REMOVING SICCATIVE COATINGS FROM SUBSTRATES

Abstract: An aqueous alkaline hot stripper composition having in­ creased effectiveness and bath life when used at elevated temperatures to remove siccative coatings from substrates coated therewith contains one or more alkaline compounds and a synergistic combination of at least two of the following three activator materials, namely (i) tetrahydrofurfuryl alcohol, (ii) an ethoxylated furfuryl alcohol and (iii) an ethoxylated tetra­ hydrofurfuryl alcohol. This hot stripper composition also pref­ erably contains a sequestering agent and/or a composition-­ stabilizing compound and/or a surfactant.

Description: "Removing Siccative Coatings from Substrates. This invention relates to removing siccative coatings from substrates coated therewith. More particularly, the invention is concerned with an aqueous alkaline solution and processes employing it for stripping siccative coatings from metallic substrates. The term "siccative coatings" is used herein in its accepted meaning i.e. to embrace protective and/or decorative coatings of the kind which when applied in liquid form to a substrate form a film thereon which adheres to and dries on the surface to form the coating. Examples of such siccative coatings are shellac varnishes, phenolic varnishes, paints of the drying-oil types, cathodic electrodeposition paints, and paints which fall into the classes of alkyds, modified alkyds, modified phenolics, modified melamines, baked phenolics, epoxyresins, polyurethanes, silicones, acrylics, vinyls, and the like. Although the present invention has broader applicability, it will be described in connection with the stripping of siccative coatings from metal substrates, such as steel panels. There are many known compositions intended for removing siccative coatings from a wide variety of substrates, including wood and metals. Such compositions are useful in very diverse fields, ranging from furniture stripping or other generally similar home-restoration applications all the way through a variety of industrial uses, such as in the automotive industry where siccative coatings applied during manufacture to protect various component parts must be removed prior to final painting and finishing. Perhaps the simplest of all stripping compositions are those which essentially consist of an aqueous alkaline solution, which can be used at high temperatures, usually a rolling boil. Alkaline stripping compositions of this kind are believed to function by breaking ester or ether linkages, which hold the polymer units of the paint film together, forming the corresponding soaps. This however is a relatively slow procedure, in which alkaline base is consumed, and contaminants are formed in the composition. It is possible to improve the effectiveness of aqueous alkaline solutions by adding thereto a wetting agent, which will accelerate the stripping operation by penetrating or permeating the paint film subsequent to partial removal thereof by degradation. Further improvements can be achieved by the incorporation of detergents and emulsifiers, which will accelerate the stripping process by deterging and emulsifying or solubilizing plasticizer and unpolymerized binder in the paint film. From what has been said above it should already be clear that when removing siccative coatings from substrates coated therewith the stripper composition employed will desirably be one which acts in one or more of the following ways: - to break ester or ether linkages using strong alkali; - to deterge and emulsify plasticizer or other components of lower molecular weights with appropriate surfactants; - to permeate cracks and fissures in the paint, especially through, voids or around pigment particles by a wetting-out action; - to dissolve water-soluble solvent in resinous polymers, to facilitate permeation; - to dissolve soaps formed by reaction with the alkali, using primary alcohols and gycols to avoid having these soaps hinder further reaction; and - to break the bond between the substrate and the paint film by whatever means possible, including superficial action on the sub strate by use of sequestrants. The stripper composition moreover should preferably be one which will penetrate the paint film rapidly, and with only limited disintegration of the film. The aqueous alkaline compositions discussed above, which are employed at elevated temperatures and are therefore often referred to as "hot stripper compositions", generally are effective in removing most siccative finishes; but they are quite ineffective in removing cathodic electrodeposition paints, and not particularly effective in removing carbon-to-carbon bond-s. Penetration and bond-breaking mechanisms are of primary importance with acrylic and vinyl paints, and the paint tends to be sheeted off with little disintegration. It has however already been discovered that if furfuryl alcohol is added to such hot stripper compositions they become effective to remove acrylic and vinyl paints as well as cathodic electrodeposition paints. It appears that the furfuryl alcohol somehow activates the composition so that it penetrates the paint film, allowing attack on the bonds between the substrate'and the paint film. Another such composition-activating compound is tetrahydrofurfuryl alcohol. It has moreover been found that a combination of these two activators is more effective than either one of them alone. Another material which has been used in stripping compositions is an alkoxylated furfuryl alcohol. There are however problems about the use of these