JP5723571B2 - Wood processing method - Google Patents

Description

  The present invention relates to a method of treating wood, wherein the wood is contacted with a liquid or water-soluble ammonium organic carboxylate and an invertebrate control agent. The present invention also relates to a wood preservative composition containing an ammonium organic carboxylate and an invertebrate control agent. In addition, the present invention relates to a composition containing an ammonium organic carboxylate and an invertebrate control agent.

  Example 2 of WO patent specification 95/27600 discloses a wood preservative comprising, in addition to zinc acetate and copper acetate, a quaternary ammonium compound such as ammonium acetate, preferably didecyldimethylammonium chloride.

US patent specification No. 4,929,454 (column 2 line 60 - column 3 line 6) are zinc, it can be composed of tertiary _C 8 _{-C 20} alkyl ammonium salt of copper, and fatty acids Disclosed is a method for preparing wood by impregnating wood with a quaternary ammonium compound. However, the use of copper and zinc can cause environmental and corrosion problems.

EP Patent Specification 1,114,704 A2 discloses a wood preservative that is free of copper and zinc and contains a water-soluble ammonium organic carboxylate. The ammonium ion of this quaternary ammonium carboxylate comprises a C _{1 to} C ₂₀ alkyl group or an aryl-substituted alkyl group and at least one, preferably two alkyl groups containing 8 to 20 carbon atoms (see above specification). (See paragraph [0051] of the book). The carboxylate can be, for example, acetate (see paragraph [0224]) or propionate (see paragraph [0219]). In addition to microbicidal properties, the preservatives containing the quaternary ammonium carboxylates of the above references have enhanced retention and should be used without metal stabilizers such as combinations of arsene, chromium, copper and zinc. (See paragraph [0032] of the reference above).

  However, the ammonium carboxylates of these references are associated with the problem that they are not absorbed by wood in adequate amounts or are poorly retained in wood.

  There are several well known agents that can be used to control insects such as termites.

  Disodium octaborate tetrahydrate (DOT) is used against fungi, insects and termites. DOT maximizes solubility, dissolution rate and boron oxide content, making borate active ingredients far superior to traditional boric acid or borax. At levels used in professional applications, pest metabolism is inhibited on a cell-based basis to prevent pest invasion. The tetrahydroxyborate anion forms a chelate complex with the cis-adjacent hydroxy group in the ribose sugar of nicotinamide adenine dinucleotide (NAD), along with the cationic nitrogen of the nicotinamide moiety, resulting in electrostatic stability of the chelate. In this arrangement, glycolytic dehydrogenase enzymes that are pentose phosphate pathways or tricarboxylic acid pathways cannot use NAD and NADP, thus blocking cellular energy production systems including adenosine triphosphate production.

  Permethrin is one of many synthetic pyrethroids. Permethrin is a neurotoxin and is used against a variety of pests on nuts, fruits, vegetables, cotton, ornamental plants, mushrooms, potatoes and grains. Used for greenhouse, home garden and termite control. It also controls animal ectoparasites, flies and cockroaches. Permethrin kills insects by strongly exciting the nervous system. Instead of sending a single impulse to the stimulus, nerves exposed to permethrin send a series of impulses, similar to the organochlorine insecticide DDT. Membrane ATPase is the target of the neurotoxic effects of pyrethroid compounds, which can explain the effect on the immune apparatus. Permethrin is toxic to bees and other beneficial insects, fish, aquatic insects, crayfish and shrimps. For many species, concentrations below 1 part per billion are lethal. Permethrin causes malformations and other developmental problems in tadpoles and reduces the number of oxygen-carrying cells in the bird's blood.

  The above agents, which are widely used for insect control, are relatively harmful to beneficial insects, which severely restricts their use, for example in the treatment of wood, When impregnated, the concentration should be kept very low.

  There are also some prior art methods of wood preparation in which wood is impregnated with copper compounds, reaction mixtures or complexes of ammonium carboxylate and copper compounds (eg US 6,352,583 and EP 238,051). Such wood preservatives have the disadvantage of using toxic copper compounds and / or poor retention in the wood and / or poor absorption into the wood.

