CA2196975A1 - Flavonoid aldehydes and use in paint - Google Patents
Flavonoid aldehydes and use in paintInfo
- Publication number
- CA2196975A1 CA2196975A1 CA 2196975 CA2196975A CA2196975A1 CA 2196975 A1 CA2196975 A1 CA 2196975A1 CA 2196975 CA2196975 CA 2196975 CA 2196975 A CA2196975 A CA 2196975A CA 2196975 A1 CA2196975 A1 CA 2196975A1
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- Prior art keywords
- paint
- formulation
- compound
- substituent containing
- organic substituent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/38—Aromatic compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Materials Engineering (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
Methods and compositions are provided based upon flavonoid aldehydes, which find use as antimicrobials for paint and wood preservatives. The compositions can be added prior to shipment of the paint or wood preservative. Methods of preventing microbial contamination of a coated substrate are also provided.
The substrate includes walls, tiles, sidewalks, and boat hulls.
The substrate includes walls, tiles, sidewalks, and boat hulls.
Description
WO 96/40831 r~ u_,~/{7u48 ~ 21 96975 FLAVONOID ALDEHYDES AND USE IN PAINT
INT~ODUCTION
Field of thP InVP"rinn This invention relates to flavonoid aldehydes as biocides in paints and wood 10 ~c~.v.llivc products ~or use in, and on the surfaces of, homes, boats, offices and imdustrial buildings.
n . I~ U . UUl/d ~
Biocides are required in many paint and wood ,u~ V- Liv~, r ,. ", '-I;n -c to 1~ prevent microbial ~ l;n~ during shipment, storage or use. Biocides are also required in these formulated products to help protect a substrate ~ubac~_.l.ly coated with these formulated products from harmful Illi.luUl~;~A._..ls such as bacteria and fungi and the like. Biocides used in paint products may be grouped into three major classes: ,ulc~clva-iv~, mildewicides and a ' ' P~e~lva,iv~, are widely used ~0 in water-based paint systems to prevent in-can bacterial and fungal ~Pgr~ rinn durmg storage and shipment. They are particularly useful in latex systems such as syntnetic rubber, pulr~-,-y' , and natural rubber latexes. Mil-l.,w;,id,, are employed to prevent ~ dl", of the dried paint films and underlying substrate by Illi~.lUUll;.lll..~lll~. Antifoulant paints are used to prevent the growth of organisms on 25 the hulls of both commercial and pleasure boats. The attachment of such organisms decreases the operatmg efficiency of the boats and increases their "~h,r~ - costs.
Mercurial-type biocides have been widely used as both ,UlC~ClVO.~iV~.~ and ~uild.w;.;de~ in paints. They have excellent L,~,lru~ ,l. c in both functions in many situations. They offer fast kill time and can control high levels of bacterial 30 r U r ~ they are ha~ardous to handle and may present cuvhullll~.l~l problems. Thus, their use may be limited to certain ~ppli~rin~c Various IlUllllA,II.,Ulia.l ~ ,lv~l.iV~ and mildewicides have been hl~ ly considered as substitutes for mercurial rnmrolln~l~
SUBSTITUTE SHEET (RULE 26) 2 1 (~6975 A wide variety of biocides have been tried as marine: r but the has been dominated by r ~ of cuprous oxide and organotin Cuprous oxide has been popular because it is efficient, relatively ~ l, and is specified in many military antifouling p~unt r as the 5 exclusive biocide. However, this chemical causes UpUlU ~;L~/ in the paint film, which adversely affects efficiency, and it limits the paint colors which can be formulated to those of a dark reddish brown. The use of organotin ~ l~ ' has been growing in recent years; however, these l ' are more expensive than cuprous oxide and also more difficult to l into punt r o r they do not leach out completely during use so that when ships are " ' 1, the disposal of the resulting I ' sand poses ~I rr However, paint r ~ containing organotins yield uniform, tight films without the 1~ UIJUIUalt~ problems associated with those formulated with cuprous oxide and may be formulated in a wide variety of bright or light colors. For these latter 15 reasons, they are widely used on pleasure boats. Since both cuprous oxide andorganotin ~ r present technical or c~lv;lum.~ l problems, there is a need for new and better antifoulant paint biocides.
Biocides also are employed as wood l,.~.valive products in order to prevent ~. ~. ;...,l;.~.~ of wood products that are exposed to conditions which promote 20 microbial growth and decay. For example, utility poles, cross ties, piling timbers, freshly milled lumber and fence posts as well as wood chip piles used in pulp r require the ~ . of biocides to stop or control fungal In the past, two classes of biocides have been employed as wood V~lfiv~. One class is oil-bome ~-~.v,.Li~. . (e.g., creosote and 25 p_~hlu~ ) while the second class is water-bome salts (e.g., mi~ctures of inorganic ~ , ' such as copper, chromium, arsenic and zinc salts). The oil-bome ~ vdfivl,.~ have been the most widely used biocides for wood ~ IV~ ;UI~.
However, products treated with these mixtures may have messy oily surfaces. Alsoboth creosote and ~ , ' ' have been objected to as being . ,.v;., 'ly 30 hazardous. The water-bome salts are also toxic chemicals which are dissolved in water and injected into wood products where they become bound to or within the wood. These salts have certain advantages over the oil-bome treatments. They leave a cleaner surface that may be more readily painted. Also, their water soluble ~ WO96/40831 2 1 9 6975 ~ . ru48 provide savings in solvent costs. However, the use of chromium and arsenic saits in particuiar presents e.,.;., I problems.
Mosses are a nuisance in hu~ lt~ i and landscape More ih~ Li~ in certain geographic wnes favoring moss growth on surfaces frequented 5 by people (e.g., stairs, walkways, ioaths~ decks, patios), there is an ongoing concem about slip and fall injuries. Particuiar interest has been expressed conceming the safety of senior citizens in outdoor areas of nursing and r~-h~ ~tir~n centers where the results of such siip and fail accidents are of more medicai (~ L ' '~/
orthopedic) concern. Products on the maricet for control of moss include zinc 10 chioride and ferric sulfate. Zinc chloride solutions have severai L~h.u.~6~. Tney may cause injury to the respiratory tract; they are corrosive to the eyes resulting in severe damage which may be followed by biindness; on skin contact they will severely irritate or burn the skin; and upon swailowing, they are extremely corrosive to the mouth and throat, where they burn the tissue, atld in sufficient quantities they can cause death to the animai. Ferric sulfate is corrosive to the eye and is listed as toxic to aquatic iife.
It therefore is of interest to develop biocides for use in paint and wood ati~w which do not pose heaith and/or ~ ' hazards.
20 ~ Li~ ure Antifouiing paint is disclosed in USPN 4,313,800. Miidew resistant paint are disclosed in USPN 5,073,582. Skin diseases and contact sensitivity in house painters using water-based paints, glues and putties is described in Fischer, a 61., (1995) Contoc~ Denm~uids 32:39-45.
Sln~rM AR Y O F TllF DNn~E~rD10 N
The present invention provides ~ and methods for controliing pathogenic organisms using flavonoid aidehydes in paint and wood ~lc~l~a~
The method includes the step of including an ~ , ~ agent in the paint or 30 wood ~JI~I~dti~ '- in an amount sufficient to control growth of target pathogenic organisms. The growth modulating product has a formula shown in (1) below:
21 96~75 s ~n~ R
wherein R represents -CH20H or -C~O; n is an integer from O to 3; each R, , represents OH or an organic substituent containing from 1 to 10 carbon 10 atoms and from O to S 1,~ wherein the total number of carbon and in all R! ' of said compound is no more than 15, and R~
represents hydrogen or an organic constituent containing from I to 10 carbon atoms.
These include natural compounds such as ~ d, coniferyl aldehyde, and closely related . ' Also of interest are alpha substituted IS aldehydes, such as ~-hexyl cinnamic aldehyde (HCA). The method finds use in treating l ~ and ~ ~ ' crops for pathogenic organisms.
DE~ PrlON OF T~F. SPECl~IC El~RODTMl~ TS
Paint and wood ~ ..u~O substantially free of pathogenic organisms such 20 as fungi and bacteria are provided together with a method to biocontrol pathogen ~ r - on painted or treated surfaces using flavonoid aldehydes. By "biocontrol~
h intended control of pathogens via direct ~ ". - activity. A fungus andlor bacteria colonizing ~ ' or coated substrate such as a roof and roof shingles, barns, boat hulls, railroad ties, tree trunks, wooden ~jungle gyms,~ decks, docks, 2S wallcways, stairs, wooden patios, or wharves with brick surfaces, are contacted with a paint or ,ul~l~ldti~ containing a flavonoid aldehyde. By "colonizing" is intended association of a , ~ or insect with a surface or with a paint or ~ t;~
r... ~ ~;.. The flavonoid aldehydes can be isolated from a natural source, bewholly or partially synthetic, or be produced by ~l ' ~ techniques.