known activated hot stripper compositions. Above all, with continued use the activator is lost as it is boiled off. Furfuryl alcohol for instance forms an azeotrope with water, and the boiling point of that azeotrope falls within the operative temperature range for the hot stripper composition. Therefore, either the bath of composition must be dumped and a fresh bath made up, or the furfuryl alcohol and water lost as the azeotrope boils off must be replaced either continuously or at least periodically. We however have now found that it is possible to formulate a hot stripper composition which both is effective and has an increased bath life, and which moreover is particularly effective in the stripping of electrodeposited paint films. According to one aspect of the present invention there is provided an aqueous alkaline stripper composition, for use at elevated temperatures to remove siccative coatings from substrates coated therewith, comprising one or more alkaline compounds in a concentration such as to impart a pH of about 9.5 or more to the composition, together with an effective amount of at least two of the following three activator materials: (i) tetrahydrofurfuryl alcohol and furfuryl and/or tetrahydrofurfuryl alcohol ethoxylates of the general formulae EMI4.1 EMI5.1 wherein m and n, which may be the same or different, each represent the average degree of ethoxylation in the respective ethoxylates, and each of them lies in the range of from about 0.5 to about 10. As should be apparent, the average degree of ethoxylation represented respectively by m and n is in each case the number of moles of ethylene oxide per mole of the alcohol (reacted and unreacted) in the reaction product of ethylene tide with either furfuryl alcohol or tetrahydrofurfuryl alcohol. Thus for example when m or n is 1, the reaction product will be a mixture containing predominantly monc-ethoxylated furfuryl or tetrahydrofurfuryl alcohol-tAut also small amounts of the unreacted alcohol and of polyethoxylated alcohol(s). When m or n is a fraction less than 1, relatively larger quantities of unreacted alcohol will be present in the mixture; whereas when m or n is greater than 1, relatively larger quantities of polyethoxylated alcohol(s) will be present. All the ingredients of the aqueous stripper composition must naturally be present in concentrations effective to remove the siccative coating from a substrate coated therewith. The ingredients will preferably be present in concentrations. effec- tive to strip cathodic electrodeposition paint from a substrate coated therewith in a period within the range of from about 5 seconds to about 1 hour, working at a composition temperature in the range of from about 1800 to about 2200F (approx. 820- 140 C). As will emerge below, it appears that the unique combination of ingredients in the compositions of this invention together exert synergistic effects. As will be further explained subsequently, the compositions will preferably also contain a sequestering agent in an amount effective substantially to prevent precipitation, and/or a composition-stabilizing compound, selected from the group consisting of aliphatic primary alcohols, aliphatic secondary alcohols, alkylamines and mixtures thereof, in an amount effective substantially to prevent separation of the composition upon standing, and/or one or more surfactants at a concentration of about 0.5 to about 20 g/l. While effective compositions may be formulated that do not contain any of the aforementioned, it is preferred that one or more of these three kinds of optional additives should be present in the hot stripper compositions of this invention. The total concentration of the activator materials (i) - (iii) present should preferably be at least about 7 g/l, with at least two of these activator materials being each present in a concentration of at least about 2.5 g/l. The alkaline compound(s) for use in the compositions of this invention may be any of the compounds known to the art that produce a strongly alkaline solution when dissolved in water. Preferably, the alkaline compound is supplied in the form of a compound or a mixture of compounds selected fron the group consisting of alkali metal and ammonium hydroxides, carbonates, silicates and phosphates, as well as amines. We particularly prefer to employ an alkali metal hydroxide or a mixture of two or more alkali metal hydroxides, and above all a mixture of sodium hydroxide and potassium hydroxide. The alkaline compound(s) must be present in the aqueous alkaline composition of this invention in a concentration effective to impart a pH to the composition in the range of from about 9.5 to about 14+, and preferably in the range of from about 12 to about 14+. Generally speaking, the concentration of the alkaline compound and thus the pH value of the composition should be greater when the composition is employed at lower temperatures than when working at higher temperatures. For most purposes we have found that the concentration of alkaline compound(s) in the composition should be at least about 80 g/l, and more preferably in the range of from about 150 to about 350 g/l. One of the essential activator ma terials amongst the ingredients of the compositions of the present invention is tetrahydrofurfuryl alcohol hereinafter for brevity referred to as "THFA". As already previously explained, it was known to use this material in stripper compositions, even indeed in combination with furfuryl alcohol; but as will be seen from the test data reported below, we have found that the use of THFA