It is a figure which shows the anti-corruption effect of a commercially available and new active ingredient when it mixes with MHEA and MHEA + PREA support | carrier. It is a figure which shows the anti-corruption effect of the mixture of the active ingredient and carrier prepared by Granula Oy. It is a figure which shows the effect of the said extraction procedure with respect to the anti-corrosion characteristic of wood material. It is a figure which shows the antifungal effect of a commercially available and new active ingredient when it mixes with MHEA and MHEA + PREA support | carrier. It is a figure which shows the antifungal effect of the mixture of the active ingredient and carrier prepared by Granula Oy. It is a figure which shows the effect of the said extraction procedure with respect to the anti-corrosion characteristic of wood material.

  Accordingly, the object of the present invention is to provide a method and composition for preparing wood, where the composition is well absorbed and has good retention.

  Another object of the present invention is to provide a method for preparing wood that does not require the use of an arsene, chromium, copper or zinc compound as a stabilizer.

  Yet another object of the present invention is to provide methods and compositions for protecting wood against invertebrates, in particular against insects, and more particularly against ants and termites, the composition comprising wood When impregnated with material, it is non-toxic to harmless invertebrates or insects so that it can be used in sufficiently large quantities.

  The above objective is accomplished here by a new method of preparing wood with a liquid or water soluble organic ammonium carboxylate of the type described above in combination with a wood preservative active ingredient containing an invertebrate repellent chelator. The active ingredient is preferably a mixture or reaction product of an organic active ingredient salt and an organic active ingredient acid.

Organic ammonium carboxylates have the formula (1):
^{[NR 1 R 2 R 3 R} 4] + n [R 5 (COO) n] -n (1)
Wherein R ¹ , R ² and R ³ are selected from the group comprising hydrogen, substituted alkyl containing 1 to 6 carbon atoms and unsubstituted alkyl containing 1 to 6 carbon atoms; ⁴ is substituted alkyl containing 1 to 6 carbon atoms or unsubstituted alkyl containing 1 to 6 carbon atoms, R ⁵ is hydrogen, substituted hydrocarbyl containing 1 to 6 carbon atoms Or an unsubstituted hydrocarbyl containing 1 to 6 carbon atoms, where n is an integer from 1 to 6. Such ammonium carboxylates are readily absorbed in wood in very large quantities and are then retained in the wood. The wood preservative active ingredient contains a chelating agent that repels invertebrates, the chelating agent being aminopropyl carboxylic acid or salt thereof, hydroxy acid or salt thereof, phosphonate (ie organic phosphonate, ie organophosphate) or this Selected from the group comprising a mixture of chelating agents belonging to two or more of the groups.

Wood preparation involves contacting the wood with another material. Organic ammonium carboxylate means a salt or complex formed from an ammonium cation and a carboxylate anion. Accordingly, one or more ammonium ions of the salt or complex may be primary (RNH ₃ ⁺ ), secondary (R ₂ NH ₂ ⁺ ), tertiary (R ₃ NH ⁺ ) or quaternary (R ₄ N ⁺ ). The carboxylate ion of the salt or complex can be monovalent (RCOO ⁻ ) or multivalent (R (COO ⁻ ) _{n> 1} ), in which case it can also contain non-neutralized carboxyl groups (—COOH). it can. In the latter case, R ⁵ is defined as being substituted with carboxyl.

  Solutions containing ammonium carboxylate and wood preservatives are here intended primarily for invertebrates, which mean insects such as termites and ants. However, the solution may also be useful against worms and snails. Additionally, some forms of the compositions of the present invention may be useful against harmful vertebrate pests.

  FI patent specifications 103704B and 110661B disclose a method for preserving livestock feed with ammonium carboxylate having a structure similar to the compound of formula (1). Nevertheless, the problem that arises in the preservation of livestock feed is different from that associated with the wood preparation method of the present invention, which is that livestock feed is not prepared with chelating agents and toxic metals such as copper and preservatives. This is because impregnation of livestock feed with an agent does not involve the same problem as impregnation of wood with a wood preservative. The purpose of preserving livestock feed is lactic acid fermentation, along with prevention of the growth of harmful microorganisms, yeast and mold.