The method of the subject invention is carried out by adding an effective palllu~_l. ~ ' ~' ~", amount of a compound of the invention to a paint or ~
r ' '- The compound preferably is added at the time of placing the ~ - in a shipping container, but can be added " 1~, prior to use of the ~ W096~4W31 21 96975 r~l,u.,,~,l,u4s product. The amount of , ~~ ~ agent that is added depends to some e~tent upon the paint or ~ ' ' and the specific: . ' ,, used and therefore is empirically determined for best results. By "~ ' r '~ O ~ I~ is intended controlling the growth of pathogens and can involve ~illing the pathogen and/or 5 slowing or arresting its ~
The cwmpounds of the present invention offer several advantages over those currently in use. They possess good ~.t;,..;~.u~ l activity and are not ~ . ' ' with: . of w.... ' paint and wood ~.v~ti.., products. The ~ also are non-volatile, L~l~ul~ stable, thermally stable, and 10 depending upon their chemical structure, may be soluble in water and organic solvents. r. generally they form no undesirable wlors in the paint and wood ~.~.vd~ or in the resulting dried films. Still further, they are wst , .~ with known biocides used in various paints and wood ~ iVC
products while having low or no toxicity toward humans and wildlife. The present15 invention also overwmes the problem of migration of previously available u~ by bonding the bioactive wmpounds to the wood.
A preferred ~ dtiVi cwmpound is shown in formula (2) below:
R~
~ Q' (2) Rl~
25 wherein Rl 1l . CHO, R2 represents-OH or an organic substituent wntainingfrom l to 10 carbon atoms, R3 represents a methoxy group or organic substituent wontaining from I to 10 catbon atoms, and R~ represents a hydrogen or an organicsubstituent wntaining from I to 10 carbon atoms. Of particular interest are havonoid ~ aldehydes, ~ u~ aromatic aldehydes. Examples of aromatic aldehydes of use 30 in the present invention are cilmamic aldehyde ((3) below):
WO 96/40831 2 1 9 6 9 7 5 PCT/US95/17048 ~
C h o ~ (3) and conifcryl aldehyde ((4) below):
C ~3C~
C H0 (4) flO~
Other compounds of interest include analogs of the compound of formula (I) such as ' substituted at the alpha position with an alkyl, such as a hexyllS group, or a branched alkyl group such as an amyl group Generally the group at the alpha position is from C-5 to C-10. Such compounds include alpha hexyl d~ and alpha amyl lAPhyde. The chemical structure of alpha-h_A~ ~ aldehyde (HCA) is shown in (5) (below).
CH~
(CH2)5 (5) 2S ~/
The Chemical Abstracts Service (CAS) name of HCA is 2-(~L~,IIJ~ ' jl....~) octanal and the CAS Registry Number is [101-86-0]. The compound is also described by thechemical name of 2-hexyl-3-phenyl-2-propenal. The formula of the compound is Cl5H~oO and the molecular weight is 216.3. HCA is a low to moderately volatile compound, having a vapor pressure of 70 x 10' mm Hg at 25~C. Its parent compound, cimlamic aldehyde, has a vapor pressure ~ 'y 40 times higher (2970 ~ 10' mm Hg at 25~C). (R~ifPn~th W.G. (1995) Volatile .~ ' Cosmetics and Toiletries, 110: 85-93).
~ W096140831 21 96975 P~,l/u~
The arornatic and aliphatic aldehydes of the subject invention can be prepared by various synthetic methods known to those skilled in the art. For example, sec, J.
March, ed., Appendix B, Advanced Orgar~ic Chemistry: Rcacdors, ~' ' . and Structure, 2nd Ed., McGraw-Hill, New York, 1977. t' ' ' ' ydu can be S prepared a.~ '' " "y, for example, by oxidation of cinnamyl alcohol (Traynelis er al., J. Am. Chcm. Soc. (1964) 86:298) or by ~ of styrene witb .~h~ ' (Brit. patent 504,125). The subject aldehydes also can be obtained by isolation from natural sources. For example, ~ 1. h~d., can be isolated from ~ fungus, Stereum r~hr;l Birkinshaw et al., Biochcm.
10 J. (1957) 66:188.
HCA can be synthesiz_d as described, for example, in USPN 5,055,621. On a laboratory scale, HCA can be synthesized by reaction of l,~..~W~ h~lc with octanal under a nitrogen: . ' (aldol ' ) (Personal r- ~ ~ Eric Walborsky, Firmenich Chemical r~ g Center, Port Newark, New Jersey).
15 The reaction is conducted in a stirred flask charged with methanol, 309 ppm ~'i,' .~' ~ , potassium hydroxide and ' '' ' ~d~ . Following tbe slow addition of octanal, the reaction mixture is brought to a pH of 7.5-9.5 with acetic acid.Following c~..~.~l;u-- of methanol and wash of the reaction mixture with water, the organic phasc is transferred to a distillation unit. A~ 'y 2û-24% of the pot charge is removcd as l ' ' ' ~d~ and alights", with the remaining distillate ~: 'i ' h~ h~ uuh, aldehyde "heart cut." The "hcart cut" is subjectPd to an additional r.r l:-~ - in which 1-5% (by weight) of the material is removedin ~light~ fracfions, dcpending upon odor cvaluation. The final product is a light yellow oil having a specific gravity of 0.955-0.965 at 20~C, a refractive index of 1.548-1.562 at 20~C, a boiling point of 305~C at I atrn~r~rhPrP~ and a melting point of 26~C.
HCA also can be obtained from Firmenich; their product is composed principally of the (E)-cis isomer (93.8% maximum), and the (Z)-trans isomer (6%
maximum). Among minor ~ . is the self aldol ' product of octanal (1-1.5% (Personal ~' June Burkhardt, Finnenich, Plainsboro, New Jersey). The ~ ~.;ol product is stabilizcd with the addition of 0.04% 2, 6-di-tert-butyl-p-cresol (butylatcd ~ dlUA~,h~ or BHT), which seNes as an anti-o~cidant (Technical Data Sheet, IIw~ aldehyde 907600, Revision 853, WO 96140831 2 1 q 6 9 7 5 PCT/llS95/17048 ~
Frmenich Inc., Plainsboro, New Jersey). HCA can be isolated from rice where it has been reported to occur naturally. (Givaudan-Roure Index, Gi~ n,~
~'nTn~tinn Clifton, New Jersey, 1994, p. 89).
The compounds can be used by hlcul~l~Lil.g an effective paint ~lc~vdLiv~
5 amount of the compound into a paint or wood IJlc~ LilC. By "an effective paintamount~ is intended any amount which will prevent or control d~ of the paint. In-can ~L'- I l;~n of paints is often caused by gram-positive bacteria such as Pacillus cereus and S~ .'l aureus or gram-negativebacteria such as those of the r ~ or Y ~/~ classes. This 4c~
10 of the p~unt ingredients results in viscosity loss or generation of offensive odors.
Generally, paint p.~ ld~ J are employed in aqueous-based paint systems such as latex systems. Solvent-based p~unts usually do not require a p.w~.~di.~
since the . ' ' will not support fungal and/or bacterial growth. In-can ~JIC~.~tiV~ are fungicidal and/or I - ' ;; l-~ and their killing action preferably 15 is rapid to prevent production of enzymes by the ~ ., which are actually the cause of the latex paint dewtruction.
When the present bioactive .~ . ' are employed as p~unt ~ Li~w~ it is usually dwirable to add them to the paint ' ' in the same manner as other ingredients are i r ' ~ It is preferred to . them as a substitute for 20 ' "~, all of the non-bioactive non-paint . in the p~unt r... ,....1 .l;, ...
The actual amount of ~).WCI~ used varies depending upon many p~m~-t~
Generally, it is preferred to employ from about 0.5 to 5 volume % of a compound of formula (I) as~part of a total paint r ~ ~ for this purpose.
The compounds of the subject invention also find use for the prevention and/or 25 killing of mildew (-..ilJ~ ;Ji~). Accordingly, the term "effective ' ' ..;ci~hl amount" is intended to include any amount which will kill or control the growth of mildew-causing ~ ,, Mildew or mold causing . ~ vary according to the exposure e..vh.,n..l~.,.. A ,, ' ' pullulans is the most commonly found species in temperate and colder climates. Tropical and subtropical 30 conditions favor the growth of, u,, of the classes A.., ,~spergillus and Penicillium as well as the alg~ ri~ . UL6LLU.. virides. The effective ' ' . ;.,;J~I amount is varied empirically based up changew in the parameters of the h.~' ' and the substrate having the . li ' of the subject invention ~ l therein. Generaily, it is preferred to employ from about 0.5 to 5 volume % of a compound shown in formula (I) as part of a totai paint r .. . 1- ...