in combination with the ethoxylated form of furfuryl alcohol yields improved results. The effectiveness of a composition containing both the ethoxylated material described below and THFA in stripping siccative coatings from substrates coated therewith has been found to be greater than that of a composition containing either of the ingredients in equivalent amounts, thus evidencing a synergistic action. THFA is preferably used at a concentration of at least about 2.5 g/l, especially at a concentration in the range of from about 2.5 to about 200 g/l, and above all at a concentration in the range of from about 4 to about 100 g/l. The inclusion of the ethoxylate(s) (i) and/or (ii) above exhibits certain definite advantages. They do not form an azeotrope with water (as does furfuryl alcohol) and they therefore do not become rapidly depleted from a working bath by nonfunctional mechanisms. Because the ethoxylated material remains in the bath, the stripper cbmposition displays an increased effectiveness (more coating stripped/volume of composition) and thus one achieves a longer bath life. Indeed, we have found that a typical hot stripper composition of this invention can be used to strip siccative coatings from substrates coated therewith for a significantly extended period, perhaps two to three times longer than is possible with otherwise comparable compositions instead containing either furfuryl alcohol alone or furfuryl alcohol together with tetrahydrofurfuryl alcohol. A preferred ethoxylate for use in the compositions of this invention is the reaction product of furfuryl alcohol with ethylene oxide wherein m is in the range of from about 0.5 to about 1.5. Particularly preferred is such a product in which m is from about 0.85 to about 1.08. Another preferred ethoxylate for use in the compositions of this invention is the reaction product of tetrahydrofurfuryl alcohol with ethylene oxide wherein n is in the range of from about 3 to about 8. The ethoxylate(s) used in the composition must naturally be present in an effective concentration, which will depend on the type of siccative coating to be removed, as well as on the thickness of the coating. Higher concentrations are generally required to remove siccative coatings such as a cathodic electrodeposition paint than are required to remove ones such as an alkyd paint. The ethoxylate will preferably be present in a concen tration effective (in a fresh composition, i.e.that has not previously been used to strip siccative coatings) to remove cathodic electrodeposition paint from a substrate coated therewith in a period within the range of from about 5 seconds to about 1 hour, at a composition temperature in the range of from about 1800 to about 220 0F (approx. 82 - 104 C). For most purposes we have found that the ethoxylated material should be present in a concentration of at least about 5 g/l, and prefer ably within the range of from about 5 to about 200 g/l. Particularly preferred concentrations are in the range of from about 10 to about 100 g/l, and above all from about 20 to about 50 g/l. The addition of a sequestering agent to the compositions of this invention has been found to be very advantageous, since its presence ensures that the composition may be effectively employed regard less of the hardness of the water used to formulate it, without generally experiencing precipitation of the calcium and magnesium ions that cause water hardness; and more surprisingly, its presence addi tionally improves the ability of the compositions to remove siccative coatings from substrates coated therewith. While we do not wish to be limited by any theoretical considerations, we assume that this can perhaps be explained upon the basis that the sequestering agent aids in breaking the bond between the substrate and the paint film, through super ficial action on the substrate. Representative of the sequestering agents which may be employed singly or in admixture in the compositions of this invention are hydroxy-carboxylic acids such as gluconic, citric and tartaric acids, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, and various commercial preparations - such as Belzak AC, manufactured by Belzak Corporation. The currently-preferred sequestering agents are gluconic acid and/or Belzak AC. The sequestering agent should preferably be added in a concentration which will be effective substantially to prevent precipitation of the calcium and magnesium ions that are the primary cause of water-hardness. Generally speaking, greater amounts of the sequestering agent will therefore be required when the hardness of the water is high than when it is low. For most purposes we have found that the concentration of sequestering agent should be at least about 1 g/l, and preferably in the range of from about 1 to about 100 g/l. A composition-stabilizing compound can also with advantage be incorporated in the compositions of this invention. Such composition-stabilizing compounds include aliphatic primary alcohols, aliphatic secondary alcohols, alkylamines and mixtures thereof. Without limiting ourselves by any theoretical considerations, we think that such stabilizing compounds probably act as a secondary solvent, miscible in water, which functions to provide a more uniform solution that will not separate upon standing. The stabilizing compounds are believed also to increase the effectiveness of the composition by functioning to dissolve soaps that are formed by reaction of the siccative coating with the alkaline compound, thereby rendering the soaps ineffective to hinder further