The group R ⁵ of formula (1) is preferably hydrogen, substituted alkyl containing 1 to 6 carbon atoms or unsubstituted alkyl containing 1 to 6 carbon atoms, more advantageously hydrogen, 1 A substituted alkyl containing ˜4 carbon atoms or an unsubstituted alkyl containing 1-4 carbon atoms. The terms “substituted” and “unsubstituted” basically refer to groups containing heteroatoms (eg, —OH, —NH ₂ , —COOH).

Since the group R ⁵ is associated with a carboxylate group, the ammonium carboxylates of formula (1) are preferably based on lower organic carboxylic acids and can be prepared from such acids or salts thereof. Lower organic acids include formic acid, acetic acid, propionic acid, n- and i-butyric acid, and lower fatty acids such as n- and i-pentanoic acid. Useful acids also include benzoic acid and oxycarboxylic acids such as glycolic acid and lactic acid. Lower dicarboxylic acids such as oxalic acid, malonic acid, succinic acid and glutaric acid are also applicable.

The group R ⁵ of formula (1) is most advantageously hydrogen, methyl or ethyl. In formula (1), n is preferably 1 or 2, most advantageously 1. Therefore, the most advantageous organic ammonium carboxylates used in the process of the present invention are based on lower fatty acids.

As described above, the ammonium ion of formula (1) can be primary (RNH ₃ ⁺ ), secondary (R ₂ NH ₂ ⁺ ), tertiary (R ₃ NH ⁺ ) or quaternary. Can be secondary (R ₄ N ⁺ ), where R is typically substituted or unsubstituted alkyl containing 1 to 6 carbon atoms. Typical ammonium ions containing unsubstituted alkyl are generated from water-soluble amines such as methylamine (g), dimethylamine, trimethylamine, ethylamine, diethylamine.

Ammonium ions containing substituted alkyl are typically generated from water-soluble amines in which the alkyl is substituted with one or more hydroxyl groups. In formula (1), R ¹ is preferably hydrogen, and R ² and R ³ are preferably from the group comprising C ₁ -C ₆ alkyl substituted with hydrogen and a hydroxyl group, preferably hydrogen And selected from the group comprising C ₁ -C ₄ alkyl substituted with a hydroxyl group. R ⁴ is preferably C ₁ -C ₆ alkyl substituted with a hydroxyl group, most advantageously C ₁ -C ₄ alkyl substituted with a hydroxyl group.

  Accordingly, ammonium organic carboxylates produced from lower alkanolamines are particularly useful. Among the lower alkanolamines, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, mono-sek-butanolamine, di-sek-butanolamine and triethanolamine -Sek-butanolamine can be cited.

  One important group of useful alkanolamines includes lower alkyl alkanolamines such as methylethanolamine, dimethylethanolamine, diethylethanolamine, butylethanolamine, methyldiethanolamine and ethyldiethanolamine. Additional information on useful alkanolamines can be found in the book Kirk-Othmer, Encyclopedia of Chemical Technology 3rd Ed. , Vol. 1, p. 944 (incorporated herein).

R ¹ is hydrogen and R ² and R ³ are selected from the group comprising ethyl substituted with hydrogen and a hydroxyl group, preferably from the group comprising hydrogen and 2-hydroxyethyl, and R ⁴ is a hydroxyl group It is particularly recommended that it be ethyl substituted with, preferably 2-hydroxyethyl. The ammonium carboxylates according to the invention are therefore preferably based on the usual mono, di or triethanolamine.

  In the most advantageous embodiment, the ammonium organic carboxylate of formula (1) is selected from the group comprising formic acid and monoethanolamine salts or complexes and propionic acid and monoethanolamine salts or complexes. These agents provide maximum absorption of the material into the wood and retention in the wood. In one optional embodiment, the ammonium organic carboxylate is a mixture of a formic acid and monoethanolamine salt and a propionic acid and monoethanolamine salt, preferably in a weight ratio of 80:20 to 20:80.

