WO1994010231A1 - Procede de suppression de l'adhesivite de peintures au moyen d'une dispersion polymere a teneur en formaldehyde limitee - Google Patents

Procede de suppression de l'adhesivite de peintures au moyen d'une dispersion polymere a teneur en formaldehyde limitee Download PDF

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Publication number
WO1994010231A1
WO1994010231A1 PCT/US1993/010132 US9310132W WO9410231A1 WO 1994010231 A1 WO1994010231 A1 WO 1994010231A1 US 9310132 W US9310132 W US 9310132W WO 9410231 A1 WO9410231 A1 WO 9410231A1
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WIPO (PCT)
Prior art keywords
formaldehyde
melamine
range
polymer
composition
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Ceased
Application number
PCT/US1993/010132
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English (en)
Inventor
Scott J. Beleck
Wilbert J. Roberts
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Henkel Corp
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Henkel Corp
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Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of WO1994010231A1 publication Critical patent/WO1994010231A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/71—Paint detackifiers or coagulants, e.g. for the treatment of oversprays in paint spraying installations

Definitions

  • This invention relates to the detackification of paint and similar materials entrained in water, particu- larly circulating water in a conventional automobile plant spray booth.
  • "Paint” as used herein is to be un ⁇ derstood as a generic term which encompasses all common varieties of water insoluble organic binder containing coatings commonly applied in spraying operations, includ- ing but not limited to oil based paints, enamels, lac ⁇ quers , high solids solvent based automotive body base coat, high solids solvent based automotive body clear coat , water borne auto body base and clear coats , ure- thane polymer containing auto body top coats , and solvent and water borne primers .
  • paints may utilize as- phaltic, acrylic, polyester, melamine-formaldehyde , iso- cyanate, epoxy, alkyd, melamine alkyd, and blocked poly ⁇ urethane resins among others , along with appropriate sol ⁇ vents , pigments , and ancillary additives .
  • Paint "over- spray” the portion of the sprayed paint which does not fall on the surface (s) it is intended to protect, if left untreated, readily adheres to the walls of spray booths and any other surfaces that it contacts, such as the sur ⁇ faces of water distribution piping, spray nozzles, and the like.
  • Use of a process according to this invention converts the paint overspray to a non-sticky sludge suit- able for convenient disposal.
  • a melamine-aldehyde polymer particularly a melamine-for aldehyde resin acid colloidal solution
  • the previously known polymers of this type made from formaldehyde usually contain substan ⁇ tial amounts of free formaldehyde.
  • most commercial liquid melamine-formaldehyde resins contain at least 0.2 % by weight of free formaldehyde.
  • Formaldehyde is be ⁇ lieved to be a carcinogen, so that use of materials con ⁇ taining more than a minimal amount of it is undesirable in general. It is an object of this invention to provide detack- ifying processes at least as effective as those taught by the prior art while minimizing exposure of workers who use the process to free formaldehyde.
  • the content of free formaldehyde in a given volume of either the starting res ⁇ in or the modified resin is defined as the product of the free formaldehyde concentration and the volume.
  • the thus modified melamine-formaldehyde resins may advantageously be combined with other materials, such as flocculants, de- foamers, and the like, to maximize the practical value of their detackifying and flocculating effect, in a manner generally known per se in the art for using unmodified melamine-formaldehyde resins in detacki ication.
  • Various embodiments of the invention include aqueous liquid compositions including modified dispersions of mel ⁇ amine-formaldehyde polymers that are useful in detackify ⁇ ing when added to the circulating water in spray booths, processes for making such modified dispersions, and de- tackifying processes using the compositions containing the modified melamine-formaldehyde polymer dispersions.
  • detackifying processes are especially advantageously used as part of processes comprising steps of (I) detackifying and flocculating paint entrained in a circulating water based liquid to produce a flocculated sludge, (II) separating detackified and flocculated paint solids from residual water based liquid, and (III) using the residual water based liquid to entrain additional paint.
  • detackifying may be achieved according to this invention in a variety of other ways which are generally, except for the particular detackifying agent used, known per se in the art and are all within the broad scope of this invention.
  • the preferred water-soluble diketo compound for use in the invention is acetoacetamide, also known as ⁇ -keto- butyramide (CAS Registry No. 5977-14-0) .
  • acetoacetamide is often mentioned, but it should be understood that the invention is not limited thereby.