such reaction. The composition-stabilizing compound will preferably be one or a mixture of more than one of the following, namely methanol, monoethanolamine, diethylene glycol, propylene glycol, dipropylene glycol and n-butyl amine. The most preferred stabilizing compounds are methanol, monoethanolamine, diethylene glycol and n-butyl amine. The composition-stabilizing compound will preferably be present in a concentration effective substantially to prevent separation of the composi tion of the invention. For most purposes we have found that the composition-stabilizing compound should be added in a concentration of at least about 10 g/l, and preferably in the range of from about 50 to about 200 g/l. Although not essential, the composition of this invention will preferably also contain one or more surfactants or wetting agents, which presumably may serve to deterge and emulsify plasticizers or other components of lower molecular weights in the film of the siccative coating, thereby promoting removal thereof. There appears to be nothing critical about the choice of surfactant or wetting agent employed; and amphoteric, non-ionic and anionic surfactants may all be employed. Currently preferred surfactants are: Miranol JEM Concentrate, manufactured by Miranol Chemical Co.; and Sulfonate OA-5, manufactured by Cities Service Co.["Sul-fon-ate OA-5" is a trademark for an anionic wetting agent said to be sulphonated oleic acid, sodium salt]. The composition will preferably contain a con centration of at least about 0.5 g/l of one or more surfactants; particularly advantageous concentrations are in the range of from about 0.5 to about 20 g/l. Preferred compositions in accordance with this invention are those which contain an alkaline component in a concentration within the range of from about 150 to about 350 g/l, the alkaline component in turn comprising from 3.5 to about 350 g/l of sodium hydroxide and/or from 3.5 to about 350 g/l of potassium hydroxide, said composition also containing from about 1 to about 100 g/l of a sequestering agent, from about 50 to about 100 g/l of one or more composition-stabilizing compounds being methanol, monoethanolamine, diethylene glycol and/or n-butyl amine, from about 2.5 to about 200 g/l of tetrahydrofurfuryl alcohol, and from about 5 to about 200 g/l of an ethoxylate (ii) being the reaction product of furfuryl alcohol and ethylene oxide wherein m is in the range of from about 0.5 to about 1.5. In these preferred compositions the ethoxylate (ii) will desirably be one in which m is in the range of from about 0.85 to about 1.08. They will also advantageously include one or more surfactants in a concentration in the range of from about 0.5 to about 20 g/l. According to another aspect, this invention also provides a process for stripping siccative coatings from substrates coated therewith, in which the coated substrate is contacted with a stripper composition in accordance with the present invention as herein described, at a composition temperature and for a time sufficient to remove the siccative coating from the substrate. The process of this invention displays itself to best advantage when the siccative coating being stripped is a cathodically-electrodeposited paint film. Siccative coatings may be stripped from sub strates coated therewith by contacting the coated substrate with the hot stripper composition at elevated temperatures, preferably when maintained at a rolling boil. The compositions of the invention are for most purposes best employed at a temperature of at least about 1400F (600C), and especially in the range of from about 1800 to about 2200 F (approx. 82-1040C). The minimum period of contact between the composition and the substrate which will be sufficient to remove the siccative coating from the substrate will depend on a number of factors, including the nature of the siccative coating, the number of substrates previously contacted with the composition, the temperature of the composition, the total coated surface area of the substrate in contact with the composition, the thickness of the siccative coating, and the concentration of various of the constituents. Generally speaking, we have found that contact times effective to remove the siccative coating from a substrate coated therewith will be within the range of from about 5 seconds up to about 1 hour at a temperature within the range of from about 1800 to 2200F (approx. 82-1040C) for a fresh composition, i.e. a composition that has not previously been used to remove the siccative co atings. It should be borne in mind that the contact period required to remove the siccative coating will tend to increase when the temperature of the composition is decreased, when the number of coated substrates previously contacted with the composition is increased, when the surface area of coated substrate in contact with the composition is increased, when the thickness of the coating to be stripped is increased, and/or when the concentration of the compositionactivating compound of the invention is decreased. The coated substrates to be stripped may be contacted with the compositions of the invention according to any of the methods known to the art. Generally speaking, the coated substrate to be stripped will be immersed in a bath of the composition. Once the siccative coating has been removed, the substrate will preferably be rinsed with water and then dried. The hot stripper composition may be initially formulated as an aqueous concentrate, which subsequently is diluted with water to make-up the aqueous alkaline