  Wood preservative active ingredients used in combination with the described ammonium carboxylates of formula (1) are aminopropyl carboxylic acids or salts thereof, hydroxy acids or salts thereof, phosphonates (ie organic phosphonates or organophosphates) or these A chelating agent selected from the group comprising a mixture of:

  Chelation is the formation or presence of two or more separate bonds between a multidentate (multiple bond) ligand and a single central atom. Usually these ligands are organic compounds and are called chelants, chelators, chelating agents or sequestering agents. Chelating agents are chemicals that produce soluble complex molecules with specific metal ions that inactivate ions so that they do not normally react with other elements or ions that produce precipitates or scale.

  Preferably, the chelating agent of the present invention is a chelating agent capable of binding iron and manganese ions and containing phosphorus (P) in the molecular structure such as HEDP.

  When the chelating acid is a complexing agent, ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), n-hydroxyethyl-ethylenediainine triacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediamine-di-o -Hydroxyphenylacetic acid (EDDHDA), diethanolglycine (DEG), ethanoldiglycine (EDG) or a salt thereof, or 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetria It can be selected from the group comprising imine pentamethylene phosphonic acid (DTPMP) or a salt thereof or a mixture thereof.

  Preferably, the chelating agent includes phosphorus. The most preferred phosphorus-containing chelating agent is 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriiminepentamethylenephosphonic acid (DTPMP) or a salt thereof, or a mixture thereof. .

The ammonium carboxylate of formula (1) can be brought into contact with the wood by in situ preparation from the starting material, in other words it can also be brought into substantial contact with the wood. Typical starting materials here include hydroxides or salts produced by ammonium ions of formula (1), such as chlorides and acids or salts produced by acid ions of formula (1), such as sodium salts. , Mainly resulting in the following reaction (2):
^{nNR 1 R 2 R 3 R 4} X + R 5 (COOM) n → [NR 1 R 2 R 3 R 4] + n [R 5 (COO) n] -n + nMX (2)
Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are the same as in formula (1), and X and M are anions and cations, respectively, that form stable acids or salts. is there. Typical anions X include hydroxyl and halide, and typical cations M include protons, as well as alcal and alkaline earth metals.

  In practice, the ammonium carboxylate of formula (1) is mixed, for example, with an ammonium cation source and a carboxyl anion source in the desired molar ratio, using no medium or a suitable solvent such as water as the medium. It is prepared by. If the starting materials are amine and acid, they are simply mixed with gentle heating if necessary. If the starting materials are composed of salts, these are typically dissolved separately in water and then the solutions are combined. If the salt or complex so produced is hydrophobic, it can leave the aqueous phase as an oily or paste-like deposit or wax-like precipitate and can be separated from the aqueous phase by known methods. If both the starting material and the product produced are hydrophobic, the preparation can be carried out with an organic solvent instead of water.

  The result of the preliminary step is that when the ammonium carboxylate of formula (1) is eg fluid pair: ethyleneamine-formic acid, it can be reacted under certain circumstances to produce an amide when no solvent is present. An increase in temperature is preferred for amide formation. Little ester is produced.

  Ammonium organic carboxylates of formula (1), and compositions and solution raw materials obtained from these ammonium carboxylates are reused of the freezing point depressing composition described in US Patent Application No. 12/639109 to Ahlnas et al. Obtained by.

  In the wood treatment method of the present invention, the organic ammonium carboxylate of formula (1) is preferably in the form of an aqueous solution. The aqueous solution is preferably, for example, 5-95% by weight, typically 15-45% of the total composition composed of ammonium carboxylate, organic active ingredients, and possibly water, additives and surfactants. It has a concentration by weight.

  Presently, the ammonium carboxylate of the ammonium carboxylate of formula (1) has been found to be particularly suitable for transferring wood preservative active ingredients into wood containing chelating agents that provide wood properties to termites. Has been. The active ingredient is preferably a mixture or reaction product of an organic active ingredient salt and an organic active ingredient acid.

