Fungal growth control method

FIELD: fungicides.

SUBSTANCE: invention proposes use of strobilurines as fungicidal agents designed to be applied in the form of dispersions in industrial process water and in the form of pulp both used in paper industry. Application areas include preservation of wet sheet, protection against mildew, in particular protection of paper products, or other areas wherein fungicidal or mildew-controlling agents are required. Water systems, which can be treated with strobilurines include papermaking machine systems, fibrous intermediate and paper systems, cooling towers, and heat-exchangers.

EFFECT: increased availability, reduced toxicity, and avoided involvement of volatile and inflammable organic solvents.

38 cl, 2 tbl, 4 ex

 

BACKGROUND of INVENTION

1. The technical field to which the invention relates.

The present invention relates to the use of strobilurin fungicides and antifungal tools designed for use in industrial process water, such as in the composition of the fibrous mass and used in the paper industry.

2. Discussion current level of technology

In many engineering fields, such as industrial production, including the paper industry, and in cooling towers is important to prevent or slow the growth of microorganisms, such as fungi, mildew, algae, protozoa and bacteria, in water or aqueous fluids. For this purpose, use biocides, such as fungicides. However, fungicides are characterized by low solubility in water, due to their applications in prescribed order require special arrangements.

Fungicides are also of major industrial importance in the conservation of raw sheet. The concept of "raw list" refers to paper and other cellulosic products, which is not fully dried after fabrication. Crude leaf get, when storing paper, intended for further processing in a wet state prior to the beginning of this further processing. When provided excerpt of siropolis in the wet state for a long period, for example, for several days or longer, the raw sheet may be exposed to fungi or other biological attack. Thus, it is important to protect the raw sheet, for example using an appropriate biocide, in particular treatment with antifungal composition.

Used for fungicides in organic solvents, for example in the manufacture of paper, can be a harmful volatile flammable substances, the use of which is regulated by government regulations. Fungicides, such as, for example, Amical 48 (composition diiodomethyl-pair-of tamilselvan), can be contained in a benzothiazole or a heavy aromatic ligroin uniform.

One of the classes of biocides, which are widely used in farming as a means of protecting crops constitute strobilurin.

The first identified strobilurin, strobilurin a and b, were isolated from basicially mushrooms Strobilurus tenacellus and Crepidotus fulvotomentosus. It was found that although these antifungal compounds, which consists in the suppression of mitochondrial respiration, is quite effective as a means of crop protection in the fight against harmful and pathogenic fungi of various kinds, they are simultaneously low toxicity mlekovita them.

Because of strobilurin are characterized by low solubility in water, they are technically available in the form of dispersions based on clay or suspensions of microparticles intended for processing of agricultural crops, agricultural products and other farming products. For example, in US patent No. 5021581, which fully included in the present description by reference, presents strobilurines compositions, including examples 17 to 21 clay or talc. In example 16 this document also described strobilurines composition comprising benzyl alcohol, dodecylbenzenesulfonate calcium, nonylphenoxyacetic and alkyl benzenes.

However, despite the wide range of biocidal action exhibited by strobilurins outside agriculture these last are of limited use. Think outside the field of agriculture strobilurin can be limited only used as antifungal agents for humans and in veterinary medicine as part of preparations for topical use. Thus, in particular, strobilurines the product is used in human medicine and veterinary medicine drug called MUCIDERMIN SPOFA.

Although strobilurin fungicides for use, as noted above, agricultural conditions can be prepared in the form of d is of sparse based clays or talc, in General I believe that in an industrial environment, for example in systems for process water, fungicides for industrial applications should be mainly in the form of a solution, rather than a dispersion. For this reason, among others, outside the field of agriculture agricultural fungicides into account not accept.

Moreover, the presence of clay or talc in systems for process water, for example in papermaking machines, avoid, because such substances may affect the equipment and produced products. In the case of paper machines, for example, the quantity and quality of the added clay and/or talc, and if that happens, hard to regulate, because such components can affect the quality of paper products. In addition, as a rule believe that the presence of clay or talc in cooling towers and heat exchangers could cause problems, for example, due to clogging and abrasion of machine parts. Thus, the fungicidal compositions for use in the system for process water, for example in a paper machine or the tower, usually prepared as described above, mainly in organic solvents, but not in the form of dispersions using, for example, clay or talc.

Due to the toxicity, volatility and environmental problems is m, which is associated with the application of fungicides, prepared in volatile organic compounds, there is a need for a more harmless fungicides and fungicidal compositions for use in industry, in particular in the manufacture of paper, in heat exchangers and cooling towers.

There is a need to biocidal compositions, such as antifungal compositions, for use in process water and/or systems for process water, in particular for treatment of fibrous semi-finished product and paper and in cooling water. There is also a need to develop ways of biocidal treatment, such as methods of suppressing the growth of fungi, for use in such systems.

There is a need to develop new ways to suppress the growth of fungi for use in industrial systems, in particular in the system of fibrous semi-finished product and paper and in heat exchangers. Such methods include the preservation of paper and raw sheet, protection from fungi and retaining fluid in the cooling towers. Moreover, there is a need to create systems, such as systems for biocidal compositions, such as antifungal compositions, the preparation of which does not require the use of volatile or flammable organic solvents.

SUMMARY of the INVENTION

<> It was established that strobilurin, including new compositions, as well as technically available dispersion of clays and dispersion of microparticles can be used in industrial systems to fight the growth of fungi.

