US 20120028333A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2012/0028333 A1 Piatesi et al. (43) Pub. Date: Feb. 2, 2012 (54) USE OF ENZYMES TO REDUCE ALDEHYDES (30) Foreign Application Priority Data FROMALDEHYDE-CONTAINING PRODUCTS Apr. 7, 2009 (EP) .................................. O9157522.5 Publication Classification (76) Inventors: Andrea Piatesi, Mannheim (DE); (51) Int. Cl. Tilo Habicher, Speyer (DE); CI2N 9/02 (2006.01) Michael Bischel, Worms (DE); CI2N I/00 (2006.01) Li-Wen Wang, Mannheim (DE): CI2N 15/63 (2006.01) Jirgen Reichert, Limburgerhof A62D 3/02 (2007.01) (DE); Rainer Packe-Wirth, C7H 2L/04 (2006.01) Trostberg (DE); Kai-Uwe (52) U.S. Cl. ... 435/189: 435/262:536/23.2:435/320.1; Baldenius, Heidelberg (DE); Erich 435/243 Kromm, Weisenheim am Sand (57) ABSTRACT (DE); Stefan Häfner, Speyer (DE); Carsten Schwalb. Mannheim (DE); The invention relates to the use of an enzyme preparation Hans Wolfgang Höffken, which catalyzes the degradation of formaldehyde for reduc Ludwigshafen (DE) ing the formaldehyde content in a formaldehyde-containing formulation. In a preferred embodiment, the enzyme prepa ration contains a formaldehyde dismutase from a Pseudomo (21) Appl. No.: 13/262,662 nas putida Strain. Further, the invention refers to a process for reducing the formaldehyde content in cross-linking agents for textile finishing or in polymer dispersions used, e.g. in con (22) PCT Filed: Mar. 31, 2010 struction chemistry. Further the invention relates to the use of an enzyme preparation which catalyzes the degradation of (86). PCT No.: PCT/EP1OAS4284 aldehydes for reducing the formaldehyde content in an alde hyde-containing formulation. Furthermore, the invention S371 (c)(1), relates to a novel variant of the formaldehyde dismutase from (2), (4) Date: Oct. 3, 2011 Pseudomonas putida. Patent Application Publication Feb. 2, 2012 Sheet 1 of 9 US 2012/0028333 A1 Figure 1 (A) (B) (C) Patent Application Publication Feb. 2, 2012 Sheet 2 of 9 US 2012/0028333 A1 Figure 2 00:00 00:30 01:00 01:30 02:00 02:30 reaction time h) -4-301 FDM aSax. F93A assy F93A 301 Patent Application Publication Feb. 2, 2012 Sheet 3 of 9 US 2012/0028333 A1 Figure 3 Formaldehyde R 1750 1500 250 1g0l . Formic acid 750 - s r 500- s | Methanol is s l 1i t ( s', \\ s, Al A is: N. - - Silf Sease e- ses--4 Se= 1, s 1. 1. -- 2 54 R &OOO- f - Acetaldehyde 15'g 7000 - | \ 8O co 5) (OC) 4000 3000 2000 1R a 2 1 3. M f retention time (min) Patent Application Publication Feb. 2, 2012 Sheet 4 of 9 US 2012/0028333 A1 Figure 4 140 120 100 SS, e 80 2 60 8 40 20 O temperature (C) Patent Application Publication Feb. 2, 2012 Sheet 5 of 9 US 2012/0028333 A1 Figure 5 8 FDM 301 25 35 45 55 65 temperature (C) Patent Application Publication Feb. 2, 2012 Sheet 6 of 9 US 2012/0028333 A1 Figure 6 Patent Application Publication Feb. 2, 2012 Sheet 7 of 9 US 2012/0028333 A1 Figure 7 Patent Application Publication Feb. 2, 2012 Sheet 8 of 9 US 2012/0028333 A1 Figure 8 Patent Application Publication Feb. 2, 2012 Sheet 9 of 9 US 2012/0028333 A1 Figure 9 US 2012/0028333 A1 Feb. 2, 2012 USE OF ENZYMES TO REDUCE ALDEHYDES finishing of woven and knitted fabrics composed of cotton, FROMALDEHYDE-CONTAINING other cellulosic fibres, and their blends with synthetic fibres. PRODUCTS 0006 Initially, resin-finishing agents were developed to improve the shrinkage of Viscose staple fabrics. These com FIELD OF THE INVENTION pounds were usually derived from formaldehyde and urea. In order to improve the competitiveness of cotton on the textile 0001. The present invention relates to the enzymatic market, heterocyclic cross-linking reagents based on formal removal of formaldehyde from formulations containing dehyde, urea and glyoxal have been developed and are com formaldehyde and from products treated with said formula monly used for easy-care and wrinkle-free finishing. Due to tions. the Suspected harm in humans, FA levels in products and industrial processes have to be kept as low as possible. BACKGROUND OF THE INVENTION 0007. The prior art discloses various technologies for the 0002 Formaldehyde (for the purposes of convenience purpose of removing FA, e.g. air-borne when released from hereinafter often referred to as “FA) is an important chemi products or directly from well-known and widely used resins cal used widely by industry to manufacture building materials as introduced supra. U.S. Pat. No. 5,352.274 discloses air and numerous household products. FA is used for example for filtration utilizing a plurality of corrugated base sheets which crease-resistant finishing in the textile industry, for the pro are stacked or nestled and which have entrapped carbon dust duction and coating of chipboards in the wood processing for adsorption of impurities such as FA, acetaldehyde, and industry, and for the production of synthetic resins like phe acrolein. This technology