composition of the invention. Such an aqueous concentrate should be so formulated that when it is added to water at a concentration in the range of from about 10 to about 99% by volume, it will make-up an aqueous alkaline hot stripper composition with a pH within the range of from about 9.5 to about 14+, which will be effective at elevated temperatures to remove siccative coatings from substrates coated therewith. The aqueous concentrate will preferably be added to water at a concentration of from about 40% to about 60% by volume; and when so added the alkaline component therein will desirably be present in a concentration which imparts a pH in the range of from about 12 to about 14+ to the resultant composition. For most purposes we have found that the alkaline component should preferably constitute from about 10 to about 50 wt. % of the concentrate. The THFA and the ethoxylate(s) should also be present in the concentrate in such concentrations that the hot stripper composition produced by diluting the concentrate will contain concentrations of these ingredients which will be effective to remove cathodic electrodeposition paint from a substrate coated therewith in a period in the range of from about 5 seconds to about 1 hour, at a composition temperature in the range of from about 1800 to 2200F (approx. 82-104 0C). We have found that for most purposes THFA typically can constitute at least about 1 wt. %, and preferably in the range of from about 1 to about 20 wt. %, of the concentrate. The concentrate may also optionally but desirably contain one or more of the following other components, each as previously defined herein, namely a sequestering agent in concentration of at least about 0.1 wt. % and preferably in the range of from about 0.1 to about 10 wt. %; a compositionstabilizing compound in a concentration of at least about 1 wt. %, and preferably in the range of from about 1 to about 20 wt. %, and one or more surfactants, at a concentration of at least about 0.1 wt. %, and preferably in the range of from about 0.1 to about 10 wt. %. Particularly preferred concentrates contain: from about 10 to about 85 wt. % water; from about 10 to about 50 wt. % of an alkaline component, which in turn comprises from 0.5 to about 50 wt. % of sodium hydroxide and from 0.5 to about 50 wt.% of potassium hydroxide; from about 0.1 to about 10 wt. % of a sequestering agent; from about 1 to about 20 wt. % of composition-stabilizing compound(s) being one or more of the following, namely methanol, monoethanolamine, diethylene glycol and n-butyl amine; from about 1 to about 20 wt. % of the reac-tion product of furfuryl alcohol and ethylene oxide being an ethoxylate (ii) wherein m is in the range of from about 0.5 to about 1.5, and preferably in the range of from about 0.85 to about 1.08. This preferred concentrate will moreover also advantageously contain one or more surfactants, at a concentration in the range of from about 0.1 to about 10 wt. % Even though the ethoxylate(s) included in the compositions may properly be regarded as nonvolatile when compared with furfuryl alcohol (a property which as already stated results in an increased effectiveness and bath life relative to conventional compositions containing furfuryl alcohol) these ethoxylate(s) nevertheless are gradually depleted during continuous use of the composition. It does therefore become desirable to replenish a bath of the composition after a certain period of use. The point in time at which replenishment becomes necessary may be readily determined by monitoring the period needed to strip a siccative coating from a substrate; as the activator is depleted, this period will increase, until eventually it will reach a stripping period that is commercially unacceptable. In this way one can readily determine when the addition of a replenishing composition is required. We have found that when replenishing the composition, it is generally speaking best to restore the concentration of the ethoxylate(s) to about the initial concentration without increasing the concentration of alkaline compound beyond its concentration in the initial composition. The replenisher composition of the invention will therefore generally contain a higher concentration of the ethoxylate(s) and a lower concentration of the alkaline compound than may b desirable in the hot stripper composition itself. A replenisher composition suitable for use in replenishing the hot stripper composition of this invention will frequently contain about 1 to about 200 g/l of the alkaline compound, sufficient to impart a pH to the replenisher of about 9.5 to about 14+, preferably about 12 to about 14+, as well as from about 50 to about 200 g/l of the ethoxylate(s) and at least about 50 g/l, and preferably from about 50 to about 200 g/l, of the THFA. Although not essential, the replenisher composition will preferably contain one or more of the following previously defined components, namely a sequestering agent in a concentration of from about 2.5 to about 100 g/l; a composition-stabilizing compound in a concentration of from about 10 to about 200 g/l; and one or more surfactants, in a concentration of from about 1 to about 100 g/l. In passing it may be observed that, although the primary utility of the replenisher composition is naturally in the replenishment of the hot stripper composition of this invention, yet we have found that the replenisher composition may also be effectively employed to replenish those prior art compositions which contain furfuryl alcohol and/or THFA. EXAMPLES In order that the invention may be well understood it will now be described in more detail, though only by way of illustration,in and with reference to the following examples: It should be noted that the reaction product (FA/ETO) of furfuryl alcohol (FA) and ethylene oxide (ETO) employed in the following examples is an ethoxylate, manufactured by the Quaker Oats Company, of Chicago, Illinois, United States of America, of general formula (ii) wherein m is in the range of from about 0.86 to about 1.08; and which may be further defined by the following experimentallydetermined values: specific gravity, 1.132-1.134 at 250C; refractive index, Nd20 = 1.4844 - 1.4846; flash point (approx.) 