  On the other hand, the present invention is based on the fact that both polar poles of formula (1), ie ammonium cations and carboxylate anions, are easily adsorbed and absorbed on the treated wood material. The small molecular size of both polar molecules, low surface tension, and the special ability to bind both polar molecules to hydrophobic and hydrophilic materials, constituents and molecules of wood use organic ammonium carboxylates in wood treatment Make it extremely effective. Wood materials can be easily treated with organic carboxylates, which remain inside the wood material without leaching.

  When wood is treated with a solution comprising an organic ammonium carboxylate of formula (1) and a chelating agent containing an active ingredient, the wood material becomes more resistant to invertebrates and in addition to fire. Better properties can be obtained (fire protection). Resistance to target invertebrates, particularly insects such as ants and termites, is based on the repellent effect of chelating agents on the target invertebrates.

  Wood can be treated with a sufficiently large amount of solution containing the described chelating agents, which are harmless invertebrates, especially harmless, because their effects are based on repellent effects on insects. Not toxic to insects.

  By using the described chelating agents that repel insects in the wood preservative solution, additional unexpected advantages can be obtained because the use of chelating agents also improves the fire protection properties of the wood material.

  In another embodiment, the ammonium organic carboxylate of formula (1) is well absorbed by the wood, so that it can be used as a further carrier for other active ingredients such as active ingredients that protect the wood from microorganisms.

  In another embodiment, the organic ammonium carboxylate of formula (1) is well absorbed by the wood, so in another embodiment it can be used as a carrier for other types of active ingredients such as active ingredients that protect the wood from microorganisms. Here, the carrier dissolves the active ingredient, moves in large amounts into the wood, and holds it in the wood. Thus, the quality and amount of ammonium carboxylate considered can be selected to move the wood preservative into the wood.

  The ammonium organic carboxylates of formula (1) are particularly suitable for transferring wood preservatives into wood that also contains a microbicidal wood preservative. The microbicidal wood preservative is preferably a mixture or reaction product of an organic active ingredient salt and an organic active ingredient acid.

  The microbicidal organic active ingredient salt component of the active ingredient is preferably an alkali metal, alkaline earth metal and ammonium salt of an aromatic acid, an alkali metal, alkaline earth metal and ammonium salt of an aliphatic and aromatic sulfonic acid As well as the acid salts of amines. Particularly preferred organic active ingredient salts include sodium benzoate, sodium alkylbenzenesulfonate, cetylpyridinium chloride and salts of formic acid and ethanolamine. The latter also acts as an ammonium organic carboxylate of formula (1) that is sufficiently absorbable.

The organic active ingredient acid component of the active ingredient used to protect the wood from microorganisms is preferably from the group comprising aromatic carboxylic and sulfonic acids, fatty acids, organic hydroxyl acids, and oligomers and chelating acids thereof. Selected. Preferred materials, benzoic _acid, C 6 _{-C 20} fatty acid, preferably a _C 12 _{-C 18} fatty acid and ethylenediaminetetraacetic acid, such as stearic acid (EDTA). Mixtures of C ₁₂ -C ₁₈ fatty acids such as benzoic acid and stearic acid are particularly advantageous components of organic active ingredients.

  An advantageous combination of organic active component acid and organic component salt / ammonium carboxylate is a salt of EDTA + ethanolamine combined with formic acid and / or propionic acid.

  The organic ammonium carboxylate of the formula (1) of the present invention also contains acidic copper chromate, ammoniacal copper zinc arsenate, chromium-containing copper arsenate, and ammoniacal copper quaternary. Other types of wood preservatives such as grade salts, copper bis (dimethyldithiocarbamate), ammoniacal copper citrate, copper azole A and borate compounds function to move into the wood. Other applicable commercially available wood preservatives (such as fungicides, insecticides, termites) include the active ingredients used in the Preventol® and K-Othrine® brands. Examples of these are Preventol (R) A8 (Tebucanazole), Preventol (R) MP100 (IPBC), Preventol (R) HS11-N (Pyrethroide) and K-Othrine (R) 100 (Deltametrin). .