The present invention proposes a method of suppressing the growth of fungi or mildew, comprising the combination with a water system fungicide containing strobilurin where this water system includes at least one of the systems of the paper machine, wet sheet and a heat exchanger.

The present invention also offers a method of preserving raw sheet, comprising the combination of a wet sheet and fungicide containing strobilurin. Moreover, the present invention proposes a method of preserving raw sheet, comprising the combination of raw sheet fungicide effective amount of strobilurin.

In addition, the present invention proposes a method of protection from mold or protection from mildew cellulose products such as paper products, comprising the combination with a pulp product composition, including strobilurin. The present invention also offers a method of protection from mold or protection from mildew cellulose products such as paper products, comprising the combination with a pulp product fungicide effective amount of strobilurin.

According to the present invention it is also proposed paper product, including fungicide effective amount of strobilurin.

As strobilurin in accordance with the present invention can be used any of strobilurin or adamantin with antifungal properties. Preferred strobilurin includes at least one kresoximmethyl, AZOXYSTROBIN, compound 5 (described below), strobilurin And or strobilurin Century

Preferred water system to implement the methods and compositions of the present invention include at least one of the systems of the paper machine and heat exchanger. Scope of the present invention encompasses methods in which the water system includes a papermaking machine, which has a pulp VAT, and in stock a VAT of strobilurin combined with the composition on the fiber. The volume also covers the ways in which the water system includes a papermaking machine, which has refiner fibrous mass, and in this refiner fibrous mass of strobilurin combined with the composition on the fiber. In addition, the volume covers the ways in which the water system includes a papermaking machine, which has massin pool, and in this massin pool of strobilurin combined with the composition on the fiber. The volume also covers the ways in which the water system includes a paper machine is, having a headbox, and this pressure mailbox strobilurin combined with the composition on the fiber. Moreover, the volume covers the ways in which the water system includes a fibrous semi-finished product for the manufacture of paper, and this fibrous semi-finished product for the manufacture of paper combine strobilurin. The volume also covers the ways in which the water system includes a raw sheet, and with this raw sheet combine strobilurin.

In addition, the volume covers the ways in which the water system includes the fluid in the heat exchange system, and this fluid environment combine strobilurin. In a preferred embodiment, the heat exchange system is a cooling tower.

When strobilurin use in a wet sheet, in a preferred variant of strobilurin or fungicide, comprising strobilurin, contained in the raw sheet in fungicide effective amount. In a preferred variant of strobilurin contained in the raw sheet in a concentration of at least about 1 part./million, more preferably at least about 25 ppm million, in terms of raw sheet with a water content of 50 wt.%. In a preferred embodiment, the upper limit concentration of strobilurin raw sheet is less than about 5000 ppm million, more preferably less than about 1000 ppm million, more preferably less is about 500 ppm million, in terms of raw sheet with a water content of 50 wt.%.

In a preferred embodiment of the wet sheets are made with a bulky product and it is voluminous product is treated strobilurines with a flow rate of at least about 20 mg/m, preferably at least about 30 mg/m2more preferably at least about 40 mg/m2in terms of the surface area of the bulky products. In a preferred embodiment, the voluminous product is treated strobilurines with a preferred flow rate of less than about 600 mg/m2more preferably less than about 300 mg/m2, more preferably less than about 150 mg/m2.

In accordance with the present invention the raw sheet can be made of the composition of the fiber, including the fungicide.

When strobilurin put on cellulose products, such as paper products, preferably different from the raw sheet, in the preferred embodiment, is applied fungicide effective amount of strobilurin. In a preferred embodiment, such a cellulose product includes at least about 50 ppm million strobilurin, more preferably at least about 100 ppm million strobilurin, more preferably at least about 150 ppm million strobilurin, calculated on the dry weight of the paper product. In predpochtitel the nom embodiment, in the case of paper products, preferably different from the raw sheet, it includes about 1000 ppm million or less strobilurin, more preferably about 500 ppm million or less strobilurin, even more preferably about 250 ppm million or less strobilurin.

When strobilurin used in aqueous compositions, such as being in a heat exchange system, the preferred concentration of strobilurin greater than about 100 ppm million, more preferably greater than about 200 ppm million, even more preferably greater than about 300 ppm million, where the concentration is the weight of strobilurin on the total weight of the aqueous composition. The concentration of strobilurin in aqueous compositions, in particular in heat-exchange system, is usually about 5000 ppm million or less, more preferably about 1000 ppm million or less, even more preferably about 500 ppm million or less.

DETAILED description of the INVENTION

In the present description details examples are only to illustrate the discussion of various embodiments of the present invention and are presented for the reason that they are considered to be means for the most effective and simple perception of the description of the principles and contemplative aspects of the present invention. In this regard, any on ytki to show structural details of the present invention in more detail, than is necessary for a fundamental understanding of the invention, no, description clearly demonstrates specialists in the art the possibility of practical implementation of some embodiments of the invention.

In this application the results of all determinations of the percentage of all cases, unless otherwise stated, expressed in terms of 100 wt.% sample of a given mass. So, for example, 30% correspond to 30 wt. frequent. for each 100 wt. frequent. sample.

In all cases, unless otherwise specified, reference to a compound or component covers the connection itself or the component, as well as in combination with other compounds or components, such as mixtures of compounds.

