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US 20030017565A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0017565 A1 ECHIGO et al. (43) Pub. Date: Jan. 23, 2003 (54) COMPOSITION AND METHOD FOR Publication Classi?cation TREATING A POROUS ARTICLE AND USE THEREOF (51) Int. c1.7 ............................ .. C12N 9/02; C12N 9/04; C12N 9/06; C12N 9/08 (76) Inventors: TAKASHI ECHIGO, CHIBA (JP); (52) Us. 01. ....................... .. 435/189; 435/190; 435/191; RITSUKO OHNO, TOKYO (JP) 435/192 Correspondence Address: (57) ABSTRACT SUGHRUE MION ZINN MACPEAK & SEAS A method for treating a porous article by ef?ciently per 2100 PENNSYLVANIA AVENUE NW forming macromoleculariZation in a porous article using an WASHINGTON, DC 200373202 enZyme having a polyphenol oxidizing activity in an alka line pH region, a phenolic compound and/or an aromatic ( * ) Notice: This is a publication of a continued pros amine compound, a composition for use in the treatment ecution application (CPA) ?led under 37 method, and treated products from the porous article CFR 1.53(d). obtained by the treatment method Which are given or increased in strength, Wear resistance, Weatherability, rust (21) Appl. No.: 09/319,384 preventing properties, ?ame resistance, antibacterial prop erties, antiseptic properties, sterilizing properties, insect (22) PCT Filed: Oct. 21, 1997 repellent properties, insecticidal properties, antiviral properties, organism-repellent properties, adhesiveness, (86) PCT No.: PCT/JP97/03798 chemical agent-sloW-releasing properties, coloring proper ties, dimension stability, crack resistance, deodoriZing prop erties, deoXidiZing properties, humidity controlling proper (30) Foreign Application Priority Data ties, moisture conditioning properties, Water repellency, surface smoothness, bioaf?nity, ion exchangeability, form Dec. 6, 1996 (JP) ........................................... .. 8-327252 aldehyde absorbing properties, chemical agent elution pre venting properties, or properties preventing the migration of May 30, 1997 (JP) ........................................... .. 9-142386 inorganic compounds onto the surface of the porous article. Patent Application Publication Jan. 23, 2003 US 2003/0017565 A1 Fig. 1(A) Fig. 1(B) Fig. 2 US 2003/0017565 A1 Jan. 23, 2003 COMPOSITION AND METHOD FOR TREATING A contain no formaldehyde using a laccase as a macromolecu POROUS ARTICLE AND USE THEREOF lariZation catalyst in the manufacture of coating composi tions or adhesives, has been used as an ancient Japanese TECHNICAL FIELD lacquer, and is also tried to apply in order to increase the Water resistance of a cardboard or corrugated paper by [0001] This invention relates to a method for treating a coating a polyphenol oxidiZing enZyme, such as laccase, porous article such as a sintered metal article, a cast article, together With its substrate. HoWever, the use of urushi or the an alloy, a die-cast article, a ceramic, a brick, concrete, like technique essentially utiliZes a macromoleculariZation Wood, processed Woody material, Wood chips, Wood poW reaction on the surface of a solid or the lamination surface der, chaffs, rush, straW, bamboo, ?bers, paper, pulp, foamed betWeen solids and the additives are limited to those pig synthetic resin, etc., to a composition useful in the treatment, ments used for coloring or Water-soluble polysaccharides and to use thereof. imitating the natural urushi, so that utiliZation of urushi-like [0002] More particularly, this invention relates to a reactions in industry have also been limited. method for treating a porous article by impregnating it With [0005] Furthermore, since the laccase or polyphenol oxi an enZyme Which oxidiZes polyphenols in an alkaline pH dases produced by fungi have optimum reaction pH values range, a phenolic compound and/or an aromatic amine in an acidic region, the reaction has heretofore had to be compound, as Well as an unsaturated compound or a chemi carried out in an acidic to neutral regions in order to promote cal agent under pressure or reduced pressure for macromo the macromoleculariZation reactions With the enZymes, and leculariZation reaction in the porous article, to a composition in addition, the rate of the macromoleculariZation reaction is for use in the treatment method, and treated products from not so high. Further, many natural organic compounds on the porous article obtained by the treatment method Which Which these enZymes are active are polyphenol compounds, are imparted or increased in strength, Wear resistance, Whose solubility decreases in acidic to neutral pH regions Weatherability, rust-preventing properties, ?ame resistance While the optimum reaction pH of the enZyme remains in the antibacterial properties, antiseptic properties, steriliZing acidic