  Examples of non-metallic wood preservatives that can be transferred into wood by the described ammonium carboxylate support are botulin and benzalkonium chloride (alkylbenzyldimethylammonium chlorides of various alkyl chain lengths) and environmentally safe biocides Polyhexamethylene guanidine (PHMG), which is a particularly advantageous biocide because it acts as Furthermore, the drying properties of PHMG are very good, speeding up the process.

  When ammonium carboxylates of formula (1) are used to transfer the copper compounds used as the active ingredient into the wood material, these copper compounds are water insoluble, so ammonium carboxylates and copper The compounds react to form a two-phase mixture. Here, the first phase contains an insoluble copper compound, and the second phase contains an ammonium carboxylate complex or an ionized ammonium carboxylate. The present invention does not simply relate to a method for transferring the reaction product of ammonium carboxylate and a copper compound into wood.

  However, when the wood preservative contains a copper compound, borate, chromate or other metal compound, the concentration of these metals is kept relatively low. A suitable range is about 1 to 1.5% by weight of the total weight of the composition (ammonium carboxylate of formula (1) and wood preservative). The concentration of the metal compound is kept sufficiently low so as not to interfere with the function of the polar axis of the ammonium cation and carboxylate anion in the ammonium carboxylate of formula (1). Since the purpose is to move the wood preservative into the wood and keep it there, the metal-containing preservative is moved into the wood so that the free ammonium carboxylate is always present and possible metal compounds are It is transferred as an ionized state or as an ammonium carboxylate-metal compound complex.

  In one embodiment of the present invention, the wood is treated from the viewpoint that it is also protected from microorganisms. In this case, the ammonium organic carboxylate of formula (1) can itself act as a wood preservative, the quality and quantity of which are chosen to protect the wood from microorganisms. In aqueous solutions, the weight ratio of the organic ammonium carboxylate of formula (1) to water is in particular in the range from 1:20 to 20: 1, preferably in the range from 1: 6 to 1: 1. In this embodiment, the wood preservative typically contains 5 to 95% by weight of the agent of formula (1), preferably 15 to 45% by weight of the agent of formula (1).

  In view of significantly better absorption into and retention in wood, one aspect of the present invention does not require the environment to contain environmentally harmful copper and / or zinc.

  Some of the above microbicidal organic active ingredients can also be used for other purposes. For example, it can be used against termites (ethylenediaminetetraacetic acid (EDTA)) or as a surfactant (sodium alkylbenzenesulfonate and benzalkonium chloride).

  In one embodiment, the ammonium carboxylate of formula (1) is also used to move other materials into the wood. Exemplary such materials are antioxidants, free radical scavengers, UV protectants described in Granula Ltd's WO 2009/101261 or WO 2009/101262 (WO publication is fully incorporated herein). And wood extracts such as tannins.

  The wood is so adsorbed and absorbed by the wood to be treated over its entire thickness or from the surface to a certain depth by the solution of ammonium carboxylate of formula (1) in combination with the above organic active ingredients. To be processed. Since there are various alternatives, the treatment can be carried out at an appropriate point in the wood processing, for example during the final drying of the wood. The wood treatment solution of the present invention can be heated and / or high temperatures can be used in this process, thereby further improving adsorption and absorption. The present invention allows a convenient procedure for processing wood materials in a cost-effective manner, said procedure comprising one stage of the processing line comprising a continuous process of processing wood products or articles, for example the first process being pressure Using impregnation, the second step is easily incorporated into other common methods, such as spraying, coating or using other surface treatment methods that impregnate wood with an agent or aqueous solution under vacuum. Typical impregnation times are 1-120 minutes and typical processing temperatures are 80-160 ° C. After impregnation, the wood is usually rinsed.