225 F (107 C); hydroxyl number, all00 + 14; Gardner colour, 18; viscosity, 13 cps. EXAMPLES 1 to 3 Concentrates 1, 2 and 3 were first prepared, which contained the components in the concentrations indicated below. Stripping compositions 1, 2 and 3 were then prepared (each from the concentrate bearing the same number) by diluting a given volume of the concentrate with an equal volume of water. Concentrate & Composition No.1 Ingredient Concentrate 1 Composition 1 (wt. %) (g/l) Water 8.0 Sequestering agent (Belzac AC) 1.5 10.31 Sodium hydroxide (50%) 34.0 233.75 Potassium hydroxide (50%) 32.0 220.00 Diethylene glycol 10.0 68.75 FA/ETO 9.0 61.88 THFA 5.0 34.38 Amphoteric surfactant Miranol JEM Conc.) 0.5 3.44 100.0% Concentrate & Composition No.2 Ingredient Concentrate 2 Composition 2 (wt. /O) (g/l) Water 8.0 Sequestering agent 1.5 10.59 (Belzac AC) Sodium hydroxide (50%) 30.0 211.80 Potassium hydroxide (50%) 30.0 211.80 Diethylene glycol 13.0 91.78 FA/ETO 9.0 63.54 THFA 5.0 35.30 Monoethanolamine 1.0 7.06 Composition-stabilizer (Dowanol EPh, manufactured by Dow Chemical Company) 1.0 7.06 Amionic surfactant (Sulfonate OA-5) 1.0 7.06 Amphoteric surfactant 0.5 3.53 (Miranol JEM Conc.) Concentrate & Composition No.3 Ingredient Concentrate 3 Composition 3 (wt. %) (g/l) Water 11.0 Sequestering agent (Belzac AC) 1.5 10.22 Sodium hydroxide (50%) 34.0 231.54 Potassium hydroxide (50%) 32.0 217.92 Diethylene gycol 10.0 68.10 FA/ETO 6.0 40.86 THFA 5.0 34.05 Amphoteric surfactant 0.5 3.41 (Miranol JEM Conc.) Equal volumes of Composition 1, Composition.2, and Composition 3 were placed in three baths, which were heated toad maintained at a temperature within the range 210-220 F (99-104 C) during the course of use, except as otherwise noted below. Five sets of stel panels (3 per set) each measuring 4 inches by 12 inches (approx. 10.2 cm X 30.5 cm) were precoated with a cathodic electrodeposition paint, and thereafter employed in this experiment, which was designed to simulate continuous use of the compositions to strip numerous panels. One of the panels in each set was then immersed in Composition 1, the second in Composition 2, and the third in Composition 3, in accordance with the sequence of operations which with a description of the test conditions and the results of testing are set forth in Table 1 below: TABLE 1 Bath Conditions Panel Immersion Time/Percentage Sequence of of Paint Removed From Panels Alteration During Said Immersion Time Composition 1 Composition 2 Composition3 initial bath; no paint added; no panels previously immersed therein First set of panels immersed 6-7mins./10Z0% 6-7 mins./100% 8-9mins.z00% panels removed; 5 grams of paint added to each bath; baths maintained at a boil for about 15 minutes. CABLE 1 continued) Composition 1 Composition2 ComposiFion 3 second set of panels immersed 8-8anins./100% 82 mins./100% 11-12mins./100% Panels removed; 5 grams of paint added to each bath; baths maintained at a boil for about 15 minutes third set of panels immersed 10-11mins./100% 9-10mins./100% 13mins./100% panels removed; 5 grams of paint added to each bath; baths maintained at a boil for about 15 minutes fourth set of panels immersed 12 mins./100% 10-11 mins./100 ; 16 mins./100% panels removed; 5 grams of paint added to each bath; baths maintained at a boil for about 15 minutes fifth set of panels immersed 20 mins./100% 17-18mins.1100% 20 mins./60- 70% EXAMPLES 4 and 4-A Concentrate 4 was first prepared containing the ingredients and concentrations thereof noted below. Two compositions were then prepared from the concentrate; Composition 4 was formulated by diluting a given volume of Concentrate 4 with an equal volume of water; while Composition 4-A was prepared by diluting a given volume of Concentrate 4 with sufficient water to form a solution comprising 45% by volume of Concentrate 4. Concentrate 4 & Compositions 4 & 4-A Ingredient Concentrate 4 Composition 4 Composition (wt. %) (g/l) 4-A (g/l) Water 7.0 Sequestering agent (Belzac AC) 1.5 10.34 9.32 Sodium hydroxide (50%) 34.0 234.80 211.32 Potassium hydroxide (50%) 34.0 234.80 211.32 Diethylene glycol 12.0 82.87 74.58 FA/ETO 6.0 41.44 37.29 THFA 5.0 34.53 31.08 Amphoteric surfactant (Miranol JEM Conc.) 0.5 3.45 3.11 100.0% Equal volumes of Compositions 4 and 4-A were then employed in stripping operations, as follows. Using sets of steel panels measuring 1 inch by 4 inches (approx. 2.5 cm X 10.2 cm) precoated with cathodic electrodeposition paint, the time required to remove 100% of the paint from the panels immersed in the two compositions at various composition temperatures was recorded. At each temperature, 1 panel was immersed in Composition 4 and 1 panel was immersed in Composition 4-A. The results are summarized in Table 2 below. TABLE 2 Composition Time Required to Strip 100% of Paint Temperature From Panels Immersed in Composition Composition 4 Composition 4-A 220 0F (-.104 C) 3-4 minutes 52 - 6 minutes 2100F (- 99 0C) 4-5 minutes 6 - 7 minutes 2000F (. 