Another use for the subject compounds is as an antifoulant. An effective antifouiant amount of one or more of the compounds of formuia (1) is ~ , ' 5 into a hull coating ' ~ By the term "effective antifouling amount" is intended any amount which wiil prevent or control fouiing on the huii. Fouling organisms include plant forms such as aigae and animai forms such as those of the classes Anthropeda, ('oPIP~.t~'~ and Mollusca. The green aigae L.t~.l , ' is the organism most often found on the hulls of large ships. The effective antifouiing 10 amount will vary because of changes in the parameters of the cn~;-- and the substrate on which it is applied to the huiis. Generaiiy, it is preferred to empioy from about 0.5 to 5 volume % of the active moiety shown in formula (1) as part of a totai paint ' ' for this purpose.
An additionai use of the subject r ~ " is as a wood l~G~~ .,. An lS effective wood-preserving amount of one or more of these compounds is into a wood treatment product. The term "effective wood ~ amount~ is intended to include an amount of the compound which prevents or controls ~1. ~" .- 1 ~ ;.... of the wood product to which it is applied. Wood products not in water are subject to two forms of fungai attack, surface attack (e.g., soft rot) and internai 20 attack (e.g., white and brown rots). Fungi imperfecti and A ~ are the major cause of soft rot and the P ' ,y~tt.~ class of fungi is the major cause of internai attacic. White rots attack the lignin and brown rots attack the cellulose. The commonly l~nown dr,v rot is a brown rot. Also, wood products exposed to seawaterare attacked by marine organisms such as Pholads, 7'eredo, and Lin~noria tripunctata.
25 The effective amount of compound employed in this appiication is empiricaily determined based upon parameters which include the specific preserving employed, the type of wood product to be protected, and the type of .,..~i-, the wood product is exposed to. Generaily, it is preferred to employ from about 0.5 to 5 volume % of the active moiety shown in formula (I) as part of a totai wood The biocides of the present invention can be added to the wood products by dther pressure or , ~UIG ' . ~, '' If pressure ~ ~ is employed, air, hydrostatic pressure or vacuum methods, or ~- 5. ~ . thereof, can be used.
WO 96140831 2 1 q 6 9 7 5 PCT/US95117048 ~
If . ~ l, " of wood is desired, dipping, spraying, brushing or the lilce can be used.
The bioactive . ' of the present invention can be either added directly to cellulosic materials such as the wood products in a preformed state, or the . ' of formula (1) can be added to, for example, bound to a cellulose binding protein. In this latter case, the bioactive compounds bond to the pul.~l.~ide structure of the cellulosic material (e.g., wood, paper and the like) upon contact.
Paper products can be treated to make a ' '~ LollL paper, cardboard boxes or the like using the flavonoid compound - pc ly ~ binding conjugate. A
sufficient portion of a cellulose binding domain up to the full length cellulose can be used when the target p~ ~h.uide is a cellulose. The preparation of cellulose binding domains is described in U.S. Patent Nos. 5,340,731; 5,202,247 and 5,166,317. Bindir,g proteins from scaffold proteins also can be used. See Shoseyev et al. (PCT application EP/0594/04132). The conjugate can be prepared with or.
without a cleavable bond using methods known to those sl~lled in the art.
Paint and wood ~ di~ products which may contain the biocidal of the invention as ~ h~ and l ~ ..h,;d~,i, include such as latex and solvent interior and exterior punts, coatingS for new and existing structures. Other p~unt products include industrial finishing products such as interior 20 and exterior coatings and marine antifouling paints.
The following examples are offered by way of illustration and not by way of limitation.
F.
n~ ntl M~thn~i~
The chemicals used in the examples given below were obtained from the following sources: cinnamic aldêhyde, Spectrum Chemical Company, N.J.; coniferyl aldehyde, APIN Chemical, U.K.; Tween 80 and sodium l,;~. Spectrum Chemical Company, Gardena, Ca. 1'~ are given as the, of the indicated solution before dilution.
~ WO 96/40831 2 1 9 6 q 7 5 PCT/US95/17048 E3~
E~al and ~ P~PllPnry Test of C
The bioactive . , ' are tested for fungal and algal repellency.
~ ~irmcrl~r slides are used as the substrates in both cases. One half of each slide is S coated on one side with a film of polymer containing the active agent to be tested, while the other half of the slide is not treated with the active agent. The total slide is exposed to the challenge of either fungi or algae with the expectation that the half of the slide containing the active agent will prevent growth of the challenging organism, while the untreated half will not.
In the fungal test, the slide is placed on the surface of an agar plate which isseeded with fungi. After incubation for about 14 days, the slide is examined forextent of growth or lack thereof on the treated surface of the slide. Since leaching of the active agent would create an ~. .l. -.,.1,1. zone-of ' ' outside the perimeter of the treated surface of the slide, no growth on the treated surface along with a small, or no, zone of inhibition is the desired result.
In the algal test, the slide is immersed in a nutrient broth which has been inoculated with the alg~ r~ After an incubation for 30 days (under light) and a water rinse, the slide is exannined . ~ ~ly and the extent of algal attachment is noted. Total lack of attachment on the treated surface is the desired result. Additional i r~ is obtained by comparing the extent of growth of alg~ throughout the broth. Significant leaching of the active agent from the treated surface would inhibit growth in the broth as well as on tbe treated surface.
Example 2 Paint ~ ,;de TPC~C
The test procedure is followed exactly from the following published procedure: R.A. Zabel and W.E. Horner, Joumal of Coanngs Technology, 53, 33-3',7, (1981), except that the organism A.., ' " pullulans M30-4 is used, isolated from mildewed exterior latex paint. Duplicates are run in each case. Two separate 30 tests are run for slightly different time periods.
WO 96/40831 2 1 9 6 9 7 5 PCTIUS95/17048 ~
E~
Wood 1'~ ,.,.\ T
This aspect of the present invention extends tne utility of the above described ~ ' ~ ' , ' to the wood ~ Liu~ area. Two general techniques are S shown. In one, a solution of the compound is applied to the wood direc~dy. In the second, a solution of compound bound to a cellulose binding protein is applied to the wocd.
Eight (about 2.5 cm x 2.5 cm x 0.5 cm) weighed pine wood blocks ~ placed in a dish and a 5-6 mm Hg vacuum applied for 30 minutes. Two solutions are prepared, one containing a compound of formula (1) and the second a compound of formula (I) bound to a cellulose binding protein. While still under vacuum, eachsolution is added to a dish and the wood blocks are submerged in one of the two solutions. After soaking for 30 minutes the wood blocks are removed from the solutions, excess compound is wiped off and the blocks are heated at 75~ C. for 16 hours. After cooling to room i r ' the blocks are weighed and analyzed to determine the ;' ' of compound throughout the wood chip.
Examp]e 4 Wood Rnt T.~ct The test procedure is based upon the following published procedure: H.P.
Sutter, l -' r J ' ;UiUiiU~ Bullenn, 14 (3), 95-99 (1978). The organisms employed are r: , ' u puteana ATCC 36336 and Lendnus lepide~s ATCC 12653 (a ~ Vt~, ~ fungus). Duplicates are run in each case. The growth of brown rot ( " ' d ~ ' ,) fungi on pine blocks after 25 days at 28~ C. is evaluated as:
Growth Key 0 - no growth 1 - slight growth 2 - moderate growth 3 - heavy growth 4 - very heavy growth ~ WO 91i/40831 2 1 9 6 9 7 5 PCr/US9S/17048 Four (~Z.5 cm x 2.5 cm ~-0.5 cm) print wood blocks are surface treatçd with either a wood ~ ti~, comprising a test ~ of a compound according to formula (I) or a commercial wood ~ ,. The wood blocks are brush coated on all surfaces and in some cases multiple coats are applied. Pressure 5 Dent is not used. These present examples correspond to what a consumer would do to apply a wood ~ . The amount of biocide applied to each wood block is calculated by ' ~ the weight increase of each wood block after treatmentand calculating the biocide present in the weight increase.
Example S
~ 111' ' ' ' ' TPCtj~
p- r '~ ~ e ~ I are tes~ed in a standard Minimum Inhibitory ~'. (MIC) tçst against 8 different bacteria and 8 different fungi. Also tested in this MIC test are Tween 80 (2%), NaHCO3 (6%) and Tween 80 (2%) plus 15 NaHCO3 (6%) ac blanks.