The present invention also relates to a wood preservative composition that provides protection against invertebrates, particularly insects such as ants and termites. The composition contains an ammonium organic carboxylate and an organic active ingredient containing a chelating agent that repels invertebrates. The organic ammonium carboxylate has the following formula:
^{[NR 1 R 2 R 3 R} 4] + n [R 5 (COO) n] -n (1)
Wherein R ¹ , R ² and R ³ are selected from the group comprising hydrogen, substituted alkyl containing 1 to 6 carbon atoms and unsubstituted alkyl containing 1 to 6 carbon atoms; ⁴ is substituted alkyl containing 1 to 6 carbon atoms or unsubstituted alkyl containing 1 to 6 carbon atoms, R ⁵ is hydrogen, substituted hydrocarbyl containing 1 to 6 carbon atoms Or an unsubstituted hydrocarbyl containing 1 to 6 carbon atoms, where n is an integer from 1 to 6. The active ingredient is selected from the group comprising aminopolycarboxylic acids or salts thereof, hydroxy acids or salts thereof, phosphonates or salts thereof or a mixture of chelating agents belonging to two or more of these groups.

  Thus, the wood preservative composition of the present invention contains the same organic ammonium carboxylate of formula (1) and the same active ingredient that repels invertebrates, which are used in the wood preparation method described above. Therefore, the technical special functions described above for ammonium organic carboxylates in combination with active ingredients and these compositions also apply to the wood preservative compositions of the present invention. For this reason, only some important functions of the composition are repeated below.

In the organic ammonium carboxylate of formula (1) of the wood preservative composition, R ⁵ is preferably hydrogen, methyl or ethyl. R ¹ is preferably hydrogen, R ² and R ³ are preferably selected from the group comprising hydrogen and 2-hydroxyethyl, and R ⁴ is preferably 2-hydroxyethyl.

  The active ingredient that repels invertebrates is preferably an insect repellent active ingredient, more advantageously a termite and / or an ant repellent active ingredient. Preferably, the chelating agent binds iron and manganese ions and contains phosphorus (P) in the molecular structure. Typical chelating agents of this type are 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriimine pentamethylenephosphonic acid (DTPMP) or mixtures thereof.

  Accordingly, the ammonium organic carboxylate of formula (1) in the composition is preferably selected from the group comprising a salt of formic acid and monoethanolamine, a salt of propionic acid and monoethanolamine or a mixture of these salts. The weight ratio of the mixture is preferably in the range of 80:20 to 20:80.

  An organoammonium carboxylate of formula (1) is typically a wood preservative composition comprising an ammonium carboxylate of formula (1) and a chelating agent that protects wood from invertebrates, particularly insects such as termites and ants. In the form of an aqueous solution having a concentration of typically 5 to 95% by weight of the whole composition.

  Chelating agent-containing wood preservative solutions for invertebrates preferably have an active ingredient concentration of 0.01 to 95% by weight, more advantageously 0.01 to 45% by weight, and 1 to 50% by weight of carboxylic acid It is in the form of an aqueous solution or dispersion having an ammonium concentration. This type of aqueous wood preservative solution is a surfactant and other types of active ingredients, viscosity modifiers, biocides, colorants, UV protection substances, agents that modify the water repellency of the composition, improve stability Additives including agents can also be included.

  Surfactants are wetting agents that reduce the surface tension of a liquid to allow easy diffusion and reduce the interfacial tension between two liquids. Surfactants can be classified by the presence of formal charged groups in their heads. Nonionic surfactants do not have a charged group at the head. The head of the ionic surfactant has an effective charge. When the charge is negative, the surfactant is referred to as anionic among other things, and when the charge is positive, it is referred to as cationic. If the surfactant contains two oppositely charged groups in the head, it is called zwitterionic.

  Instead of sodium alkylbenzene sulfonate, other surfactants can be used depending on the composition to be prepared. The use of surfactants, i.e. surfactants, further improves the distribution and penetration of the organic ammonium carboxylate of formula (1) and the wood preservative active ingredient, resulting in film-forming resins and fatty acids and / or polysaccharides. Promotes dissolution of the base emulsion, i.e. prevents phase separation in ready-made wood preservatives.

  Some of the commonly encountered surfactants of each type include sulfates such as sodium dodecyl sulfate, ammonium lauryl sulfate, sulfonate or carboxylate anions and sodium laureth sulfate, alkylbenzene sulfonates or fatty acid salts, etc. Anionic based on other alkyl sulfates; Cationic based on quaternary ammonium cations such as cetylpyridinium chloride; Nonionic such as fatty alcohols including alkylpolyglucosides, cetyl alcohol and oleyl alcohol Is included.

