KR20220044326A - Synergistic Wood Preservation Composition Comprising Polymer Betaine and Carbamate - Google Patents

Abstract

A synergistic wood preservation composition comprising polymer betaine and 3-iodo-2-propynyl butyl carbamate (IPBC) is described herein. Also described herein are methods of controlling microorganisms that produce mold and/or sapwood on wood or wood products by applying to the wood or wood products a synergistic wood preservation composition for controlling microorganisms.

Description

Synergistic Wood Preservation Composition Comprising Polymer Betaine and Carbamate

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application No. 62/884,738, filed on August 9, 2019, entitled "SYNERGISTIC WOOD PRESERVATIVE COMPOSITION COMPRISING POLYMERIC BETAINE AND CARBAMATE," the content of which is incorporated herein by reference in its entirety. incorporated herein by

background of the invention

1. Field of invention

The present invention relates to synergistic compositions suitable for use in the treatment and preservation of wood and wood products. The antimicrobial composition of the present invention comprises a wood preservation composition comprising a polymer betaine and an iodopropynyl compound. These combinations are particularly useful for protecting wood and wood products from spoilage due to the growth of microorganisms, particularly mold and sapstain producing microorganisms.

2. Description of the invention

Substrates of all types are susceptible to attack, spoilage and various kinds of destruction by several species of microorganisms including fungi, yeast, bacteria, algae and mold when exposed to normal environmental conditions. As a result, there has always been a great need for effective and economical means for long-term protection of various materials from breakage, deterioration, and destruction caused by these microorganisms. Materials requiring protection against such microorganisms include, for example, wood and wood products which are susceptible to degradation by the action of harmful microorganisms. Such degradation can lead, inter alia, to deterioration, discoloration, the formation of noxious odors, and other adverse effects on the substrate.

Much effort has been made to develop a wide variety of materials that are effective to varying degrees in retarding or preventing the growth of and resulting destruction of these microorganisms in a variety of circumstances. Such antimicrobial materials included halogenated compounds, organometallic compounds, quaternary ammonium compounds, phenolic, metal salts, heterocyclic amines, formaldehyde adducts, organic sulfur compounds, and the like.

There is no single organic antimicrobial compound that can provide protection against all microorganisms and is suitable for all applications. In addition to these limitations of efficacy, other limitations may limit the usefulness of certain antimicrobial agents. For example, stability, physical properties, toxicological profile, regulatory considerations, economic considerations or environmental concerns may render a particular ingredient unsuitable for a particular use. Therefore, there is a continuing need to develop new combinations that will provide a wide range of protection against a variety of needs.

A wise choice of composition can provide a way to maximize benefits while minimizing problems. Ideally, a combination with enhanced antimicrobial activity and suppressed or reduced less desirable properties would provide a better product. The task is to find a combination that provides protection against a wide variety of microorganisms in question, does not adversely affect the product to be protected, maintains its integrity for a long period of time and will not exhibit any strong adverse effects on health or the environment. will be.

Summary of invention

The present invention relates to certain synergistic preservative compositions comprising a polymeric betaine and an iodopropynyl compound. The present invention also relates to a method for controlling mold and/or sapwood on wood or wood products by applying an effective amount of such a composition to the wood or wood product substrate.

DETAILED DESCRIPTION OF THE INVENTION

When an iodopropynyl compound such as 3-iodo-2-propynyl butyl carbamate (IPBC) is combined with a polymer betaine such as didecyl bis(hydroxyethyl) ammonium borate (DPAB), they are surprisingly It has been found to form a wood preservation composition that is more effective against microorganisms that produce mold and/or sapwood on wood or wood products than a single component alone. In the combination of the present invention, the polymeric betaine and iodopropynyl compound have been found to complement each other in unexpected ways. The polymeric betaine and iodopropynyl compounds exhibit synergistic activity. This unexpected synergistic activity provides a number of advantages for the preservation of wood and wood products.