  • Other suitable diketo modifying reagents in ⁇ clude other ⁇ -ketocarboxylic acids and their salts, es ⁇ ters, amides, and the like, such as acetoacetic acid or its ethyl ester and ⁇ -diketones, such as acetylacetone.
  • the base melamine-formaldehyde polymer for use in this invention preferably is made by reacting melamine and formaldehyde, in a manner known in the art, with each other in a molar ratio of formaldehyde to melamine in the range from 6:1 to 1:1, preferably from 4:1 to 1:1, or more preferably from 3.0:1.0 to 1.0:1.0.
  • the concentration of dispersed polymer solids preferably is in the range from 1 to 20, more preferably from 3 to 15, or still more preferably from 6.0 to 12.0, %;
  • the con ⁇ centration of free formaldehyde preferably is in the range from 0.10 to 0.35, more preferably from 0.10 to 0.30, or still more preferably from 0.20 to 0.30, %;
  • the pH preferably is in the range from 1.0 to 3.0, more preferably from 1.5 to 2.3, or still more preferably from 1.7 to 2.1, all these values being those before reaction with the diketo modifying reagent.
  • the same pH values are preferred for the modified detackifying resin.
  • the concentration of melamine-formaldehyde resin is reduced to too low a value by the addition of large amounts of a diketo modifying reagent or of solvent such as water in which the diketo modifying reagent may be dissolved, the detackifying effectiveness of the modified resin dispersion will suffer.
  • the amount of modifying reagent is within the preferred ranges, the detackifying effectiveness in many cases is actually increased over that of the unmodified polymer dispersion.
  • the amount added should not be so large as to result in any visible formation of precipitate within 15 days after addition.
  • the amount of acetoacetamide added should have a ratio by weight to the initial free formaldehyde content of the polymer disper ⁇ sion reacted with it in the range from 135:1.0 to 6:1.0, more preferably from 80:1.0 to 13:1.0, or still more preferably from 52:1.0 to 33:1.0.
  • the amount added be such as to result in a free formaldehyde content of the modified resin dispersion, at the time of use, that is within the range from 15 - 65, more preferably from 17 - 50, or still more preferably from 20 - 40 % of the free formaldehyde content of the starting resin dis ⁇ persion used to make the modified resin dispersion.
  • the modified detackify- ing composition have a concentration of melamine-form ⁇ aldehyde polymer solids that is at least 50, more pref ⁇ erably at least 62, or still more preferably at least 75, % of the concentration of melamine-formaldehyde polymer solids in the starting resin from which the detackifying composition is made.
  • a modi ⁇ fied concentrated detackifying composition consisting essentially of water and:
  • (B) from about 0.008 to about 0.20, more preferably from 0.01 to 0.10, or still more preferably from 0.030 to 0.060, % of free formaldehyde;
  • (D) unreacted ⁇ -diketo modifying reagent molecules unreacted ⁇ -diketo modifying reagent molecules.
  • the free formaldehyde content for purposes of this invention is preferably measured, and for the specific values given below was measured, by a method utilizing quantitative spectrophotometric absorbance of light with a wave length of 550 nanometers (hereinafter "nm") in conjunction with commercially supplied reagents and apparatus which convert the formaldehyde in a sample to a colored reaction product.
  • the needed reagents and appa ⁇ ratus are supplied by CHEMetrics, Inc. of Calverton, Vir ⁇ ginia and are believed to be described in U. S. Patent 3,634,038.
  • the Vacu-vials® needed have the Catalog No.
  • the reaction between acetoacetamide or other diketo modifying reagent and the formaldehyde containing polymer may be effected at any temperature at which the polymer dispersion is liquid.
  • ambient human comfort temperature in the range from 20 - 30 ° C is preferred, both for convenience and because higher temperatures have been observed to increase the amount of free formaldehyde present in the starting melamine-formaldehyde resin and thereby require the addition of more of the diketo modi ⁇ fying reagent.
  • the normal time between commercial manu- facture and use of the modified resins will be sufficient for reaction at ambient temperature, as will be apparent from the data in the examples below.
  • Modification of polymer dispersions as contemplated by this invention includes not only the reduction of the initial free formaldehyde content but the retention with ⁇ in the modified polymer dispersion of any products of re ⁇ action between the free formaldehyde initially present and the added diketo modifying reagent, along with any unreacted diketo modifying agent.
  • a modified melamine-formaldehyde polymer dispersion according to this invention as de ⁇ scribed above is added to water containing entrained paint to be detackified and/or flocculated, preferably in an amount to give a ratio of solids content in the modi- fied polymer dispersion to solids content of the paint to be detackified within one of the following ranges, which are listed in order of increasing preference: from 0.01:1 to 5:1, from 0.01:1 to 2:1, from 0.05:1.0 to 0.50:1.0, or from 0.15:1.0 to 0.23:1.0.