In addition, when an amount, concentration, or other value or parameter is given as a list of upper preferable values and lower preferable values, they should be seen as a specific indication of all intervals defined by any pair of upper preferable values and lower preferable values, regardless presents these intervals separately or not.

The methods of the present invention encompass the use of the compositions of the present invention to achieve a biocide, preferably antimicrobial, preferably fungicide the defense and/or mildewcides actions. The compositions of the present invention can be used in systems of fibrous semi-finished products and paper; in heat exchange systems, such as cooling tower; and oil and gas systems, preferably in systems of fibrous semi-finished products and paper.

The invention can be applied in any system of fibrous semi-finished product and paper, for example in the system of production of paper, at any point in the system where possible, the use of fungicides, and any method by which it is possible to use fungicides in the paper industry. Compositions of the present invention, for example strobilurines compositions can be applied directly or mixed with one or more other components. For example, for use in the paper manufacturing process, the composition of the present invention may, but need not, contain one or more additives for the manufacture of paper.

Acceptable well as any combination of the above plots before (during the process) in any of the above areas, at any point between such sections or any other acceptable site or combination of sites at the same time or at different times.

Non-limiting examples of acceptable uses in the system of fibrous semi-finished product and issue include:

a) a refiner and prefinery olonilua a lot in stock tanks;

b) the elevation of fibrous material held in the refiner for fibrous material;

in) treated fiber semi-finished product stored in stock basins;

g) fibre pulp for making paper, available from stock pools; and

d) headbox, the point at which the fibrous material for the manufacture of paper will end with an adjustable flow rate on long grid;

e) preservation of raw sheet;

g) protection from mold and/or mildew;

C) the size press;

and section of a machine for coating.

In addition, an object of the present invention is an industrial antimicrobial compositions, preferably fungicidal and/or mildewcide compositions comprising strobilurin, preferably with at least one dispersant agent and solubilizer. The object of the invention are methods of preparing such compositions and methods of use thereof.

In all cases, unless otherwise stated, the concept of "strobilurin" and "strobilurin" includes any representatives from a number of fungicidal substances known to specialists in this field of technology as strobilurin, and cover strobilurin that are currently known and those that are not yet known. Moreover, as outlined in the work of Clough and others (J.M. Clough and others, "Strobiluin Analogues as Inhibitors of Mitochondrial Respiration in Fungi", Anti-infectives: Recent Advances in Chemistry and Structure-Activity Relationships, edited by P.H.Bentley and others, Royal Society of Chemistry, cc.176-179, 1997), the contents of which are fully integrated into the present description by reference, strobilurin structurally related adamantinum, which also have a biocidal effect. Thus, the notion of strobilurin" in the present description should be understood as encompassing biocides, such as fungicides, the number of Adamantine. This concept also applies to mixtures strobilurines, mixtures of Adamantine and mixtures of at least one of strobilurin and at least one Adamantine. In the method or composition according to the present invention can be used any of strobilurin or a mixture strobilurines. Strobilurin can be natural, semi-synthetic or synthetic. Some of strobilurin described in the publication "Natural Products in Crop Protection: fungicides", posted on the web site http://ecsoc2.hcc.ru/posters/d1001/fungicides.html 31.08.99, the contents of which are fully integrated into the present description by reference.

Nature of strobilurin include those derived from fungal source, such as Strobilurus tenacellus and Crepidotus fulvotomentosus, and use without prior chemical modification. Examples of natural strobilurins are strobilurin and strobilurin, which have the structure

where X represents N and Y represents N in the case of strobilurin A, and X denotes co3and Y denotes Cl in the case of strobilurin Century of Natural strobilurin are very light sensitive, therefore, if and when they get into the environment, their effects may be weakened and/or decrease.

Semi-synthetic of strobilurin include those substances that are chemically modified derivatives of one or more natural strobilurines.

To synthetic strobilurins include compounds strobilurines series, which in nature do not occur. They include kresoximmethyl {methyl-(E)-2-methoxyimino-2-[2-(o-tolylacetic)phenyl]acetate}:

which is available on the company BASF, AZOXYSTROBIN:

which is available on the company Zeneca, and the SSF product 126:

Another strobilurin is the methyl(E)-2-{2-[6-(trifluoromethyl)pyrid-2-intoximeter]phenyl}-3-ethoxyacrylate, which corresponds to the formula

This strobilurin, which is believed to produce the company Zeneca, in the present description designated as compound 5.

Preferred of strobilurin include kresoximmethyl, AZOXYSTROBIN, compound 5, strobilurin, strobilurin In and with whom thou.

Kresoximmethyl available on the BASF product technical grade with a basic substance content of 94 wt.%. Kresoxim composition available under the trade names CYGNUS (EBRA File Symbol 7969-REU) and SOVRAN fungicide (EPA File Symbol 7969-RLU), which are both believed to be the active component include to 50.0 wt.% kresoximmethyl. Assume that both CYGNUS and SOVRAN include dispersion kresoximmethyl in clay and surfactant. AZOXYSTROBIN technically available on the company Zeneca under the trade names of the fungicide QUADRIS FLOWABLE and HERITAGE.

Despite the possibility of using such compositions strobilurines, as described above, it should be noted that the scope of the present invention is not limited to the above strobilurines compositions.

Strobilurines composition for use according to the present invention may include a solubilizer, dispersant and/or agent combinations. Moreover, with strobilurins composition, such as described above, it is possible to combine any combination of solubilizer, dispersant and agent combinations.