The present invention relates to a polymer betaine, or more precisely, didecyl bis(hydroxyethyl) ammonium borate (DPAB), and 3-io A synergistic wood preservation composition comprising do-2-propynyl butyl carbamate. Suitable polymeric betaines are described, for example, in US Pat. No. 5,304,237, which is incorporated herein by reference in its entirety. The structural formula of DPAB is:

The anti-staining bacteria composition of the present invention can be prepared as a solution or an emulsion by conventional means by using water or an organic liquid as a solvent. A preferred form is to combine an aqueous solution of polymer betaine with an organic solvent solution of IPBC. The process conditions for the preparation of the compositions of the present invention are ambient temperature.

The amount and ratio of polymer betaine and IPBC will depend on the particular application. Generally, the wood preservation composition will contain from about 1 to 100 parts by weight polymeric betaine per about 1 to 100 parts by weight IPBC. More preferably, the composition comprises about 1 to 90, 1 to 80, 1 to 70, 1 to about 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, or 1 to 40 parts by weight IPBC per weight part IPBC. 60, 1 to 50, or 1 to 40 parts by weight of polymeric betaine. A preferred weight ratio of polymeric betaine to IPBC is from about 30:1 to about 1:30, more preferably from 20:1 to 1:20, even more preferably from 10:1 to 1:10. A particularly preferred ratio of polymer betaine to IPBC is 5:1 to 10:1 parts by weight, ie about 5 to 10 parts by weight, polymer betaine per part by weight IPBC. Other preferred ratios of polymeric betaine to IPBC are 1:1, 2:1 to 1:2, 3:2 to 2:3, 3:1 to 1:3, 4:1 to 1:4, 4:3 to 3:4, 5:1 to 1:5, 5:2 to 2:5, 5:3 to 3:5, 5:4 to 4:5, 6:1 to 1:6, 6:5 to 5: 6, 7:1 to 1:7, 7:2 to 2:7, 7:3 to 3:7, 7:4 to 4:7, 7:5 to 5:7, 7:6 to 6:7, 8:1 to 1:8, 8:3 to 3:8, 8:5 to 5:8, 8:7 to 7:8, 9:1 to 1:9, 9:2 to 2:9, 9: 4 to 4:9, 9:5 to 5:9, 9:7 to 7:9, 9:8 to 8:9, 10:9 to 9:10, 10:7 to 7:10, and 10:3 to 3:10. According to another aspect of the invention, any upper limit of these ranges may be combined with the lower limit of other ranges, and vice versa.

Providing the preservative composition in a concentrated form having from about 15, 20, 25, 30, 35, 40, or 45 weight percent solvent to about 50, 55, 60, 65, 70, 75, or 80 weight percent solvent can be advantageous According to another aspect of the present invention, the composition comprises more than 80% by weight of a solvent, for example 80 to 99.9, 85 to 99.9, 90 to 99.9, 90.5 to 99.9, 91 to 99.9, 91.5 to 99.9, 92 to 99.9 , 92.5 to 99, 93 to 99.9, or 95 to 99.9 weight percent of a solvent. Typical solvents include water and/or organic solvents, including aromatic organic solvents, polar and non-polar organic solvents, and aliphatic organic solvents.

The concentrate is usually diluted about 10-200 fold to the strength of the working solution by addition of water (or another solvent). The diluted solution or emulsion may be applied to the wood by conventional treatment methods such as immersion, brush, spray, flooding or pressure.

These antimicrobial mixtures provide high levels of activity over a long period of time, providing the strengths of the individual components while minimizing the weaknesses of each. This type of complementary activity allows the use of fewer biocides in combination to achieve the desired effect at levels not achievable with either of the individual ingredients.

Most of the halopropynyl compounds that can be used in accordance with the present invention are well known and can generally be identified by the following structures:

YC=C-CH ₂ X

wherein Y is halogen and X is (1) oxygen which is part of an organic functional group; (2) nitrogen as part of an organic functional group; (3) sulfur which is part of an organic functional group; or (4) carbon that is part of an organic functional group.

The functional group of which oxygen is a moiety is preferably an ether, ester, or carbamate group. The functional group of which nitrogen is a moiety is preferably an amine, amide, or carbamate group. The functional group of which sulfur is a moiety is preferably a thiol, thiane, sulfone, or sulfoxide group. The organic functional groups of which carbon is a moiety are preferably esters, carbamates or alkyl groups.

