???----????---- ?9.0??????9.0?????9.0????9.0????----???----???9.0?????9.0 ? ?----?????----????----???----???----???----???----????---- ?----?????----????----???----???----???----???----????---- ?0.2??????0.2?????0.2????0.2????0.2????0.2????0.2?????0.2 ?----?????----????----???----???----???----???----????---- ?4.0??????15.0????4.0????15.0???4.0????4.0????4.0?????4.0 ?0.03?????0.03????0.03???0.03???0.03???0.03???0.03????0.03 ?41.77????30.77???41.77??30.77??50.77??50.77??51.77???51.77 |
Test 16 and be used for identical aluminium alloy plate (5.5 * 8.5 inches) commercial and yellow epoxide resin type priming paint of being coated with of amusement aircraft and grey lines type polyurethane finish paint.Under room temperature (20 ℃), with eight in 16 blocks of plates coated with cream type composition film, remaining eight are immersed in the liquid composition.To assess the effect of these compositions as the depainting coating percentage ratio of the function of time, will the results are shown in table C then:
Table C
| The percentage ratio time of composition depainting coating (minute) observations |
| P-1 100 45 P-2 100 60 P-3 100 55 P-4 100 80 P-5 80 90 no H2O 2P-6 80 240 no H 2O 2P-7 95 120 no oxyacetic acid P-8 90 270 no oxyacetic acids |
| L-1 100 25 L-2 100 30 L-3 100 35 L-4 100 30 L-5 90 120 no H2O 2L-6 90 130 no H 2O 2L-7 90 45 no oxyacetic acid L-8 90 60 no oxyacetic acids |
Above data clearly illustrate that, compare with the Comparative Examples (P-5 to P-8 and L-5 to L-8) that does not have oxyacetic acid and hydrogen peroxide, paste formulation of the present invention and liquid formulations (composition P-1 to P-4 and L-1 to L-4) are all showing excellence aspect depainting speed and the depainting integrity.
Claims (15)
1. aqueous depainting prescription comprises:
(a) aromatic alcohol of the formula II of 5-50 weight part and III, choosing contains the aromatic oxide of formula IV arbitrarily, and composition thereof:
R
1-CH
2-O-CH
2-R
2
Formula II formula III formula IV
Wherein X, Y and Z are hydrogen atom or two hydrogen atoms and a methyl, and R can be ethyl, propyl group or sec.-propyl, and R
1And R
2For hydrogen atom and benzyl or all be benzyl;
(b) hydrogen peroxide of 5-30 weight part;
(c) hydroxycarboxylic acid of the formula I of 3-20 weight part:
HOOC-(CH
2)
n-(CH
2)
m-OH formula I
Wherein n and m are the integer of 0-3, and n and m sum equal 1; With
(d) deionized water of 15-60 weight part or distilled water.
2. according to the prescription of claim 1, wherein said aromatic alcohol is benzylalcohol or xylyl alcohol.
3. according to the prescription of claim 1, wherein said aromatic alcohol is 1-phenoxy group-2-propyl alcohol.
4. according to the prescription of claim 1, wherein said aromatic oxide is a benzylic ether.
5. according to the prescription of claim 1, it is hydrogen peroxide that wherein said superoxide generates agent.
6. according to the prescription of claim 1, wherein said hydroxycarboxylic acid is an oxyacetic acid.
7. a depainting prescription wherein comprises the mixture of being made up of following material: (a) benzylalcohol of 5-50 weight part, (b) hydrogen peroxide of 5-30 weight part, (c) oxyacetic acid of 3-20 weight part and (d) deionized water or the distilled water of 15-60 weight part.
8. cream type depainting prescription with composition of claim 7 wherein comprises the polyethoxylated Isosorbide Dinitrate of 0.5-5 weight part or its mixture as solubilizing agent-emulsifying agent.
9. according to the prescription of claim 1, it also comprise the 0.4-1 weight part be selected from hydroxypropylcellulose, Vltra tears, precipitated silica, and composition thereof rheology modifiers.
10. according to the prescription of claim 1, the silicone liquid, paraffin oil or the water based wax emulsion that wherein comprise the 0.1-3.0 weight part are as evaporation suppressor.
11. according to the prescription of claim 1, it also comprises the 2-mercaptobenzothiazole, azimido-toluene, benzotriazole or 2 (3H)-benzothiazole-second diketone of 0.1-0.5 weight part as inhibiter.
12. according to the prescription of claim 1, it also comprises two (hexa-methylene) triaminos-five (methylene radical-phosphonic acids), citric acid or the EDTA of 0.1-1.0 weight part as sequestrant.
13. according to the prescription of claim 1, the benzotriazole that it also comprises the 0.1-1.0 weight part as two (hexa-methylene) triaminos-five (methylene radical-phosphonic acids) of inhibiter and 0.1-1.0 weight part as sequestrant.
14. method that is used to prepare cream type paint removing composition, comprising, first mixture that will comprise 5-50 weight part benzylalcohol is dispersed in second mixture that comprises 5-30 weight part hydrogen peroxide, the acid of 3-20 parts by weight of ethanol and 15-60 parts by weight of deionized water or distilled water, and described dispersion liquid also comprises the polyethoxylated Isosorbide Dinitrate of 0.5-5.0 weight part, the hydroxypropylcellulose of 0.4-1.0 weight part and silicone liquid, paraffin oil or the emulsifying wax (solid) of 0.1-3.0 weight part.
15. method that is used to prepare cream type paint remover, comprising: the polar phase that will comprise the acid of 3-20 parts by weight of ethanol, 5-30 weight part hydrogen peroxide and 15-60 parts by weight of deionized water or distilled water is dispersed in the nonpolar phase that comprises 5-50 weight part benzylalcohol, obtain final product composition having, described final product composition having also comprises the polyethoxylated Isosorbide Dinitrate of 0.5-5.0 weight part, the hydroxypropylcellulose of 0.4-1.0 weight part and silicone liquid, paraffin oil or the water based wax emulsion of 0.1-3.0 weight part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180811 CN1241200A (en) | 1996-12-19 | 1997-12-18 | Water-based alcohol hydroxycarboxylic peroxide compositions, preparation, and uses thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/770,093 | 1996-12-19 | ||
| CN 97180811 CN1241200A (en) | 1996-12-19 | 1997-12-18 | Water-based alcohol hydroxycarboxylic peroxide compositions, preparation, and uses thereof |
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|---|---|
| CN1241200A true CN1241200A (en) | 2000-01-12 |
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|---|---|---|---|
| CN 97180811 Pending CN1241200A (en) | 1996-12-19 | 1997-12-18 | Water-based alcohol hydroxycarboxylic peroxide compositions, preparation, and uses thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058691B (en) * | 2006-04-19 | 2010-11-03 | 比亚迪股份有限公司 | Paint remover composition |
-
1997
- 1997-12-18 CN CN 97180811 patent/CN1241200A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058691B (en) * | 2006-04-19 | 2010-11-03 | 比亚迪股份有限公司 | Paint remover composition |
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