Solubilizer suitable for use in the present invention can be any substance that increases the solubility of strobilurin, or a mixture strobilurines in the water. Preferred solubilization include benzilate; N-is ethylpyrrolidin; propylene carbonate; alcohols such as benzyl alcohol, ethanol and methanol; and mixtures thereof.

As mentioned above, as a solubilizer for strobilurin can be used propylene carbonate. The preferred composition with propylene carbonate and strobilurines contain a sufficient number of strobilurin to achieve a biocide, such as fungicidal, action, preferably at least about 1 wt.% strobilurin relative to propylene carbonate. Preferred compositions of propylene carbonate, strobilurin contain up to about 40 wt.% strobilurin relative to propylene carbonate, more preferably up to about 20 wt.%, even more preferably up to about 15 wt.%, preferably up to about 10 wt.%, strobilurin relative to propylene carbonate. Specific strobilurines composition contains about 10 wt.% strobilurin. For example, a particularly preferred composition of strobilurin and propylene carbonate contains about 9.4 wt.% strobilurin relative to propylene carbonate.

The choice of the solubilizer may be made by an ordinary specialist in the field of technology for each specific purpose, and for different purposes of use may be preferred by different solubilization. Thus, in particular, despite the fact that propylene carbonate is excellent with what labilization, he may have an adverse impact on the felt elements of the press of the paper machine, so that it seems less desirable to implement methods that strobilurines composition comes in contact with a felt element of the paper machine.

In strobilurines compositions proposed in accordance with the present invention can also be used dispersant. The dispersing agents include any agent that promotes the dispersion of particles of strobilurin in a fluid environment. Some of the dispersant include, though not limited to, surfactants, clay and talc.

In addition, the compositions of the present invention may also include an agent combinations. Agent combination performs the function of a mediator between strobilurins and solubilizer, on the one hand, and the aqueous phase on the other. In other words, the agent combinations combined with strobilurins and solubilizer, increasing the dispersibility of strobilurin in the water and preventing the crystallization with the release of strobilurin. As agent combinations in the methods and compositions of the present invention may be used any substance or mixture of substances, which improves the dispersibility of strobilurin in the water.

Each agent of the combination may include one or not is how many of polymers, containing hydrophilic and hydrophobic areas, such as hydrophilic polyalkyleneglycol, hydrophilic cellulose derivatives. Some examples of polymeric agents combinations include polyethylene glycol (PEG), polypropyleneglycol (BCP), hydroxyethyl cellulose (SCE), hydroxypropylcellulose (GOC) and mixtures thereof. Polyalkyleneglycol and cellulose derivatives suitable for use in the present invention are available from a variety of technical sources.

In a preferred variant of the preparation process strobilurines compositions containing strobilurin dissolved, the dissolution of strobilurin accelerate mixing and/or heating of the composition. In the case of heating in a preferred embodiment, the composition is heated to a temperature below the temperature of decomposition of each of its components, and it is preferable to heat the composition to a temperature below the boiling point of this composition. For example, the composition can be heated to a preferred temperature of from about 40 to 60°C or higher. Heating and/or mixing can be accomplished in any way.

As mentioned above, the composition for use according to the present invention can include strobilurin dissolved in the composition or in any other form, for example in the form of disperse the particles of strobilurin. In a preferred embodiment, compositions that include strobilurin in dissolved form, for example compositions of strobilurin and propylene carbonate are resistant to precipitation. Under "resistance to precipitation" refers to the lack of any appreciable precipitate during storage of the composition for extended periods of time (e.g., within 24 h, preferably 30 days or longer) at a low temperature (for example, if 5°).

Scope of the present invention includes compositions, and the use of the compositions. As mentioned above, the compositions of the present invention can be used in industrial systems, such as systems with process water, including cooling systems, oil and gas systems, and systems of fibrous semi-finished products and paper. Industrial system in accordance with the present invention include systems in which the water mass of the fluid contained in these conditions, in which there is opportunity for growth of fungi and/or mildew. Such systems include, for example, fibrous semi-finished products and paper (for example, fibrous composition or raw leaf), heat-exchange system (for example, cooling towers and other industrial system, which is a rather closed systems, in order existed in the opportunity for growth of microorganisms, for example mushrooms. The growth of microorganisms, such as fungi, usually becomes detectable within three to five days or longer after preparation of the aqueous fluid.

Preferred fields of application for the compositions of the present invention are fibrous semi-finished products and paper. Some preferred area of application in systems of fibrous semi-finished products and paper include the use in stock tanks; refiners fibrous pulp in pulp basins; in the fibrous material for the manufacture of paper; in the pressure boxes, for storing raw sheet and for protection against the growth of mold fungus and/or mildew.

When the composition of the present invention is used to save the raw sheet, which can be applied to any part of the paper machine, such as a wet portion and a dry portion. Preferred sites include the press section, such as section size press or a portion of a machine for coating. The composition can also be applied in any way, preferably using a roller or rod atomizer, preferably moulded canvas.

The number of strobilurin, which can be used to preserve raw sheet, may depend on a number of factors, including the nature of the applications and conditions of use Relevant factors include, for example, the method of processing, the nature of the composition of the fiber, the types and amounts of additives used, the water content of the raw sheet, the grinding conditions, the type and species of microorganisms (microorganisms) (e.g., fungi, mildew, Aspergillus niger and so on), the growth of which it is necessary to suppress, storage conditions, light levels and estimated time within which provided for the preservation of the raw sheet. Ordinary specialist in the art can determine the appropriate number of strobilurin to save raw sheet for a specific application, and can be used any biocide effective amount of strobilurin.