WO 96/40831 2 1 9 6 9 7 5 PCT/llS95/17048 ~
The organisms included in the MIC test are:
S ~
aeruginosa ATCC 9028;
2 - F ' acruginosa ~pyrithione resistant);
3 F 'I Ul~aLic~ aerogenes ATCC 13048;
4 - 5~ 7 aureus ATCC 6538;
5 - F. 7~ syriugac ATCC 19310;
INT~ODUCTION
Field of thP InVP"rinn This invention relates to flavonoid aldehydes as biocides in paints and wood 10 ~c~.v.llivc products ~or use in, and on the surfaces of, homes, boats, offices and imdustrial buildings.
n . I~ U . UUl/d ~
Biocides are required in many paint and wood ,u~ V- Liv~, r ,. ", '-I;n -c to 1~ prevent microbial ~ l;n~ during shipment, storage or use. Biocides are also required in these formulated products to help protect a substrate ~ubac~_.l.ly coated with these formulated products from harmful Illi.luUl~;~A._..ls such as bacteria and fungi and the like. Biocides used in paint products may be grouped into three major classes: ,ulc~clva-iv~, mildewicides and a ' ' P~e~lva,iv~, are widely used ~0 in water-based paint systems to prevent in-can bacterial and fungal ~Pgr~ rinn durmg storage and shipment. They are particularly useful in latex systems such as syntnetic rubber, pulr~-,-y' , and natural rubber latexes. Mil-l.,w;,id,, are employed to prevent ~ dl", of the dried paint films and underlying substrate by Illi~.lUUll;.lll..~lll~. Antifoulant paints are used to prevent the growth of organisms on 25 the hulls of both commercial and pleasure boats. The attachment of such organisms decreases the operatmg efficiency of the boats and increases their "~h,r~ - costs.
Mercurial-type biocides have been widely used as both ,UlC~ClVO.~iV~.~ and ~uild.w;.;de~ in paints. They have excellent L,~,lru~ ,l. c in both functions in many situations. They offer fast kill time and can control high levels of bacterial 30 r U r ~ they are ha~ardous to handle and may present cuvhullll~.l~l problems. Thus, their use may be limited to certain ~ppli~rin~c Various IlUllllA,II.,Ulia.l ~ ,lv~l.iV~ and mildewicides have been hl~ ly considered as substitutes for mercurial rnmrolln~l~
SUBSTITUTE SHEET (RULE 26) 2 1 (~6975 A wide variety of biocides have been tried as marine: r but the has been dominated by r ~ of cuprous oxide and organotin Cuprous oxide has been popular because it is efficient, relatively ~ l, and is specified in many military antifouling p~unt r as the 5 exclusive biocide. However, this chemical causes UpUlU ~;L~/ in the paint film, which adversely affects efficiency, and it limits the paint colors which can be formulated to those of a dark reddish brown. The use of organotin ~ l~ ' has been growing in recent years; however, these l ' are more expensive than cuprous oxide and also more difficult to l into punt r o r they do not leach out completely during use so that when ships are " ' 1, the disposal of the resulting I ' sand poses ~I rr However, paint r ~ containing organotins yield uniform, tight films without the 1~ UIJUIUalt~ problems associated with those formulated with cuprous oxide and may be formulated in a wide variety of bright or light colors. For these latter 15 reasons, they are widely used on pleasure boats. Since both cuprous oxide andorganotin ~ r present technical or c~lv;lum.~ l problems, there is a need for new and better antifoulant paint biocides.
Biocides also are employed as wood l,.~.valive products in order to prevent ~. ~. ;...,l;.~.~ of wood products that are exposed to conditions which promote 20 microbial growth and decay. For example, utility poles, cross ties, piling timbers, freshly milled lumber and fence posts as well as wood chip piles used in pulp r require the ~ . of biocides to stop or control fungal In the past, two classes of biocides have been employed as wood V~lfiv~. One class is oil-bome ~-~.v,.Li~. . (e.g., creosote and 25 p_~hlu~ ) while the second class is water-bome salts (e.g., mi~ctures of inorganic ~ , ' such as copper, chromium, arsenic and zinc salts). The oil-bome ~ vdfivl,.~ have been the most widely used biocides for wood ~ IV~ ;UI~.
However, products treated with these mixtures may have messy oily surfaces. Alsoboth creosote and ~ , ' ' have been objected to as being . ,.v;., 'ly 30 hazardous. The water-bome salts are also toxic chemicals which are dissolved in water and injected into wood products where they become bound to or within the wood. These salts have certain advantages over the oil-bome treatments. They leave a cleaner surface that may be more readily painted. Also, their water soluble ~ WO96/40831 2 1 9 6975 ~ . ru48 provide savings in solvent costs. However, the use of chromium and arsenic saits in particuiar presents e.,.;., I problems.
Mosses are a nuisance in hu~ lt~ i and landscape More ih~ Li~ in certain geographic wnes favoring moss growth on surfaces frequented 5 by people (e.g., stairs, walkways, ioaths~ decks, patios), there is an ongoing concem about slip and fall injuries. Particuiar interest has been expressed conceming the safety of senior citizens in outdoor areas of nursing and r~-h~ ~tir~n centers where the results of such siip and fail accidents are of more medicai (~ L ' '~/
orthopedic) concern. Products on the maricet for control of moss include zinc 10 chioride and ferric sulfate. Zinc chloride solutions have severai L~h.u.~6~. Tney may cause injury to the respiratory tract; they are corrosive to the eyes resulting in severe damage which may be followed by biindness; on skin contact they will severely irritate or burn the skin; and upon swailowing, they are extremely corrosive to the mouth and throat, where they burn the tissue, atld in sufficient quantities they can cause death to the animai. Ferric sulfate is corrosive to the eye and is listed as toxic to aquatic iife.
It therefore is of interest to develop biocides for use in paint and wood ati~w which do not pose heaith and/or ~ ' hazards.
20 ~ Li~ ure Antifouiing paint is disclosed in USPN 4,313,800. Miidew resistant paint are disclosed in USPN 5,073,582. Skin diseases and contact sensitivity in house painters using water-based paints, glues and putties is described in Fischer, a 61., (1995) Contoc~ Denm~uids 32:39-45.
Sln~rM AR Y O F TllF DNn~E~rD10 N
The present invention provides ~ and methods for controliing pathogenic organisms using flavonoid aidehydes in paint and wood ~lc~l~a~
The method includes the step of including an ~ , ~ agent in the paint or 30 wood ~JI~I~dti~ '- in an amount sufficient to control growth of target pathogenic organisms. The growth modulating product has a formula shown in (1) below:
21 96~75 s ~n~ R
wherein R represents -CH20H or -C~O; n is an integer from O to 3; each R, , represents OH or an organic substituent containing from 1 to 10 carbon 10 atoms and from O to S 1,~ wherein the total number of carbon and in all R! ' of said compound is no more than 15, and R~
represents hydrogen or an organic constituent containing from I to 10 carbon atoms.
These include natural compounds such as ~ d, coniferyl aldehyde, and closely related . ' Also of interest are alpha substituted IS aldehydes, such as ~-hexyl cinnamic aldehyde (HCA). The method finds use in treating l ~ and ~ ~ ' crops for pathogenic organisms.
DE~ PrlON OF T~F. SPECl~IC El~RODTMl~ TS
Paint and wood ~ ..u~O substantially free of pathogenic organisms such 20 as fungi and bacteria are provided together with a method to biocontrol pathogen ~ r - on painted or treated surfaces using flavonoid aldehydes. By "biocontrol~
h intended control of pathogens via direct ~ ". - activity. A fungus andlor bacteria colonizing ~ ' or coated substrate such as a roof and roof shingles, barns, boat hulls, railroad ties, tree trunks, wooden ~jungle gyms,~ decks, docks, 2S wallcways, stairs, wooden patios, or wharves with brick surfaces, are contacted with a paint or ,ul~l~ldti~ containing a flavonoid aldehyde. By "colonizing" is intended association of a , ~ or insect with a surface or with a paint or ~ t;~
r... ~ ~;.. The flavonoid aldehydes can be isolated from a natural source, bewholly or partially synthetic, or be produced by ~l ' ~ techniques.