93 0C) 7-7- minutes' 8 - 9 minutes 1900 F ( 88 0C) 8-9 minutes 92 minutes The ability of Composition 4 to strip paint from 41,X12" (approx. 10.3 cm X 30.5 cm) panels coated with a black, cathodic electrodeposition paint was also evaluated.The total number of panels tested was 46; at a succession of separate moments during continuous use, a single such panel was immersed in Composition 4, and the time of immersion required to remove the indicated percentage of paint from each panel was recorded. In between these measurements, a succession of identical panels were immersed in the composition until 100% of the paint had been removed from each of them, and it was then replaced by the next one. This was intended to simulate the bath loading conditions encountered in commercial use. The results are summarized in Table 3 below. Number of Composition Immersion % of Paint Temperature Time Stripped Mins.) (Mins.) During Time Immersed ( F) (approx. C) Composition 4 1 190 88 5-5¸ 60 1 190 88 8-9 100 1 200 93 4-5 50 200 93 7-72 100 1 210 99 3-3¸ 80-90 210 99 4-5 100 5 210-220 99-104 ---- 100 4 210-220 99-104 ---- 100 5 210-220 99-104 ---- 100 1 200 93 6-7 90-95 200 93 72-8 100 5 210-220 99-104 ---- 100 5 210-220 99-104 ---- 100 1 200 93 8 -8 - 100 5 210-220 99-104 ---- 100 5 210-220 99-104 ---- 100 1 200 93 10-102 100 200 93 12-122 100 5 210-220 99-104 ---- 100 1 200 93 11-11¸ 100 200 93 15-15¸ 100 The experimental sequence summarized in Table 3 was continued until 100% of the paint could no longer be stripped from an immersed panel. The total painted surface area of those panels from which 100% of the paint had been stripped was calculated, and divided by the volume of the composition employed. The results are summarized in Table 4 below. TABLE 4 Painted Surface Area Composition 4 Stripped/Volume of Composition 28 sq. ft./U.S.gallon (approx. 68.72 dm2 /litre) EXAMPLE 5 An aqueous alkaline concentrate, Composition 5, was formulated as follows: Composition 5 Ingredient % by Wt. Water 34.8 Sequestering agent (Belzac AC) 0.5 Sodium hydroxide (50%) 10.0 Potassium hydroxide (45%) 10.0 Diethylene glycol 18.0 FA/ETO 10.0 THFA 2.0 Amphoteric surfactant (Miranol JEM Conc.) 2.0 Methanol 14.5 77% This concentrate was used in replenishing compositions of the present invention, as well as those prior art compositions containing either furfuryl alcohol alone or both furfuryl alcohol and tetrahydrofurfuryl alcohol. Composition 5 was added to such compositions, after continuous use thereof, in order to extend the operability of such compositions. The next group of examples represent a series of comparative tests, which exemplify the synergistic properties of hot stripper compositions within the scope of the present invention. As a first step a control composition was prepared with the following ingredients: CONTROL COMPOSITION C Ingredients % by Weight Water 26.5 Sodium hydroxide (50%) 34.0 Potassium hydroxide (50%) 34.0 Amphoteric surfactant (Miranol JEM Conc.) 0.5 Methanol 5.0 100 .0% Control Composition C was used as the basis for preparing the various other compositions identified in Table 5 below; and those other compositions, as well as Composition C itself, were used to strip the paint from steel panels prepainted with cathodically-electrodeposited green paint films having thicknesses of 1 to 1.5 mil. The painted panels were immersed in the freshly prepared compositions referred to in Table 5, and maintained therein until 100% of the film was stripped. The times required to accomplish this were recorded and are reported in Table 5. The compos- tions were then subjected to a rolling boil for six hours, and thereafter were used to strip the paint from steel panels painted like those referred to above. The times needed to strip 100% f the paint films from the panels were recorded, and are reported in Table 5. The ethoxylate used in various of the compositions referred to in Table 5 was the reaction product of ethylene oxide with THFA, of general formula (iii) above wherein n is about 1.5, and is referred to in the Table as "THFA/ETO". TABLE 5 Ex.No. Comp. Stripping Time in Minutes Fresh Comp. Boiled Comp. (880C-99 C) (99 C-105 C) C-1 100 g of C 31 not effective in 45 minutes C-2 90 g of C and 10 g furfuryl alcohol 8 23¸ C-3 90 g of C and 10 g of FA/ETO 9¸ 102-11 C-4 90 g of C and 10 g of THFA 9 10¸ C-S 90 g of C and 10 g of THFA/ETO 10 13 C-6 90 g of C, 5 g of furfuryl al cohol, 5 g THFA 6 172 C-7 90 g of C, 5 g of furfuryl al alcohol and 5 g of THFA/ETO 6 182 6 90 g of C, 5 g of FA/ETO and 5 g of THFA 6'2-7 102-11 7 90 g of C, 5 g of FA/ETO and 5 g of THFA/ETO 72-8 11 90 g of C, 5 g of THFA AND 5 g THFA/ETO 72 11-112 9 85 g of C, 5 g of fur furyl alcohol, 5 g of FA/ETO and 5 g THFA 4 912 10 85 g of C, 5 g of FA/ETO, 5 g of THFA and 5 g of THFA/ETO 52 62-7 Examples Nos. 6 onwards in Table 5 above are compositions according to this invention, and their results may be compared with those obtained using the control compositions of Examples C-2 to C-6; such a comparison reveals the synergistic effects which are displayed by compositions within the scope of the present invention. The loss of effectiveness of a composition including furfuryl alcohol as it is subjected to elevated temperature for prolonged periods is exemplified by the results shown for the compositions of Examples C-6 and C-7. The compositions of Example Nos.9 and 10 show the improved results that can be achieved by utilizing higher amounts of various of the activating ingredients.