When strobilurin use to save the raw sheet, an ordinary person skilled in the technical field may be applied to the raw sheet in any way. Typically, however, in the preferred embodiment, the crude retain the sheet according to any one of two preferred methods. In accordance with one method, which in the present description was named the method for securing raw sheet in the mass, strobilurines process crude sheet before from this raw sheet produce a bulky product such as a roll or bale. In the preferred embodiment, when implementing this method of strobilurin almost evenly distribute around a bulky product from the raw sheet. the hen carry out this method in a preferred embodiment, use fungicide and/or mildewcide effective to save raw sheet number of strobilurin, preferably greater than about 1 part./million, more preferably greater than about 25 ppm million where the amount in parts per million in the case of raw sheet is the ratio of the mass of strobilurin and mass of raw worksheet (including the water content 50 wt.%), multiplied by one million. The preferred upper limit the strobilurin is missing, but for economic reasons, the preferred concentration of strobilurin is less than about 5000 ppm million, more preferably less than about 1000 ppm million, even more preferably less than about 500 ppm million

Another preferred method of preserving raw sheet, which in the present description was named method of surface protection of the raw sheet, at the beginning of this raw sheet produce a bulky product such as a roll or stack. Then, on the surface of a roll or bale put strobilurines composition. This method may be more economical to implement, since the roll or stack of raw sheet consume less strobilurin. Suppose, however, when implementing this method ensures the efficient preservation of the raw sheet, because Strobel the Rin concentrate on the surface of the bale, where possible the settling of fungi, for example during storage. When implementing this method, strobilurin can be applied in any fungicide and/or mildewcide effective amount. However, usually the number of strobilurin is at least about 20 mg/m2preferably at least about 30 mg/m2more preferably at least about 40 mg/m2where the quantity is expressed in milligrams of strobilurin per square meter surface area voluminous products from raw sheet. The preferred upper limit the strobilurin is missing, but for economic reasons, the preferred concentration of strobilurin is less than about 600 mg/m2more preferably less than about 300 mg/m2even more preferably less than about 150 mg/m2.

It is obvious that the methods of protection of raw sheet in the bulk and on the surface can be combined, through fungicidal and/or mildewcide processing as in the bulk and on the surface. When implementing methods to protect raw sheet as in the bulk and on the surface, in the preferred embodiment, when performing at least one of the processing methods in the mass or on the surface of strobilurin use in accordance with the present invention. When both of these methods are used in conjunction the Institute, in a preferred variant of strobilurin used in the implementation of the method of securing the raw sheet as in the bulk and on the surface. For the ordinary practitioner in the art it is obvious that when implementing methods to protect raw sheet as in the bulk and on the surface, to be processed in the mass and/or surface active substance can be used in smaller quantities than specified above.

When treated paper products, other than raw sheet, the concentration of strobilurin determined in parts per million (ppm million) in terms of dry weight. When the treated paper product that is different from the raw sheet, you can use any fungicide and/or mildewcide effective amount of strobilurin. In a preferred embodiment, use at least about 50 ppm million strobilurin, more preferably at least about 100 ppm million strobilurin, even more preferably at least about 150 ppm million strobilurin. In a preferred embodiment for processing paper products other than raw sheet, use about 1000 ppm million or less strobilurin, more preferably about 500 ppm million or less strobilurin, even more preferably about 250 ppm million or less strobilurin.

When strobilurin combine with water, for example in gra is irne or before processing of paper, in the preferred embodiment, it is used in high enough concentrations to achieve the fungicidal and/or mildewcides actions. The concentration of strobilurin necessary to achieve a sufficient level of fungicidal and/or mildewcides steps can be varied depending on the subject processing systems and used strobilurin. Ordinary specialist in the art is able to determine a suitable concentration of strobilurin for specific applications in water, aqueous fluid or process water. However, usually fungicide and/or mildewcide effective concentration of strobilurin in water, aqueous fluid or process water is more than about 100 ppm million, more preferably greater than about 200 ppm million, even more preferably greater than about 300 ppm million, where the concentration is expressed in weight of strobilurin on the total weight of the composition. Applying too much of strobilurin causes the formation of waste. Thus, the concentration of strobilurin in water, aqueous fluid or process water is typically about 5000 ppm million or less, more preferably about 1000 ppm million or less, even more preferably about 500 ppm million or less.

EXAMPLES

Further, the present invention prolly is concentrated with the aid of the following examples. These examples are not limiting and not narrowing the scope of the invention.

In all cases, unless otherwise stated, amounts in these examples are expressed in weight percents, parts, etc.

Example 1

The composition of the components listed in table 1, is prepared by adding 150 mg of benzoylacetate (firm Janssen Chimica, Geel, Belgium) to 100 mg of kresoximmethyl technical grade (basic substance content of 94 wt.%, BASF Corporation, Ludwigshafen, Germany). This mixture is placed in a test tube and to facilitate the dissolution of kresoximmethyl process is carried out in hot tap water. To Supplement mixture in this solution was added 750 mg of the product of PEG 400 (firm Acros Chemical, fair lawn, PCs, new Jersey.