The method of the subject invention is carried out by adding an effective palllu~_l. ~ ' ~' ~", amount of a compound of the invention to a paint or ~
r ' '- The compound preferably is added at the time of placing the ~ - in a shipping container, but can be added " 1~, prior to use of the ~ W096~4W31 21 96975 r~l,u.,,~,l,u4s product. The amount of , ~~ ~ agent that is added depends to some e~tent upon the paint or ~ ' ' and the specific: . ' ,, used and therefore is empirically determined for best results. By "~ ' r '~ O ~ I~ is intended controlling the growth of pathogens and can involve ~illing the pathogen and/or 5 slowing or arresting its ~
The cwmpounds of the present invention offer several advantages over those currently in use. They possess good ~.t;,..;~.u~ l activity and are not ~ . ' ' with: . of w.... ' paint and wood ~.v~ti.., products. The ~ also are non-volatile, L~l~ul~ stable, thermally stable, and 10 depending upon their chemical structure, may be soluble in water and organic solvents. r. generally they form no undesirable wlors in the paint and wood ~.~.vd~ or in the resulting dried films. Still further, they are wst , .~ with known biocides used in various paints and wood ~ iVC
products while having low or no toxicity toward humans and wildlife. The present15 invention also overwmes the problem of migration of previously available u~ by bonding the bioactive wmpounds to the wood.
A preferred ~ dtiVi cwmpound is shown in formula (2) below:
R~
~ Q' (2) Rl~
25 wherein Rl 1l . CHO, R2 represents-OH or an organic substituent wntainingfrom l to 10 carbon atoms, R3 represents a methoxy group or organic substituent wontaining from I to 10 catbon atoms, and R~ represents a hydrogen or an organicsubstituent wntaining from I to 10 carbon atoms. Of particular interest are havonoid ~ aldehydes, ~ u~ aromatic aldehydes. Examples of aromatic aldehydes of use 30 in the present invention are cilmamic aldehyde ((3) below):
WO 96/40831 2 1 9 6 9 7 5 PCT/US95/17048 ~
C h o ~ (3) and conifcryl aldehyde ((4) below):
C ~3C~
C H0 (4) flO~
Other compounds of interest include analogs of the compound of formula (I) such as ' substituted at the alpha position with an alkyl, such as a hexyllS group, or a branched alkyl group such as an amyl group Generally the group at the alpha position is from C-5 to C-10. Such compounds include alpha hexyl d~ and alpha amyl lAPhyde. The chemical structure of alpha-h_A~ ~ aldehyde (HCA) is shown in (5) (below).
CH~
(CH2)5 (5) 2S ~/
The Chemical Abstracts Service (CAS) name of HCA is 2-(~L~,IIJ~ ' jl....~) octanal and the CAS Registry Number is [101-86-0]. The compound is also described by thechemical name of 2-hexyl-3-phenyl-2-propenal. The formula of the compound is Cl5H~oO and the molecular weight is 216.3. HCA is a low to moderately volatile compound, having a vapor pressure of 70 x 10' mm Hg at 25~C. Its parent compound, cimlamic aldehyde, has a vapor pressure ~ 'y 40 times higher (2970 ~ 10' mm Hg at 25~C). (R~ifPn~th W.G. (1995) Volatile .~ ' Cosmetics and Toiletries, 110: 85-93).
~ W096140831 21 96975 P~,l/u~
The arornatic and aliphatic aldehydes of the subject invention can be prepared by various synthetic methods known to those skilled in the art. For example, sec, J.
March, ed., Appendix B, Advanced Orgar~ic Chemistry: Rcacdors, ~' ' . and Structure, 2nd Ed., McGraw-Hill, New York, 1977. t' ' ' ' ydu can be S prepared a.~ '' " "y, for example, by oxidation of cinnamyl alcohol (Traynelis er al., J. Am. Chcm. Soc. (1964) 86:298) or by ~ of styrene witb .~h~ ' (Brit. patent 504,125). The subject aldehydes also can be obtained by isolation from natural sources. For example, ~ 1. h~d., can be isolated from ~ fungus, Stereum r~hr;l Birkinshaw et al., Biochcm.
10 J. (1957) 66:188.
HCA can be synthesiz_d as described, for example, in USPN 5,055,621. On a laboratory scale, HCA can be synthesized by reaction of l,~..~W~ h~lc with octanal under a nitrogen: . ' (aldol ' ) (Personal r- ~ ~ Eric Walborsky, Firmenich Chemical r~ g Center, Port Newark, New Jersey).
15 The reaction is conducted in a stirred flask charged with methanol, 309 ppm ~'i,' .~' ~ , potassium hydroxide and ' '' ' ~d~ . Following tbe slow addition of octanal, the reaction mixture is brought to a pH of 7.5-9.5 with acetic acid.Following c~..~.~l;u-- of methanol and wash of the reaction mixture with water, the organic phasc is transferred to a distillation unit. A~ 'y 2û-24% of the pot charge is removcd as l ' ' ' ~d~ and alights", with the remaining distillate ~: 'i ' h~ h~ uuh, aldehyde "heart cut." The "hcart cut" is subjectPd to an additional r.r l:-~ - in which 1-5% (by weight) of the material is removedin ~light~ fracfions, dcpending upon odor cvaluation. The final product is a light yellow oil having a specific gravity of 0.955-0.965 at 20~C, a refractive index of 1.548-1.562 at 20~C, a boiling point of 305~C at I atrn~r~rhPrP~ and a melting point of 26~C.
HCA also can be obtained from Firmenich; their product is composed principally of the (E)-cis isomer (93.8% maximum), and the (Z)-trans isomer (6%
maximum). Among minor ~ . is the self aldol ' product of octanal (1-1.5% (Personal ~' June Burkhardt, Finnenich, Plainsboro, New Jersey). The ~ ~.;ol product is stabilizcd with the addition of 0.04% 2, 6-di-tert-butyl-p-cresol (butylatcd ~ dlUA~,h~ or BHT), which seNes as an anti-o~cidant (Technical Data Sheet, IIw~ aldehyde 907600, Revision 853, WO 96140831 2 1 q 6 9 7 5 PCT/llS95/17048 ~
Frmenich Inc., Plainsboro, New Jersey). HCA can be isolated from rice where it has been reported to occur naturally. (Givaudan-Roure Index, Gi~ n,~
~'nTn~tinn Clifton, New Jersey, 1994, p. 89).
The compounds can be used by hlcul~l~Lil.g an effective paint ~lc~vdLiv~
5 amount of the compound into a paint or wood IJlc~ LilC. By "an effective paintamount~ is intended any amount which will prevent or control d~ of the paint. In-can ~L'- I l;~n of paints is often caused by gram-positive bacteria such as Pacillus cereus and S~ .'l aureus or gram-negativebacteria such as those of the r ~ or Y ~/~ classes. This 4c~
10 of the p~unt ingredients results in viscosity loss or generation of offensive odors.
Generally, paint p.~ ld~ J are employed in aqueous-based paint systems such as latex systems. Solvent-based p~unts usually do not require a p.w~.~di.~
since the . ' ' will not support fungal and/or bacterial growth. In-can ~JIC~.~tiV~ are fungicidal and/or I - ' ;; l-~ and their killing action preferably 15 is rapid to prevent production of enzymes by the ~ ., which are actually the cause of the latex paint dewtruction.
When the present bioactive .~ . ' are employed as p~unt ~ Li~w~ it is usually dwirable to add them to the paint ' ' in the same manner as other ingredients are i r ' ~ It is preferred to . them as a substitute for 20 ' "~, all of the non-bioactive non-paint . in the p~unt r... ,....1 .l;, ...
The actual amount of ~).WCI~ used varies depending upon many p~m~-t~
Generally, it is preferred to employ from about 0.5 to 5 volume % of a compound of formula (I) as~part of a total paint r ~ ~ for this purpose.
The compounds of the subject invention also find use for the prevention and/or 25 killing of mildew (-..ilJ~ ;Ji~). Accordingly, the term "effective ' ' ..;ci~hl amount" is intended to include any amount which will kill or control the growth of mildew-causing ~ ,, Mildew or mold causing . ~ vary according to the exposure e..vh.,n..l~.,.. A ,, ' ' pullulans is the most commonly found species in temperate and colder climates. Tropical and subtropical 30 conditions favor the growth of, u,, of the classes A.., ,~spergillus and Penicillium as well as the alg~ ri~ . UL6LLU.. virides. The effective ' ' . ;.,;J~I amount is varied empirically based up changew in the parameters of the h.~' ' and the substrate having the . li ' of the subject invention ~ l therein. Generaily, it is preferred to employ from about 0.5 to 5 volume % of a compound shown in formula (I) as part of a totai paint r .. . 1- ...