provides a method to adsorb FA nolic plastics or aminoplasts in the chemical industry. Due to molecules physically but not degradation by a chemical or its high volatility FA is released into the air during the pro biochemical reaction. U.S. Pat. No. 5,830,414 discloses the duction processes and is considered as an important impact treatment of carbon fibers with an active small molecule such on health and environment. as a strong acid, strong base, or strong oxidizing agent. These 0003 FA has four basic uses: as an intermediate in the chemicals can only be used to treat fibers having high chemi production of resins; as intermediate in the production of cal resistances such as activated carbon fibers. Further, fibers industrial chemicals; as a biocide; and as a component in the thus treated are potentially hazardous to handle. The use of formulation of end-use consumer items. The manufacture of formaldehyde degrading enzymes in air filters is described in resins accounts for about 65 percent of total consumption. JP2OO1340436. About one-third is used in the synthesis of high volume 0008. With respect to textile industry and building mate chemical derivatives, including pentaerythritol, hexamethyl rials, FA reducing agents should not adversely affect fabric enetetramine, and butanediol. Two percent is used in textile properties such as hand, shrinkage, strength retention and treating and Small amounts of FA are present as preservatives shade or whiteness or the mechanical properties of the par or bioicides in consumer and industrial products, such as ticleboard. And, of course, it must be economical to use in cosmetics, shampoos and glues. The largest amounts of FA production and efficient at reasonable levels. In the textile are used for producing condensates (i.e. resins) with urea, industry, compounds having active methylene groups have melamine, naphthaline Sulfonate, and phenol and, to a small been used as FA reducing agents to reduce the amount of FA extent, with their derivatives. The main part of these resins is released from durable press-treated fabrics as described in used for the production of adhesives and impregnating resins, Textile Chemist and Colorist, Vol. 16, No. 12, p. 33, Decem which are employed for manufacturing particle boards, ply ber 1984 (published by the American Association of Textile wood, and furniture. These condensates are also employed for Chemists and Colorists). FA reducing agents containing the production of curable molding materials; as raw materials active methylene hydrogens also may be added to coating for Surface coating and as controlled-release nitrogen fertil compositions containing urea/formaldehyde or melamine? izers. They are used as auxiliaries in the textile, leather, rub formaldehyde resin to reduce formaldehyde concentration ber, and cement industries. Further uses include binders for (e.g. described in U.S. Pat. No. 5,795,933). Also the addition foundry sand, rockwool and glasswool mats in insulating of urea and its derivatives is known to Scavenge formalde materials, abrasive paper, and brake linings. Very small hyde. amounts of urea-FA condensates are used in the manufacture 0009. The prior art has not disclosed FA reducing agents of foamed resins that have applications in the mining sector which are effective in reducing released FA to the low levels and in the insulation of buildings and transportation vehicles. which are currently desired without detrimental effects on the 0004 Some products based on FA contain unreacted FA in properties of the materials to be treated with said resins. excess which may be released from the product or released Currently, the FA reducing agents most widely used in through Subsequent hydrolysis. One example is urea-FA durable press finishing compositions are polyhydric alcohols, resin. Urea-FA resin is a generic name that actually represents Such as diethylene glycol and Sorbitol and in the manufacture an entire class of related formulations. About 60 percent of of particleboard nitrogen containing compounds such as urea, urea-FA resin production is consumed by particleboard and melamine, diazine, triazine and amine compounds (U.S. Pat. plywood manufacturing, where the resin is used as glue. No. 4,559,097). Compounds such as these, however, are not Urea-FA resins are also used in decorative laminates, textiles, sufficiently effective in reducing FA levels to produce the low paper, and foundry sand molds. levels which are currently desired. Moreover, they only bind 0005 Finally, FA resins are used to treat textiles to impart FA and do not catalyze its degradation. Also some formalde wrinkle-resistance to clothing. Resin or chemical finishing is hyde scavengers like urea slow down reactivity of textile in most cases the last stage of modern textile production. The cross-linkers, reducing their efficiency.