Table 1
ComponentContent (wt.%)
kresoximmethyl (technical grade)10%
benzoylacetate15%
product PEG-40075%

Example 2

100-milligrammes sample kresoximmethyl technical grade (BASF Corporation, Ludwigshafen, Germany) are added to 900 mg of propylene carbonate (company Sigma Chemical, St. Louis, PCs Missouri). This mixture is placed in a test tube and to facilitate the dissolution of kresoximmethyl process is carried out in hot bathroom si is vodnoy water.

Example 3

Preparation of spore inoculum. Two sterile Petri dishes containing potato dextrose agar, inoculant the microorganism Aspergillus niger (AKTK, American type culture collection, 6275). Cup incubated for at least 48 h at 35±1°C. Upon completion of the incubation period cups tested for the presence of mycelium and fruiting bodies of this fungus. To prepare sporadically suspension use scraping the agar surface, taken with a sterile cotton swab with a pointed tip. Disputes with a cotton swab suspended in a sterile test tube containing a solution of 0.85% salt and 0.01 vol.% product Tween 80. Sporadically the suspension is shaken or stirred with shaking to break up the clusters of spores and mycelium. Before the introduction of sporadically suspension in a test tube containing the salt and the product Tween, a spectrophotometer set at a wavelength of 650 nm and the absorption index set at zero. By using a spectrophotometer, determine the optical density (absorption) sporadically suspension. If necessary, the addition of diluent or dispute the optical density was adjusted to 0.29% absorption. When the optical density of 0.29% absorption wave length-650 nm) concentration of spores is 1×109spores/ml Sporadically suspe is the Zia diluted to 1/1000 with obtaining inoculum, used for microtiter test with a concentration of 1×106spores/ml.

Microtiter test. Protocol responses to three doses used six filter tablets MULTISCREEN (96-well transparent tablets MULTISCREEN-GV from 0.22-micrometer membrane; firm Millipore Corp., Molsheim, France). This Protocol and six tablets provide MULTISCREEN duplication of results of experiments. Three used active substances are products BAS49002F (kresoximmethyl concentration of 50 wt.%; BASF Corporation, Ludwigshafen, Germany), AF 1912 (diiodomethyl-para-tamilselvan; the company Angus Chemical Company, Buffalo grove, stillings) and MTS (methylenesuccinic; the company Aldrich Chemical Company, Milwaukee, items of Wisconsin). These active ingredients individually diluted with water to a concentration of 40 ppm million basic substance. With the use of separate blocks of cultivation for each active substance, these active substances are subjected to serial dilution to achieve the experimental doses in the range from 10 to 0,156 frequent./million Parallel processing (active substances) to each well add dextrose broth Saburo (firm DIFCO Laboratories, Detroit, pieces Michigan,) and inoculate. Microturbulence tablets incubated at 37°C for 24 h, and after this period, each well add 0.1%of astorpromocja XTT [2,3-bis(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazole-5-carboxanilide; the company Sigma Chemical, St. Louis, PCs Missouri] and 0.01%solution of the product PMS (finishingtouches; firm Sigma Chemical, St. Louis, stricture). Tablets incubated for approximately 3 hours At the filter using tablets MULTISCREEN remove the grown mycelium and not past the stage of vegetative spores of Aspergillus niger. The parameters of each microtiter wells for the recovery of the product of HTT with metabolically active cells (i.e., the change in color relative to the color of untreated, control materials provides an indication of the breathable cells mushrooms) read at a wavelength of 465 nm.

Results suppression of growth are presented in table 2, which shows the absorption after processing, converted into a percentage degree of inhibition of fungal growth in three of the tested active ingredients (BAS49002F, AF1912 and MVTS). In table 2 dashes presents negative values of inhibition, which indicates that the cells were viable, but the cycles of activity was absent.

Table 2
FungicideSampleConcentration (ppm million)
0,1560,31of 0.6251,252,5 5,010,0
BAS49002F (composition 50 wt.% kresoximmethyl in the dispersion of clay; firm BASF)Tablet 15214865707369
The tablet 212345365697158
AF1912, Amical Flowable 1912Tablet 120243889898989
The tablet 224363787888888
MVTS methylenesuccinicTablet 1----868888
The tablet 2----848989

Strobilurines composition, designated as product BAS49002F is very active, as evidenced by the results of the classification test (table 2). Believe that obviously enhanced performance Amical is partly due to the test, which is used to assess working ha is acteristic active substances.

Example 4

Testing for qualitative assessment, in which two kresoximmethyl song available on the BASF (BAS49002F and BAS4901 1F; BASF Corporation, Ludwigshafen, Germany) was injected at concentrations of 50 and 100 ppm million pieces of raw sheet, which previously inoculant sporadically suspension of Aspergillus niger. Fibrous mass concentration of 0.5 wt.% made from 70% fiber bleached pulp of hardwood and 30% fiber bleached pulp softwood. In a separate portion of this fibrous mass add chemical processing, BAS49002F and BAS4901 1F at concentrations of strobilurin 50 and 100 ppm million, calculated on the dry weight of the fibers. Casting (with a water content of about 50 wt.%) manufactured using device Britt jar. For each concentration and for each active substance, and for untreated control material produced by three castings. With the aim to minimize bacterial contamination with the castings are treated with respect aseptic conditions. Aseptically cut out the squares with sizes 2 " ×2 inches, and put them in a Cup with potato dextrose agar, DIFCO Laboratories, Detroit, pieces of Michigan). On the upper side of each piece of raw sheet with a pipette and dispense one milliliter of spore inoculum (see example 3 prigot the effect of spore inoculum). Cup tightly closed material PARAFILM (company American National Can, Menasha, PCs Wisconsin) and incubated at 35°C for seven days. Conduct supervision, daily fixing the growth and sporulation. Both compositions (BAS49002F and BAS4901 1F) at concentrations of 50 and 100 ppm million for up to 4-day exposure under such conditions prevent the growth of Aspergillus niger on potato dextrose agar in the cups, but after this period mark the growth of the fungus.