Another use for the subject compounds is as an antifoulant. An effective antifouiant amount of one or more of the compounds of formuia (1) is ~ , ' 5 into a hull coating ' ~ By the term "effective antifouling amount" is intended any amount which wiil prevent or control fouiing on the huii. Fouling organisms include plant forms such as aigae and animai forms such as those of the classes Anthropeda, ('oPIP~.t~'~ and Mollusca. The green aigae L.t~.l , ' is the organism most often found on the hulls of large ships. The effective antifouiing 10 amount will vary because of changes in the parameters of the cn~;-- and the substrate on which it is applied to the huiis. Generaiiy, it is preferred to empioy from about 0.5 to 5 volume % of the active moiety shown in formula (1) as part of a totai paint ' ' for this purpose.
An additionai use of the subject r ~ " is as a wood l~G~~ .,. An lS effective wood-preserving amount of one or more of these compounds is into a wood treatment product. The term "effective wood ~ amount~ is intended to include an amount of the compound which prevents or controls ~1. ~" .- 1 ~ ;.... of the wood product to which it is applied. Wood products not in water are subject to two forms of fungai attack, surface attack (e.g., soft rot) and internai 20 attack (e.g., white and brown rots). Fungi imperfecti and A ~ are the major cause of soft rot and the P ' ,y~tt.~ class of fungi is the major cause of internai attacic. White rots attack the lignin and brown rots attack the cellulose. The commonly l~nown dr,v rot is a brown rot. Also, wood products exposed to seawaterare attacked by marine organisms such as Pholads, 7'eredo, and Lin~noria tripunctata.
25 The effective amount of compound employed in this appiication is empiricaily determined based upon parameters which include the specific preserving employed, the type of wood product to be protected, and the type of .,..~i-, the wood product is exposed to. Generaily, it is preferred to employ from about 0.5 to 5 volume % of the active moiety shown in formula (I) as part of a totai wood The biocides of the present invention can be added to the wood products by dther pressure or , ~UIG ' . ~, '' If pressure ~ ~ is employed, air, hydrostatic pressure or vacuum methods, or ~- 5. ~ . thereof, can be used.
WO 96140831 2 1 q 6 9 7 5 PCT/US95117048 ~
If . ~ l, " of wood is desired, dipping, spraying, brushing or the lilce can be used.
The bioactive . ' of the present invention can be either added directly to cellulosic materials such as the wood products in a preformed state, or the . ' of formula (1) can be added to, for example, bound to a cellulose binding protein. In this latter case, the bioactive compounds bond to the pul.~l.~ide structure of the cellulosic material (e.g., wood, paper and the like) upon contact.
Paper products can be treated to make a ' '~ LollL paper, cardboard boxes or the like using the flavonoid compound - pc ly ~ binding conjugate. A
sufficient portion of a cellulose binding domain up to the full length cellulose can be used when the target p~ ~h.uide is a cellulose. The preparation of cellulose binding domains is described in U.S. Patent Nos. 5,340,731; 5,202,247 and 5,166,317. Bindir,g proteins from scaffold proteins also can be used. See Shoseyev et al. (PCT application EP/0594/04132). The conjugate can be prepared with or.
without a cleavable bond using methods known to those sl~lled in the art.
Paint and wood ~ di~ products which may contain the biocidal of the invention as ~ h~ and l ~ ..h,;d~,i, include such as latex and solvent interior and exterior punts, coatingS for new and existing structures. Other p~unt products include industrial finishing products such as interior 20 and exterior coatings and marine antifouling paints.
The following examples are offered by way of illustration and not by way of limitation.
F.
n~ ntl M~thn~i~
The chemicals used in the examples given below were obtained from the following sources: cinnamic aldêhyde, Spectrum Chemical Company, N.J.; coniferyl aldehyde, APIN Chemical, U.K.; Tween 80 and sodium l,;~. Spectrum Chemical Company, Gardena, Ca. 1'~ are given as the, of the indicated solution before dilution.
~ WO 96/40831 2 1 9 6 q 7 5 PCT/US95/17048 E3~
E~al and ~ P~PllPnry Test of C
The bioactive . , ' are tested for fungal and algal repellency.
~ ~irmcrl~r slides are used as the substrates in both cases. One half of each slide is S coated on one side with a film of polymer containing the active agent to be tested, while the other half of the slide is not treated with the active agent. The total slide is exposed to the challenge of either fungi or algae with the expectation that the half of the slide containing the active agent will prevent growth of the challenging organism, while the untreated half will not.
In the fungal test, the slide is placed on the surface of an agar plate which isseeded with fungi. After incubation for about 14 days, the slide is examined forextent of growth or lack thereof on the treated surface of the slide. Since leaching of the active agent would create an ~. .l. -.,.1,1. zone-of ' ' outside the perimeter of the treated surface of the slide, no growth on the treated surface along with a small, or no, zone of inhibition is the desired result.
In the algal test, the slide is immersed in a nutrient broth which has been inoculated with the alg~ r~ After an incubation for 30 days (under light) and a water rinse, the slide is exannined . ~ ~ly and the extent of algal attachment is noted. Total lack of attachment on the treated surface is the desired result. Additional i r~ is obtained by comparing the extent of growth of alg~ throughout the broth. Significant leaching of the active agent from the treated surface would inhibit growth in the broth as well as on tbe treated surface.
Example 2 Paint ~ ,;de TPC~C
The test procedure is followed exactly from the following published procedure: R.A. Zabel and W.E. Horner, Joumal of Coanngs Technology, 53, 33-3',7, (1981), except that the organism A.., ' " pullulans M30-4 is used, isolated from mildewed exterior latex paint. Duplicates are run in each case. Two separate 30 tests are run for slightly different time periods.
WO 96/40831 2 1 9 6 9 7 5 PCTIUS95/17048 ~
E~
Wood 1'~ ,.,.\ T
This aspect of the present invention extends tne utility of the above described ~ ' ~ ' , ' to the wood ~ Liu~ area. Two general techniques are S shown. In one, a solution of the compound is applied to the wood direc~dy. In the second, a solution of compound bound to a cellulose binding protein is applied to the wocd.
Eight (about 2.5 cm x 2.5 cm x 0.5 cm) weighed pine wood blocks ~ placed in a dish and a 5-6 mm Hg vacuum applied for 30 minutes. Two solutions are prepared, one containing a compound of formula (1) and the second a compound of formula (I) bound to a cellulose binding protein. While still under vacuum, eachsolution is added to a dish and the wood blocks are submerged in one of the two solutions. After soaking for 30 minutes the wood blocks are removed from the solutions, excess compound is wiped off and the blocks are heated at 75~ C. for 16 hours. After cooling to room i r ' the blocks are weighed and analyzed to determine the ;' ' of compound throughout the wood chip.
Examp]e 4 Wood Rnt T.~ct The test procedure is based upon the following published procedure: H.P.
Sutter, l -' r J ' ;UiUiiU~ Bullenn, 14 (3), 95-99 (1978). The organisms employed are r: , ' u puteana ATCC 36336 and Lendnus lepide~s ATCC 12653 (a ~ Vt~, ~ fungus). Duplicates are run in each case. The growth of brown rot ( " ' d ~ ' ,) fungi on pine blocks after 25 days at 28~ C. is evaluated as:
Growth Key 0 - no growth 1 - slight growth 2 - moderate growth 3 - heavy growth 4 - very heavy growth ~ WO 91i/40831 2 1 9 6 9 7 5 PCr/US9S/17048 Four (~Z.5 cm x 2.5 cm ~-0.5 cm) print wood blocks are surface treatçd with either a wood ~ ti~, comprising a test ~ of a compound according to formula (I) or a commercial wood ~ ,. The wood blocks are brush coated on all surfaces and in some cases multiple coats are applied. Pressure 5 Dent is not used. These present examples correspond to what a consumer would do to apply a wood ~ . The amount of biocide applied to each wood block is calculated by ' ~ the weight increase of each wood block after treatmentand calculating the biocide present in the weight increase.
Example S
~ 111' ' ' ' ' TPCtj~
p- r '~ ~ e ~ I are tes~ed in a standard Minimum Inhibitory ~'. (MIC) tçst against 8 different bacteria and 8 different fungi. Also tested in this MIC test are Tween 80 (2%), NaHCO3 (6%) and Tween 80 (2%) plus 15 NaHCO3 (6%) ac blanks.
WO 96/40831 2 1 9 6 9 7 5 PCT/llS95/17048 ~
The organisms included in the MIC test are:
S ~
aeruginosa ATCC 9028;
2 - F ' acruginosa ~pyrithione resistant);
3 F 'I Ul~aLic~ aerogenes ATCC 13048;
4 - 5~ 7 aureus ATCC 6538;
5 - F. 7~ syriugac ATCC 19310;
6 - Fs ' ~ ~ rt~ ATCC 11355;
7 - Y~ vesiculoria ATCC 11551;
8 - Y~ ' piwseoli ATCC 19315; and EY~:
1 - Aspergillus niger ATCC i6404;
2 - Tr~ ,.S~ ~ ATCC 9533;
3 - Candiara albicarrs ATCC 10231;
4 - Y ~ , oryzac ATCC 34393;
S - Fuseariurn o~ysporum ATCC 15643;
6 - Glomerella augulata ATCC 10593;
7 - Actcrnaria solani ATCC 11078;
8 - r ~ - solani ATCC 28268.