Claims: CLAIMS 1.An aqueous alkaline stripper composition, for use at elevated temperatures to remove siccative coatings from substrates coated therewith7 comprising one or more alkaline compounds in a concentration such as to impart a pH of about 9.5 or more to the composition, together with an effective amount of at least two of the following three activator materials: (i) tetrahydrofurfuryl alcohol and furfuryl and/or tetrahydrofurfuryl alcohol ethoxylates of the general formula: EMI29.1 wherein m and n, which may be the same or different, each represents the average degree of ethoxylation in the respective ethoxylates, and each of them lies in the range of from about 0.5 to about 10. 2. An aqueous alkaline stripper composition, for use at elevated temperatures to remove siccative coatings from substrates coated therewith, comprising one or more alkaline compounds in a concentration such as to impart a pH of about 9.5 or more to the composition, together with an effective amount of a combination of activator materials, said combination comprising: (i) tetrahydrofurfuryl alcohol with at least one or the furfuryl and/or tetrahydrofurfuryl alcohol ethoxylates of the general formulae: EMI30.1 wherein m and n, which may the same or different, each represents the average degree of ethoxylation in the respective ethoxylates, and each of them lies in the range of from about 0.5 to about 10. 3. A stripper ocmposition as claimed in either of the preceding claims, wh h includes an ethoxylate of general formula (-ii) which is the reaction product of furfuryl alcohol and ethylene oxide and wherein m is in the range of from about 0.5 to about 1.5, preferably in the range of from about 0.85 to about 1.08. 4. A stripper composition as claimed in any of the preceding claims, which includes an ethoxylate of general formula (iii) which is the reaction product of tetrahydrofurfuryl alcohol and ethylene oxide and wherein n is in the range of from about 3 to about 8. 5. A stripper composition as claimed in any of the preceding claims, in which the total overall concentration of all the activator materia (i) - (iii) present is at least about 7 g/l, and a least two of these activator materials are each present in a concentration of at least about 2.5 g 6. A stripper composition as claimed in any of the preceding claims, in which the ethoxylate(s) (ii) and/or (iii) is/are present in a concentration of at least about 5 g/l. 7. A stripper composition as claimed in any of the preceding claims, in which the concentration of alkaline'compound(s) present is effective to impart a pH to the composition in the range of from about 9.5 to about 14+, and preferably from about 12 to about 14+. 8. A stripper composition as claimed in any of the preceding claims, which also includes a sequestering agent in an amount effective substantially to prevent the formation of precipitants in the composition. 9.A stripper composition as claimed in any of the preceding claims, which as compositionstabilizing compound also includes one or more of the following, namely aliphatic primary alcohols, aliphatic secondary alcohols, alkyl amines and mixtures thereof, said composition-stabilizng compound(s) being present in an amount effective substantially to prevent separation of said composition. 10. A stripper composition as claimed in claims 7, 8 and 9 which contains at least about 80 g/l of the alkaline compound(s), at least about 1 g/l of the sequestering agent, and at least about 10 g/l of the composition-stabilizing compound(s). 11. A stripper composition as claimed in any of the preceding claims, which also includes at least about 0.5 g/l of one or more surfactants. 12. A stripper composition as claimed in any of the preceding claims in which the alkaline compound(s) is/are present in a concentration within the range of from about 150 to about 350 g/l, said alkaline compound (s) comprising from about 3.5 to about 350 g/l of sodium hydroxide and from about 3.5 to about 350 g/l of potassium hydroxide, said stripper composition also containing from about 1 to about 100 g/l of a sequestering agent, from about 50 to about 100 g/l of one or more compositionstabilizing compound(s) being methanol and/or monoethanolamine, and/or diethylene glycol and/or n-butyl amine, from about 2.5 to about 200 g/l of tetrahydrofurfuryl alcohol, and from about 5 to about 200 g/l of the ethoxylate(s) (ii) and/or (iii) said ethoxylate(s) preferably being those wherein m and/or n each lies in the range of from about 0.85 to about 1.08. 14. A process as claimed in claim 13, in which the siccative coating upon the -substrate is a cathodically-electrodeposited paint film. 15. An aqueous alkaline composition as claimed in any of claims 1 to 12, in the form of a concentrate intended for making up the hot stripper comosition employed in the process claimed in claim 13 or claim 14, said concentrate being such that when added to water at a concentration level of from about 10% to about 99% by volume it is effective to strip siccative coatings from metallic substrates. 16. A make-up concentrate as claimed in claim 15, which contains from about 10% to about 85 wt. % water, from about 10 to about 50 wt. % of an alkaline component which in turn comprises from 0.5 to about 50 wt. % of sodium hydroxide and from 0.5 to about 50 wt. % of potassium hydroxide, said concentrate also containing from about 0.1 to about 10 wt. % of a sequestering agent, from about 1 to about 20 wt. % of a composition-stabilizing compound being methanol and/or monethanolamine and/or diethylene glycol and/or n-butyl amine, from about 1 to about 10 wt. % of tetrahydrofurfuryl alcohol, and from about 1 to about 20 wt. % of the reaction product(s) of ethylene oxide with furfuryl alcohol and/or tetrahydrofurfuryl alcohol represented by the respective general formulae (ii) and (iii), preferably wherein respectively m and n are in the range of from about 0.5 to about 1.5, above all from about 0.85 to about 1.08. 17. An aqueous alkaline replenisher composition for replenishing hot stripper compositions, primarily those employed in the process claimed in claim 13 or claim 14, said replenisher composition comprising one or more alkaline compound(s) in a concentration in the range of from about 1 to about 200 g/l, at least about 50 g/l of tetrahydrofurfuryl alcohol, and one or more of the ethoxylates (ii) and/or (iii) in a concentration in the range of from about 50 to about 200 g/l.

Inventors: CARANDANG, CARMEN MANECLANG
Applicants: AMCHEM PRODUCTS, INC.
Application year: 1981
Main classification: C09D9
IPC codes: C09D9, C09D5