Although the present invention is described on the examples of some preferred variants of its implementation for the purpose of more fully understanding and evaluating its objects, it is necessary to consider that the scope of the invention to these specific choices are not limited. On the contrary, it should be borne in mind that all of the different options of implementation, modifications and equivalents as can be included in the scope of the invention, which is defined by the claims.

1. The method of suppressing the growth of fungi or mildew, comprising the combination with a water system fungicide containing strobilurin where this water system includes at least one of the systems of the paper machine, wet sheet and a heat exchanger.

2. The method according to claim 1, wherein the water system comprises a papermaking machine, which has massin Chan and Chang strobilurin combined with the composition on the fiber.

3. The method according to claim 1, in which water is the first system includes a papermaking machine, which has refiner fibrous semi-finished product and in this refiner fibrous semi-finished product of strobilurin combined with the composition on the fiber.

4. The method according to claim 1, wherein the water system comprises a papermaking machine, which has massin pool and this massin pool of strobilurin combined with the composition on the fiber.

5. The method according to claim 1, wherein the water system comprises a paper machine having a headbox and in the pressure box of strobilurin combined with the composition on the fiber.

6. The method according to claim 1, wherein the water system comprises a fibrous material for the manufacture of paper and with this fibrous material for the manufacture of paper combine strobilurin.

7. The method according to claim 1, in which the water system includes a raw sheet and with this raw sheet combine strobilurin.

8. The method according to claim 7, in which strobilurin contained in the raw sheet in a concentration of at least about 1 part./million in terms of raw sheet with a water content of 50 wt.%.

9. The method according to claim 8, in which strobilurin contained in the raw sheet in a concentration of at least about 25 ppm million in terms of raw sheet with a water content of 50 wt.%.

10. The method according to claim 7, in which strobilurin contained in the raw sheet in a concentration of about 5000 ppm million or less in terms of raw sheet when you provide the water and 50 wt.%.

11. The method according to claim 7, in which the raw sheet produce a bulky product and it is voluminous product is treated strobilurines with a flow rate of at least about 20 mg/m2in terms of surface area bulky items.

12. The method according to claim 11, in which the voluminous product is treated strobilurines with a flow rate of at least about 30 mg/m2in terms of surface area bulky items.

13. The method according to item 12, in which the voluminous product is treated strobilurines with a flow rate of approximately 600 mg/m2or less in terms of surface area bulky items.

14. The method according to claim 1, in which strobilurin includes at least one kresoximmethyl, AZOXYSTROBIN, methyl-(E)-2-{2-[6-(trifluoromethyl)pyrid-2-intoximeter]phenyl}-3-ethoxyacrylate, strobilurin And or strobilurin Century

15. The method according to claim 1, wherein the water system comprises the fluid in the heat exchange system and with this fluid environment combine strobilurin.

16. The method according to item 15, in which the heat exchange system includes a cooling tower.

17. The method according to item 15, in which the concentration of strobilurin is at least about 100 ppm million, calculated on the weight of the fluid.

18. The method of suppressing the growth of fungi or mildew, comprising the combination with a water system fungicide effective amount of strobilurin, Geeta water system includes, at least one of the systems of the paper machine, wet sheet and a heat exchanger.

19. The method according to p in which strobilurin includes at least one kresoximmethyl, AZOXYSTROBIN, methyl-(E)-2-{2-[6-(trifluoromethyl)pyrid-2-intoximeter]phenyl}-3-ethoxyacrylate, strobilurin And or strobilurin Century

20. The method according to p, in which the water system includes a papermaking machine, which has a pulp VAT and in stock a VAT of strobilurin combined with the composition on the fiber.

21. The method according to p, in which the water system includes a papermaking machine, which has refiner fibrous semi-finished product and in this refiner fibrous semi-finished product of strobilurin combined with the composition on the fiber.

22. The method according to p, in which the water system includes a papermaking machine, which has massin pool and this massin pool of strobilurin combined with the composition on the fiber.

23. The method according to p, in which the water system includes a paper machine having a headbox and in the pressure box of strobilurin combined with the composition on the fiber.

24. The method according to p, in which the water system includes a fibrous material for the manufacture of paper and with this fibrous material for the manufacture of paper combine strobilurin.

25. The method according to p in which water systems which includes raw sheet and with this raw sheet combine strobilurin.

26. The method according to p, in which the water system includes the fluid in the heat exchange system and with this fluid environment combine strobilurin.

27. The method of preserving raw sheet, comprising the combination of raw sheet with a fungicide, comprising strobilurin.

28. The method according to item 27, in which the fungicide is combined with the raw sheet in a concentration ranging from about 1 to about 5000 ppm million strobilurin in terms of a lot of raw sheet with a water content of 50 wt.%.

29. The method according to item 27, which from raw sheets are made with a bulky product and it is voluminous product is treated strobilurines with a flow rate ranging from about 20 to 600 mg/m2in terms of surface area bulky items.