Example 6 B~yuJ~h~ ~ 'e Activity of Fl-vr nnitl Al~i~hyde Bryophy~a (moss) bioassay studies were carried out as follows:
fifteen 9 cm plastic petri dishes were lined with Whatman filter paper discs (7.5 cm).
Three ml water were pipetted onto each filter paper disc. Mosses were placed in groups of five; each moss section was about 3.5 cm x 3.5 cm. Two ml of test solution were sprayed as a fine mist (Gilmour sprayer) from a distance of 10 cm. and the petri dishes placed on a table at ambient room i , and observed at 24, 48 and 60 hours. The area of desiccation was measured at each .' v.~li.,n time point.
See Table I (below) for results.
In a second set of ~A~ ~ ', the above pror edure was repeated with Dic~n moss using a single ~ IA~ of ciMamic aldehyde (2%) in a vehicle of 2% Tween 80 and 6% NaHCO3 as compared to the individual ~ 'J~ of the '( ~ See Table 2 for results.
~ WO 96/40831 2 1 9 ~ 9 7 5 PCT/U595/17048 ~ - Table1 l~ryophyta (Moss) Percent of Desiccation (over time) Moss r ~ o24 hrs. 48 hrs. 60 hrs.
Dicranum Fl 0 15 40 90 Spagnum (Bog Moss) Fl 0 20 60 90 Wood~nd Fl 0 20 60 85 Fl C~uLunic ~dehyde (2%) in 2% Tween 80, 6% NaHC03.
F2 Saponin (10~ Brix) 0.86 ml conc. diluted in 50 ml water.
F3 rFl + F21.
F4 -CONr~ROL H~O.
F5 2% Tween 80,6% NaHC03.
. Table2 3S Moss PercPnt ~l~cci~tjnn ~t 60 hn~
Percent r. ~Pci~tinn Cinnamic aldehyde (2%) 70 T80(2%) 10 NaHC03 (6%) 20 T80 + NaHC03 (2% + 6%) 25 Fl 90 WO 96/40831 2 1 9 6 q 7 5 PCT/lJS95il7048 ~
The most effective ' ' tested was 2% cinnamic aldehyde in 2%
Tween 80 and 6% NaHCO3; moss so treated showed 90% desiccation (Dicran~m and Bog Moss) and 85% desiccation (Woodland Moss) at o0 hours. Cinnamic aldehyde (2 %) in water produced 70% desiccation of Dicramlm Moss at 60 hours.
S Saponin (1:60in H2O) 10~ Brix caused 80%, 75% and 70% desiccation in Dicrcruvn, Bog Moss and Woodland Moss, .~L~I~. The ' ~ ' of cinnamic aldehyde a%) in vehicle and saponin (1:60 in HlO) 10~ Brix was more effective than saponin (1:60 in H2O) alone, but less effective than 2% cinnamic aldehyde in vehicle.
Exam~Le 8 Formula~ion,,~ Interios Latex Flat Paint A latex paint ' ' ' is mixed according to the p~u~ulLu.." in Table 3, below.
Table 3 IS Latex Paint r~
Ingredient Pounds Gallons Water 297.18 35.63 Propylene Glycol 35.00 4.05 Cellosize ER~1400 3.5 0.30 Kathon LX 1.5% 1.7 0.20 Drewplus L-422 2.0 0.27 Tanol 731 7.0 0.76 Triton N-101 2.0 0.23 AMP-95 2.8 0.36 Ti-Pure R-931 200.0 6.6 Optiwhite 75,0 4.09 Duramite 96.97 4.31 Ucar 379 265.50 29.35 Texanol 13.0 1.65 2.5% Cellosize ER-4400 100.0 11.92 Totals: 1103.7S 100.00 ~ WO96140831 21 9 69 75 r~ u48 Cinnamic aldehydc is substitutcd for }Cathon and propylene glycol in various One gallon batches are produced and stored in sealed one gallon paint pails.
At 30, 60, 120 and 180 days, lids are removed and the paint compared to S batches. Inspection for molds, skimming and settling is conducted. Test paints also are compared to ' flat latex on wood surfaces over the same time frame.
Tnc~tinnc are made for mold and general coating d v ;~
All I ' ' and patent A~ mentioned in this ~ are indicative of the level of sldll of those sldlled in the art to which this invention 10 pertains. All l ' ' and patent -~ are herein ~ by reference to the same extent as if each individual publication or patent application was and individually indicated to be r ' ~ by reference.
The invention now having boen fully described, it will be apparcnt to one of ordinary sldll in the art that many changes and . .I;~ - can be made thereto lS without departing from the spirit or scope of the appended claims.
1 - Aspergillus niger ATCC i6404;
2 - Tr~ ,.S~ ~ ATCC 9533;
3 - Candiara albicarrs ATCC 10231;
4 - Y ~ , oryzac ATCC 34393;
S - Fuseariurn o~ysporum ATCC 15643;
6 - Glomerella augulata ATCC 10593;
7 - Actcrnaria solani ATCC 11078;
8 - r ~ - solani ATCC 28268.
Example 6 B~yuJ~h~ ~ 'e Activity of Fl-vr nnitl Al~i~hyde Bryophy~a (moss) bioassay studies were carried out as follows:
fifteen 9 cm plastic petri dishes were lined with Whatman filter paper discs (7.5 cm).
Three ml water were pipetted onto each filter paper disc. Mosses were placed in groups of five; each moss section was about 3.5 cm x 3.5 cm. Two ml of test solution were sprayed as a fine mist (Gilmour sprayer) from a distance of 10 cm. and the petri dishes placed on a table at ambient room i , and observed at 24, 48 and 60 hours. The area of desiccation was measured at each .' v.~li.,n time point.
See Table I (below) for results.
In a second set of ~A~ ~ ', the above pror edure was repeated with Dic~n moss using a single ~ IA~ of ciMamic aldehyde (2%) in a vehicle of 2% Tween 80 and 6% NaHCO3 as compared to the individual ~ 'J~ of the '( ~ See Table 2 for results.
~ WO 96/40831 2 1 9 ~ 9 7 5 PCT/U595/17048 ~ - Table1 l~ryophyta (Moss) Percent of Desiccation (over time) Moss r ~ o24 hrs. 48 hrs. 60 hrs.
Dicranum Fl 0 15 40 90 Spagnum (Bog Moss) Fl 0 20 60 90 Wood~nd Fl 0 20 60 85 Fl C~uLunic ~dehyde (2%) in 2% Tween 80, 6% NaHC03.
F2 Saponin (10~ Brix) 0.86 ml conc. diluted in 50 ml water.
F3 rFl + F21.
F4 -CONr~ROL H~O.
F5 2% Tween 80,6% NaHC03.
. Table2 3S Moss PercPnt ~l~cci~tjnn ~t 60 hn~
Percent r. ~Pci~tinn Cinnamic aldehyde (2%) 70 T80(2%) 10 NaHC03 (6%) 20 T80 + NaHC03 (2% + 6%) 25 Fl 90 WO 96/40831 2 1 9 6 q 7 5 PCT/lJS95il7048 ~
The most effective ' ' tested was 2% cinnamic aldehyde in 2%
Tween 80 and 6% NaHCO3; moss so treated showed 90% desiccation (Dicran~m and Bog Moss) and 85% desiccation (Woodland Moss) at o0 hours. Cinnamic aldehyde (2 %) in water produced 70% desiccation of Dicramlm Moss at 60 hours.
S Saponin (1:60in H2O) 10~ Brix caused 80%, 75% and 70% desiccation in Dicrcruvn, Bog Moss and Woodland Moss, .~L~I~. The ' ~ ' of cinnamic aldehyde a%) in vehicle and saponin (1:60 in HlO) 10~ Brix was more effective than saponin (1:60 in H2O) alone, but less effective than 2% cinnamic aldehyde in vehicle.
Exam~Le 8 Formula~ion,,~ Interios Latex Flat Paint A latex paint ' ' ' is mixed according to the p~u~ulLu.." in Table 3, below.