  • Detackified paint is then re ⁇ moved from the circulating water by conventional means.
  • the starting melamine-formalde ⁇ hyde polymer dispersion was MAGNIFLOCTM 515C, a commercial product available from American Cyanamide Corp. with the following characteristics as described by its manufact ⁇ urer: A specific gravity of 1.01 - 1.035; a pH value of 1.7 - 2.1, and a solids content of 8.2 - 8.6 %.
  • the source of acetoacetamide used as the diketo mod- ifying reagent was BKBTM, commercially available from Eastman Chemical Co. and described by its supplier as a 30 % solution of acetoacetamide in water. These two in ⁇ gredients, along with additional water in some cases, were mixed, with stirring for the first eight hours, and then maintained in loosely stoppered containers for time periods up to 40 days, with samples periodically removed for assay of the free formaldehyde content. Some results are shown in Table 1 below. These results indicate that within one day at the latest after mixing, the free form- aldehyde content of the mixture had become low enough to qualify all these compositions as modified compositions within the meaning of this invention.
  • the concentration of free formaldehyde in the MAGNIFLOCTM 515C starting material ranged from about 2050 to 2750 ppm in about ten different measurements taken over a period of several weeks, with most of the individual measurements in the range from 2050 - 2200 ppm.
  • the concentration of free formaldehyde in the unmodified starting material was still at least 2000 ppm after 21 days and at least 1800 ppm after 40 days under the same storage conditions as those used to produce the data shown in the this table. Empty cells indicate that no measurement was made at the indicated time.
  • the circulating water system was turned on and the pH was adjusted to the range 9.0 - 9.5 by adding 50 % NaOH solution in water as required.
  • An amount of 230 milliliters (hereinafter "ml") of Composition 1.6 as de ⁇ scribed in Table 1 above was slug fed to the circulating system, and 2 minutes (hereinafter " in") later 30 - 40 grams (hereinafter "g") of paint (CMCTM "D03M Silver Slate Gray Metallic”) was sprayed into the booth at a rate of 40 - 60 g/min. After 5 min of circulation, the circula ⁇ tion was halted long enough to determine that the paint was still tacky.
  • Circulation was then resumed, and after 3 min an additional amount of 530 ml of Composition 1.6 was slug fed to the system. Two minutes after this ad- dition, an additional 30 - 40 g of paint was sprayed into the booth, and 3 min later, circulation was stopped long enough to determine that the paint was still tacky.
  • Example 2.2 the sequence of events was much like that of Example 2.1, with successive additions of Composition 1.6 and paint and additions of 50 % NaOH in water as needed to maintain the pH between 9.0 and 9.5, until virtually complete detackification of 936 g of paint was achieved with the addition of 427 ml of Compo ⁇ sition 1.6.
  • Comparison Example 2.2 a composition made by mix- ing 9 parts by weight of MAGNIFLOCTM 515C with 1 part by weight of water, so that it contained the same concentra ⁇ tion of dispersed melamine-formaldehyde polymer solids as Composition 1.6, was used instead of Composition 1.6. Much less effective detackification of a similar amount of the same kind of paint was achieved with a similar amount of this comparison composition.
  • the modified Composition 1.8 as de ⁇ scribed in Table 1 was used as the detackifier, and the paint was a Du Pont red-blue metallic base blend with a viscosity of 24 seconds in a ⁇ 2 Zahn Cup.
  • the pH was initially adjusted to 9.25. Before any paint had been sprayed into the test booth, foaming was observed, so that 10 ml of a conventional hydrocarbon emulsion de- foamer (P3TM Defoa er 2483, commercially available from Henkel Corporation) was added to the circulating water, and it was observed that the pH had fallen to 9.14.
  • P3TM Defoa er 2483 conventional hydrocarbon emulsion de- foamer
  • the total materials added were 880 ml of Composition 1.8, 315 ml of alkalinizer, 2550 ml of the flocculant solution, 1248 g of paint, and 16 ml of de ⁇ foamer.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Procédé de suppression de l'adhésivité de peintures consistant à mélanger avec celles-ci des dispersions de résine de formaldéhyde-mélamine et compositions contenant lesdites dispersions possédant davantage de formaldéhyde libre qu'il n'est souhaitable pour des raisons de santé et/ou de pollution; on traite ces dispersions avant leur mélange avec la peinture en y ajoutant des réactifs dicéto, de façon à limiter la teneur en formaldéhyde libre, tout en ne diminuant pas et, dans certains cas, en augmentant la capacité des dispersions à supprimer l'adhésivité de la peinture.
PCT/US1993/010132 1992-11-03 1993-10-28 Procede de suppression de l'adhesivite de peintures au moyen d'une dispersion polymere a teneur en formaldehyde limitee Ceased WO1994010231A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US97072792A 1992-11-03 1992-11-03
US07/970,727 1992-11-03