Examples of compounds that can be used as the halopropynyl compound of the present invention are, inter alia, some of which are disclosed in US Patent Nos. 3,923,870; 4,259,350; 4,592,773; 4,616,004; 4,719,227; and 4,945,109 active iodopropynyl derivatives. These iodopropynyl derivatives include compounds derived from propynyl or iodopropynyl alcohol, such as esters, acetals, carbamates and carbonates, and include pyrimidines, thiazolinones, tetrazoles, triazinones, sulfamides, benzothiazole, ammonium salts, carboxamides, and iodopropynyl derivatives of urea. Among these compounds, the preferred and most widely used are halopropynyl carbamate, 3-iodo-2-propynyl butyl carbamate. These compounds are included within a useful class of compounds having the general formula:

wherein R may have 1 to 3 bonds corresponding to n, hydrogen, substituted and unsubstituted alkyl having 1 to 20 carbon atoms, substituted and unsubstituted alkyl having 6 to 20 carbon atoms aryl, alkylaryl, and aralkyl or cycloalkyl and cycloalkenyl groups of 3 to 10 carbon atoms, m and n are independently integers from 1 to 3, ie, they are not necessarily identical.

Particularly preferred are formulations of these halopropynyl carbamates, wherein m is 1 and n is 1, having the formula:

Suitable R substituents include alkyl, such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl, alkaryl and aralkyl such as phenyl, benzyl, tolyl, and cumyl; halogenated alkyls and aryls such as chlorobutyl and chlorophenyl; and alkoxy aryls such as ethoxyphenyl and the like.

Particularly preferred are 3-iodo-2-propynyl propyl carbamate, 3-iodo-2-propynyl butyl carbamate, 3-iodo-2-propynyl hexyl carbamate, 3-iodo-2-propy iodopropynyl carbamates such as nyl cyclohexyl carbamate, 3-iodo-2-propynyl phenyl carbamate, and mixtures thereof.

Compositions of the present invention will generally be formulated by mixing or dispersing the active ingredient with a liquid vehicle in proportions selected to dissolve or suspend the active ingredient. Vehicles may contain diluents, emulsifiers and wetting agents. Prospective uses of the biocidal composition include the protection of wood, wood products, fresh slag and the like. The compositions of the present invention may be provided as liquid mixtures such as dispersions, emulsions, microemulsions, or in the form of any other suitable product that is desirable or most useful.

When preparing the formulations of the present invention for a particular application, the composition is also possibly adjuvants conventionally used in compositions intended for such application, such as organic binders, additional fungicides, auxiliary solvents, processing additives, fixatives agents, plasticizers, UV-stabilizers or stability enhancers, water-soluble or water-insoluble dyes, color pigments, desiccants, corrosion inhibitors, anti-settling agents, anti-film agents and the like.

According to the present invention, a substrate is protected from contamination by microorganisms simply by treating said substrate with a composition of the present invention. Such treatment may involve mixing the composition with the substrate, coating or otherwise contacting the substrate with the composition, and the like.

The following examples are presented to illustrate and explain the present invention. Unless otherwise indicated, all references to parts and percentages are by weight.

Example 1

To demonstrate the efficacy of the compositions of the present invention against wood-degrading microorganisms, the following solutions were prepared:

(A) 1% DPAB was obtained by diluting 0.17 g of a 60% aqueous solution of DPAB (ProTek PBT or Polymer Betaine EP or Polymer Betaine Technology Grade Active Ingredient Wood Preservative, Troy Chemical Corporation, Newark, NJ) in 9.83 g of ethanol by stirring. A concentrate containing

(B) 0.25 g of a 40% IPBC solvent solution (Polyphase AF-1, Troy Chemical Corporation, Newark, NJ) was diluted in 9.75 g of ethanol by stirring to form a concentrate containing 1% IPBC.

(C) 21.04 g of a 60% aqueous solution of DPAB (ProTek PBT or polymer betaine EP or polymer betaine technology grade active ingredient wood preservative, Troy Chemical Corporation, Newark, NJ), 6.25 g of a 40% IPBC solvent solution (Polyphase AF-1, Troy Chemical Corporation, Newark, NJ) and 22.74 g of ethanol were mixed and stirred. The resulting concentrate contained 25% polymer betaine and 5% IPBC. The weight ratio of polymer betaine to IPBC was 5:1. 0.33 g of this IPBC/polymer betaine concentrate was diluted in 9.67 g of ethanol to form a use-dilution containing about 0.83% DPAB and 0.17% IPBC.