region. This necessitates that the reaction be carried properties, insect-repellent properties, insecticidal proper out in acidic to neutral pH regions, causing a problem that ties, antiviral properties, organism-repellent properties, high concentration polyphenol compounds are dif?cult to be adhesiveness, chemical agent-sloW-releasing properties, macromoleculariZed efficiently. For many of the polyphenol coloring properties, dimension stability, crack resistance, compounds, their auto-oxidation has not been utiliZed effec deodoriZing properties, deoxidiZing properties, humidity tively since they have been subjected to enZymatic oxidative controlling properties, moisture conditioning properties, macromoleculariZation in acidic to neutral pH regions Water repellency, surface smoothness, bioaffinity, ion although their auto-oxidation is accelerated in an alkaline exchangeability, formaldehyde absorbing properties, chemi pH region. cal agent elution preventing properties, or properties pre venting the migration of inorganic compounds onto the [0006] It is knoWn that phenolic compounds can also be surface of the porous article. macromoleculariZed With bilirubin oxidase and this reaction can be utiliZed in the macromoleculariZation of lignin and BACKGROUND ART dyeing of cotton (cf. WO95-01426 and Japanese Patent Application Kokai No. H6-316874) . HoWever, even in the [0003] Hitherto, for modifying physical properties, case of the prior art technique using bilirubin oxidase, the imparting strength, manufacturing laminated articles, enZyme-catalystic macromoleculariZation of phenolic com imparting antibacterial or vermin-preventing properties or pounds has been practiced in acidic to neutral pH regions, so the like, a thermosetting resin is impregnated or coated to that the rate of the macromoleculariZation has not been so porous materials such as Wood, Wood chips, Wood poWder, high. ?bers, paper or pulp and then heated for macromolecular iZation therein. HoWever, since the thermosetting resin con [0007] Japanese Patent Application Kokai No. tains unreacted formaldehyde, its in?uences on human body S61-268729 discloses a method for impregnating Wood are feared and, hence, there has been a demand for utiliZa including the ?rst step of adding a lignin derivative to Wood tion of compounds that contain no formaldehyde. Also, use and the second step of impregnating the Wood With a Weak of thermosetting resins is disadvantageous since it requires acidic aqueous solution containing metal ions for making heating at 80 to 200° C. for curing so that special heating lignin Water-insoluble in order to prevent the attack by appliance and energy for heating are necessary. microorganisms. HoWever, in this method, the solubility in Water of a complex of the lignin derivative With the metal [0004] Further, various enZyme macromoleculariZation ions decreases While the lignin derivative itself is not ?xed processes have heretofore been practiced Which use as a as a Water-insoluble substance. Further, for the treatment, macromoleculariZation catalyst polyphenol oxidation tWo kinds of the treating agents have to be used sWitching enZyme, for example, laccase or polyphenol oxidases pro one from another, so that it is dif?cult to apply the method duced by Basidiomycetes or Deuteromycetes as disclosed in to the existing appliance for injecting CCA (chromium WO87-2939, Japanese Patent Application Kokai Nos. copper-arsenic type preservative) based aqueous solution H5-117591 and H6-287516, H7-126354, and H7-126377, Which alloWs one pack treatment and is currently used in the and Journal ofBiotechnology, 13, 229-241, 1990 and so on. main as a Wood preservative. Therefore, it has been desired HoWever, these enZymatic macromoleculariZation methods to develop a method of utiliZing a lignin derivative Which relate to enZymatic macromoleculariZation processes in a ?xes to Wood strongly and Which alloWs one pack treatment. solution or on a surface of solid and to its applications. Further, the method of applying the macromoleculariZation [0008] Furthermore, efforts have been made for impreg reaction of urushiol and the like natural substances that nating porous articles With various chemical agents to US 2003/0017565 A1 Jan. 23, 2003 modify their properties but it has been di?icult for the porous ing oxygen (air) as an oxidiZer. It is surprising that such an articles to retain their properties effectively for a long period enZyme or enZymatic system catalyZes oxidation reaction of time because of elution of the injected chemical agents or and macromoleculariZation reaction in the environment there has been the fear that leached chemical agents could inside the porous article Where oxygen is supplied at a loW cause environmental pollution or could have any adverse rate.