Publications (1)

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WO1994010231A1 true WO1994010231A1 (fr) 1994-05-11

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CN (1) CN1090308A (fr)
WO (1) WO1994010231A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753022A4 (fr) * 1994-03-29 1998-04-08 Henkel Corp Composition et procede permettant de rendre la peinture moins collante
EP0826014A4 (fr) * 1995-05-08 1998-04-08
US6384184B1 (en) 1998-05-23 2002-05-07 Henkel Kommanditgesellschaft Auf Aktien Method for decreasing the formaldehyde content in acidic solutions of melamine formaldehyde resins
EP1693393A1 (fr) 2005-02-22 2006-08-23 Lanxess Deutschland GmbH Produits de condensation contenant des groupes acides
EP1873176A1 (fr) 2006-06-23 2008-01-02 Lanxess Deutschland GmbH Produits de condensation dialdéhydes contenant des groupes acides
WO2018024559A1 (fr) * 2016-08-01 2018-02-08 Basf Se Dispersions polymères à émission d'acétaldéhyde réduite
CN110099940A (zh) * 2016-12-21 2019-08-06 巴斯夫欧洲公司 制备醚化蜜胺甲醛树脂的液体组合物的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656059A (en) * 1984-11-01 1987-04-07 Kurita Water Industries Ltd. Wet spray booth treating agent and method for treatment therewith
US5112652A (en) * 1989-08-29 1992-05-12 East Central Wax Company, Inc. Formaldehyde scavenging process useful in manufacturing durable press finished fabric

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656059A (en) * 1984-11-01 1987-04-07 Kurita Water Industries Ltd. Wet spray booth treating agent and method for treatment therewith
US5112652A (en) * 1989-08-29 1992-05-12 East Central Wax Company, Inc. Formaldehyde scavenging process useful in manufacturing durable press finished fabric

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753022A4 (fr) * 1994-03-29 1998-04-08 Henkel Corp Composition et procede permettant de rendre la peinture moins collante
EP0826014A4 (fr) * 1995-05-08 1998-04-08
US6384184B1 (en) 1998-05-23 2002-05-07 Henkel Kommanditgesellschaft Auf Aktien Method for decreasing the formaldehyde content in acidic solutions of melamine formaldehyde resins
EP1693393A1 (fr) 2005-02-22 2006-08-23 Lanxess Deutschland GmbH Produits de condensation contenant des groupes acides
EP1873176A1 (fr) 2006-06-23 2008-01-02 Lanxess Deutschland GmbH Produits de condensation dialdéhydes contenant des groupes acides
WO2018024559A1 (fr) * 2016-08-01 2018-02-08 Basf Se Dispersions polymères à émission d'acétaldéhyde réduite
CN110099940A (zh) * 2016-12-21 2019-08-06 巴斯夫欧洲公司 制备醚化蜜胺甲醛树脂的液体组合物的方法
US11739235B2 (en) 2016-12-21 2023-08-29 Basf Se Process for preparing liquid compositions of etherified melamine formaldehyde resins

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Publication number Publication date
CN1090308A (zh) 1994-08-03

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