Table 3 IS Latex Paint r~
Ingredient Pounds Gallons Water 297.18 35.63 Propylene Glycol 35.00 4.05 Cellosize ER~1400 3.5 0.30 Kathon LX 1.5% 1.7 0.20 Drewplus L-422 2.0 0.27 Tanol 731 7.0 0.76 Triton N-101 2.0 0.23 AMP-95 2.8 0.36 Ti-Pure R-931 200.0 6.6 Optiwhite 75,0 4.09 Duramite 96.97 4.31 Ucar 379 265.50 29.35 Texanol 13.0 1.65 2.5% Cellosize ER-4400 100.0 11.92 Totals: 1103.7S 100.00 ~ WO96140831 21 9 69 75 r~ u48 Cinnamic aldehydc is substitutcd for }Cathon and propylene glycol in various One gallon batches are produced and stored in sealed one gallon paint pails.
At 30, 60, 120 and 180 days, lids are removed and the paint compared to S batches. Inspection for molds, skimming and settling is conducted. Test paints also are compared to ' flat latex on wood surfaces over the same time frame.
Tnc~tinnc are made for mold and general coating d v ;~
All I ' ' and patent A~ mentioned in this ~ are indicative of the level of sldll of those sldlled in the art to which this invention 10 pertains. All l ' ' and patent -~ are herein ~ by reference to the same extent as if each individual publication or patent application was and individually indicated to be r ' ~ by reference.
The invention now having boen fully described, it will be apparcnt to one of ordinary sldll in the art that many changes and . .I;~ - can be made thereto lS without departing from the spirit or scope of the appended claims.
Claims (16)
1. A paint or wood preservative formulation comprising one or more bioactive compounds having the formula wherein R represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon andhetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms;
provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material or a copper-based components.
provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material or a copper-based components.
2. The formulation of claim 1, wherein said bioactive compound is cinnamic aldehyde, coniferyl aldehyde, or alpha hexyl cinnamic aldehyde.
3. The formulation of claim 1 or 2, comprising 0.5 to 5 vol. % of the bioactive compound.
4. A process for preserving paint formulations susceptible to bacterial degradation, said method comprising:
incorporating into said paint formulation an effective paint preserving amount of at least one bioactive compound having the formula (1), wherein R represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH
or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material.
incorporating into said paint formulation an effective paint preserving amount of at least one bioactive compound having the formula (1), wherein R represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH
or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material.
5. A process for controlling or preventing fouling on a hull of a boat, comprising treating said hull with the formulation of any one of the claims 1-3.
6. Use of one or more compounds having the formula (1) wherein R
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material, as a biocide in paint and/or wood preservative products.
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material, as a biocide in paint and/or wood preservative products.
7. Use of one or more compounds having the formula (1), wherein R
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material, as a preservative for paint.
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that when R is -CHO, R4 is hydrogen, and n=1, R1 is not o-methoxy; further provided that said formulation does not include a heat resistant clay material, as a preservative for paint.
8. Use of one or more compounds having the formula (1) wherein R
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms as a mildewicide in paint and/or wood preservative products.
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms as a mildewicide in paint and/or wood preservative products.
9. Use of one or more compounds having the formula (1), wherein R
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that said formulation does not include a heat resistant clay material or a copper-based component, as an antifoulant in paints and/or wood preservative products.
represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms; provided that said formulation does not include a heat resistant clay material or a copper-based component, as an antifoulant in paints and/or wood preservative products.
10. Use according to any one of the claims 6-9 wherein the compound having formula (1) is cinnamic aldehyde, coniferyl aldehyde, and/or alpha hexyl cinnamic aldehyde.
11. A paint or wood preservative formulation comprising a bioactive compound selected from the group consisting of coniferyl aldehyde and alpha hexyl cinnamic aldehyde.
12. A paint or wood preservative formulation comprising one or more bioactive compounds having the formula (1) in the amount of 0.5 to 5 vol. %, wherein R represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms,
13. A process for controlling or preventing fouling on a hull of a boat, comprising treating said hull with a formulation comprising one or more bioactive compounds having formula (1), wherein R represents -CH2OH or -CHO; n is an integer from 0 to 3; each R1 independently represents -OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 hetero atoms wherein the total number of carbon and hetero atoms in all R1 substituents of said compound is no more than 15; and R4 represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms, said formulation does not include a copper-based component.
14. A process for controlling or preventing fouling on a hull of a boat according to claim 13, wherein said bioactive compound is cinnamic aldehyde, coniferyl aldehyde, or alpha hexyl cinnamic aldehyde
15. A process for controlling or preventing fouling on a hull of a boat according to claim 13 or 14, wherein said formulation comprising 0.5 to 5 vol. % of the bioactive compound.
16. A paint or wood preservative formulation comprising a bioactive compound selected from the group consisting of cinnamic aldehyde, coniferyl aldehyde and alpha hexyl cinnamic aldehyde provided that said formulation does not include a heat resistant clay material or a copper-based component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48503295A | 1995-06-07 | 1995-06-07 | |
| US08/485,032 | 1995-06-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2196975A1 true CA2196975A1 (en) | 1996-12-19 |
Family
ID=23926669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2196975 Abandoned CA2196975A1 (en) | 1995-06-07 | 1995-12-29 | Flavonoid aldehydes and use in paint |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0801666A1 (en) |
| CN (1) | CN1159819A (en) |
| AU (1) | AU4691196A (en) |
| BR (1) | BR9508562A (en) |
| CA (1) | CA2196975A1 (en) |
| WO (1) | WO1996040831A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19611825A1 (en) * | 1996-03-26 | 1997-10-02 | Desowag Materialschutz Gmbh | Wood preservative |
| EP1119613A1 (en) * | 1998-09-30 | 2001-08-01 | The Procter & Gamble Company | Laundry detergent and/or fabric care compositions comprising chemical components linked to a cellulose binding domain |
| DE19847964A1 (en) * | 1998-10-17 | 2000-04-20 | Knoell Hans Forschung Ev | Non-aqueous composition containing an ester carrier based on a 1-4C monovalent alcohol and a natural vegetable oil fatty acid; useful for protecting wood against insects, bacteria and fungi |
| CN101536687B (en) * | 2008-03-20 | 2013-12-18 | 香港科技大学 | Use of flavone and isoflavone derivative as anti-biofouling substances and method and paint for preventing marine biofouling |
| DE102011077067A1 (en) * | 2011-06-07 | 2012-12-13 | Beiersdorf Ag | Active substance combination useful e.g. in cosmetic deodorants, comprises epsilon-polylysine and an aromatic aldehyde e.g. hexyl cinnamaldehyde |
| CN103788917A (en) * | 2012-10-29 | 2014-05-14 | 广东盈然木业有限公司 | Modified soy protein glue and its application in production of solid wood composite floors |
| CN106272789A (en) * | 2015-06-04 | 2017-01-04 | 东北林业大学 | A kind of water ballast type cinnamic aldehyde protectant preparation method of sill material |
| CN107322719A (en) * | 2017-07-13 | 2017-11-07 | 阜南县铭钰柳木工艺品有限公司 | A kind of wicker products surface hydrophobicity insect-prevention treatment method |
| EP3938451A1 (en) | 2019-03-15 | 2022-01-19 | Verinlegno S.p.A. | Wood coating products containing vegetal-origin anti-oxidants, and methods to make the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU520990B2 (en) * | 1979-01-29 | 1982-03-11 | Kureha Kagaku Kogyo Kabushiki Kaisha | Preservative |
| JP2796588B2 (en) * | 1989-08-24 | 1998-09-10 | 大日本除蟲菊株式会社 | Indoor acaricide |
| JPH04306269A (en) * | 1989-12-29 | 1992-10-29 | D & D Kk | Antifouling paint |
| JPH04300801A (en) * | 1991-03-29 | 1992-10-23 | Nippon Paint Co Ltd | Intercalate composition of antibacterial substance |
| FR2697133B1 (en) * | 1992-10-28 | 1995-01-13 | Transbiotech | Biocidal and / or biostatic composition and its applications. |
-
1995
- 1995-12-29 CA CA 2196975 patent/CA2196975A1/en not_active Abandoned
- 1995-12-29 AU AU46911/96A patent/AU4691196A/en not_active Abandoned
- 1995-12-29 WO PCT/US1995/017048 patent/WO1996040831A1/en not_active Application Discontinuation
- 1995-12-29 EP EP95944566A patent/EP0801666A1/en not_active Withdrawn
- 1995-12-29 BR BR9508562A patent/BR9508562A/en not_active Application Discontinuation
- 1995-12-29 CN CN 95195486 patent/CN1159819A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BR9508562A (en) | 1997-11-25 |
| CN1159819A (en) | 1997-09-17 |
| EP0801666A1 (en) | 1997-10-22 |
| AU4691196A (en) | 1996-12-30 |
| WO1996040831A1 (en) | 1996-12-19 |
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