30. The method according to item 27, in which the raw sheet made from the composition of the fiber, including the fungicide.

31. The method according to item 27, kotoro of strobilurin includes at least one kresoximmethyl, AZOXYSTROBIN, methyl-(E)-2-{2-[6-(trifluoromethyl)pyrid-2-intoximeter]phenyl}-3-ethoxyacrylate, strobilurin And or strobilurin Century

32. The way to protect against mold or protection from mildew products, representing a paper product, comprising the combination with a product, it is a paper product, the composition containing strobilurin.

33. The method according to p in which the paper product includes about 1000 ppm million or less article is amiloride in terms of dry weight.

34. The method according to p in which strobilurin includes at least one kresoximmethyl, AZOXYSTROBIN, methyl-(E)-2-{2-[6-(trifluoromethyl)pyrid-2-intoximeter]phenyl}-3-ethoxyacrylate, strobilurin And or strobilurin Century

35. Paper products, including fungicide effective amount of strobilurin.

36. Paper product according p comprising at least about 50 ppm million strobilurin in terms of dry weight.

37. Paper product according p, including approximately 1000 ppm million or less strobilurin in terms of dry weight.

38. Paper product according p in which strobilurin includes at least one kresoximmethyl, AZOXYSTROBIN, methyl-(E)-2-{2-[6-(trifluoromethyl)pyrid-2-intoximeter]phenyl}-3-ethoxyacrylate, strobilurin And or strobilurin Century



 

Same patents:

FIELD: fibrous materials.

SUBSTANCE: invention relates to method for production of fibrous semi-finished product with antibacterial properties, containing no heavy metals and useful in production of sanitary, domestic and hygienic paper as well as domestic articles (spoons, fogs, plates cups, etc.). Waste paper mass or mixture thereof with craft hardwood or coniferous cellulose is treated with potassium permanganate in amount of 0.1-0.5 % based on mass of dry cellulose in acidic medium using sulfur acid in amount of 3.1-18.6 % at 20-40°C until total reagent is absorbed.

EFFECT: semi-finished product of improved quality due to increased hygienic properties.

2 tbl, 25 ex

The invention relates to flavoring products for sanitary purposes

The invention relates to the field of pulp and paper industry and can be used in the manufacture of paper
The invention relates to the production of special kinds of paper

The invention relates to the field of obtaining the repellent and insecticidal agents and can be used in the manufacture of devices for repelling and destroying insects in the home and in agriculture for the protection of animals

The invention relates to the pulp and paper industry and the paper sanitary and domestic purposes

The invention relates to the pulp and paper industry and the paper sanitary and domestic purposes
The invention relates to the production of paper containing various means of protection against counterfeiting and unauthorized manufacture, and more particularly to securities with protective means, the action of which is based on the phenomenon of thermal sensitivity, t

The invention relates to a composition for impregnating base paper used for the manufacture of electrochemical kinds of paper

FIELD: paper-and-pulp industry.

SUBSTANCE: invention relates to production of pulps used in binder-based articles. Method of invention comprises repetitive soaking and washing of unbleached pulp in water, which is maintained in alkaline state at elevated temperature to obtain cellulose product characterized by chemical oxygen demand not above 2.0 kg per 10 kg dry cellulose.

EFFECT: improved strength characteristics of products.

14 cl, 1 dwg, 2 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: pulp for manufacturing mainly packaging cardboard contains sulfite cellulose, wood-pulp, and secondary fiber. Sulfite cellulose is, more particularly, bisulfite cellulose having rigidity 40-50 Kappa units, tear resistance 390-450 mN, and punching resistance 580-620 mN. Such bisulfite cellulose is obtained by pulping softwood at pH of cooking liquor 2.4-2.9, SO2 concentration 5.0-5.5%, and temperature 155-157°C. Wood-pulp is the one subjected to chemical, thermal, and mechanical treatment and characterized by whiteness 60-65%. Secondary fiber is ground paper waste with specified degree of grinding, optionally in the form of blend of differently ground marks.

EFFECT: improved strength characteristics and reduced manufacturing expenses.

4 cl, 1 tbl, 4 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: pulp for manufacturing mainly box-destination cardboard contains sulfite cellulose, wood-pulp, and secondary fiber. Sulfite cellulose is, more particularly, bisulfite cellulose bleached to 84-86% and having rigidity 30-35 Kappa units, tear resistance 430-460 mN, and punching resistance 430-460 mN. Such bisulfite cellulose is obtained by pulping mixture of softwood and foliferous wood at pH of cooking liquor 1.6-2.3, SO2 concentration 6.0-6.5%, and temperature 145-152°C. Wood-pulp is the one subjected to chemical, thermal, and mechanical treatment and characterized by whiteness 72-75%. Secondary fiber is ground paper waste with specified degree of grinding, optionally in the form of blend of differently ground marks.

EFFECT: improved strength characteristics and reduced manufacturing expenses.

4 cl, 1 tbl, 4 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: corn stems are reduced to fragment, boiled, ground, dispersed, flattened, and dried to produce paper sheets. Boiling is carried out for 1.5-4 h at ratio of aqueous solution of reagent to corn stem material between 3:1 and 6:1 and temperature 120-200°C.

EFFECT: achieved high quality of pulp, improved environmental condition, and reduced expenses.

5 cl, 2 tbl, 7 ex

Up!