Solutions prepared as described above were tested in 96-well plates for their ability to inhibit fungal growth. The solution was prepared as described in Rodriguez-Tudela et al. 2006 "Antifungal susceptibility testing in Aspergillus spp. according to EUCAST methodology." The solution was mixed with the fungal organisms Aspergillus niger (ATCC# 6275), Aureobasidium pullulans (ATCC# 9348), Penicillium funiculosum (ATCC#) 11797) and Trichoderma pseudokoningii (ATCC# 26801). This method is briefly described below:

(One) Preservative test wells are prepared by adding 2 microliters of each 1% preservative solution formulation in duplicate to 198 microliters of 2xRPMI-MOPS-2% glucose in each column "1".

(2) Add 100 microliters of 2x RPMI-MOPS-2% glucose to the remaining column.

(3) The column is subjected to a 2-fold dilution to column "12".

(4) A suspension of microorganisms is prepared from PDA slant aged 3-5 days by flooding the slant with 1 mL of deionized water and 0.1% Tween-20.

(5) Suspension strength is determined by hemocytometer and then adjusted to 1x106 spores/mL with sterile deionized water.

(6) Add 100 microliters of the microbial suspension to all wells except the sterile (-) control containing the test medium. The water used to prepare the fungal suspension is added to the sterile (-) control wells.

(7) The inoculated 96-well plate is incubated at 35° C. for 3 days.

(8) After incubation, fungal growth is assessed by visual growth in test wells. The minimum inhibitory concentration (MIC) is reported in ppm and is defined as the lowest bactericide concentration that does not cause a visual change in turbidity in the test well.

(9) An experiment is considered valid only if growth is observed in the positive (+) control wells and no growth is observed in the negative control wells.

Efficacy against all four tested microorganisms is presented in Tables 1-4.

These tests showed that the combination of polymer betaine (DPAB) and IPBC was significantly unexpectedly better than treatment of either component taken alone against the saplococcus organism Aureobasidium pullulans and the fungal organism Trichoderma spp . It clearly proves that it provided great protection.

While the present invention has been particularly described with respect to specific embodiments, it will be understood by those skilled in the art, in light of the present disclosure, that many changes and modifications to the invention are now possible and that such changes and modifications are not to be regarded as a departure from the spirit and scope of the invention. will be. Accordingly, the present invention is to be construed broadly and limited only by the spirit and scope of the following claims.

Claims (12)

A synergistic wood preservation composition comprising polymer betaine and 3-iodo-2-propynyl butyl carbamate (IPBC). The composition of claim 1 , wherein the polymeric betaine comprises didecyl bis(hydroxyethyl) ammonium borate (DPAB). A method for controlling microorganisms that produce mold and/or sapstains on wood or wood products, the method comprising applying to the wood or wood products an amount of the composition of claim 1 effective to control the microorganisms, Way. The composition of claim 1 , further comprising an aqueous solvent, an organic solvent, or any mixture thereof. The composition according to claim 4, in the form of a solution or an emulsion. The composition of claim 1 comprising an aqueous solution of polymer betaine and an organic solution of IPBC. The composition of claim 1 comprising from about 1 to about 100 parts by weight polymeric betaine per about 1 to about 10 parts by weight IPBC. 8. The composition of claim 7 comprising from about 5 to about 10 parts by weight polymeric betaine per about 1 part by weight IPBC. 5. The composition of claim 4 comprising from about 15 to about 80 weight percent of a solvent or mixture of solvents. 5. The composition of claim 4, wherein the solvent or solvents are selected from the group consisting of water, aromatic solvents, polar solvents, and aliphatic solvents. 5. The composition of claim 4 comprising from about 91.5 to about 99.9 weight percent of a solvent or mixture of solvents. 4. The method of claim 3, wherein the composition is applied to the wood or wood product by one or more of immersion, brush, spray, flooding or pressure.