  The wood preservative composition of the present invention can also contain one or several microbicides as additives.

  The organic ammonium carboxylate can act alone in the composition, or it can act together with another microbicidal wood preservative compound as a microbicide that additionally protects the wood against microorganisms.

  The microbicidal wood preservative compound preferably comprises a microbicidal active ingredient which is a mixture or reaction product of an organic active ingredient salt and an organic active ingredient acid. The organic active ingredient salt is typically sodium benzoate, sodium alkylbenzene sulfonate, cetylpyridinium chloride, formic acid and ethanolamine salts or mixtures thereof. The organic active ingredient acid is typically benzoic acid, stearic acid, ethylenediaminetetraacetic acid (EDTA) or mixtures thereof.

  It is particularly desirable to describe PHMG as a biocide, and preferably 0.001 to 5% by weight can be added to the wood preservative composition of the present invention to enhance protection against mold. Furthermore, the drying properties of PHMG are very good, speeding up the process. Other polymeric guanidines or polymeric compounds may also be included in the wood preservative composition.

  Paint type resins such as fatty acids and / or polysaccharides can be added to the wood preservative composition of the present invention to further improve the water repellency of the wood material.

  0.005-7% by weight of a surfactant can be added to the wood preservative composition to further improve stability or further promote adsorption and absorption of the wood preservative composition on the wood.

  The present invention also relates to the use of the above composition for preparing wood by impregnating the composition with wood. It has also surprisingly been found that the ammonium carboxylates according to the invention can be used as such or in combination with known anticorrosives which do not corrode wood, cause less corrosion or prevent corrosion. Once prepared, the wood prevents or reduces corrosion of metal bodies such as nails, screws, etc. that come into contact with the wood.

We also have the formula (1):
^{[NR 1 R 2 R 3 R} 4] + n [R 5 (COO) n] -n (1)
Wherein R ¹ , R ² and R ³ are selected from the group comprising hydrogen, substituted alkyl containing 1 to 6 carbon atoms and unsubstituted alkyl containing 1 to 6 carbon atoms; ⁴ is substituted alkyl containing 1 to 6 carbon atoms or unsubstituted alkyl containing 1 to 6 carbon atoms, R ⁵ is hydrogen, substituted hydrocarbyl containing 1 to 6 carbon atoms Or an unsubstituted hydrocarbyl containing 1 to 6 carbon atoms and n is an integer of 1 to 6], and found that it itself has invertebrate repellent properties. Yes. Invertebrates can be, for example, snails, worms or insects. Insects are especially termites.

Depending on the application, the ammonium carboxylate can be in solid form or in solution. Preferably, the ammonium carboxylate of formula (1) is used as a solution for treating wood material. Ammonium carboxylate treated wood material repels invertebrates, especially termites. Preferred structures and properties of ammonium ion [NR ¹ R ² R ³ R ⁴ ] ⁺ _n and acid ion [R ⁵ (COO) _n ] ⁻ⁿ of formula (1) have been extensively discussed above and are therefore It is not intended to be repeated.

  Wood is treated with a solution of ammonium carboxylate of formula (1) so that the solution is adsorbed and absorbed to the wood to be treated throughout its thickness or to a certain depth from the surface. The absorption and adsorption properties of ammonium carboxylate and the general method for preparing ammonium carboxylate solutions have also been extensively discussed above. In the “Examples” section that follows this specification, several established methods of impregnating, spraying and applying wood materials with solutions that are also applicable when using ammonium carboxylate-containing solutions as they are are shown. ing.

  When the ammonium carboxylate of formula (1) is used as a solution, as described above, i.e., depending on the desired molar ratio of ammonium cation source to carboxyl anion source, no medium or suitable medium such as water It is prepared by mixing using an appropriate solvent.

  When the ammonium carboxylate of formula (1) is used as a solid, preferably the ammonium component present in formula (1) mixed with an appropriate molar amount of the salt of the acid component present in formula (1). A mixture of salts with an appropriate molar ratio with the salt.

  The invertebrate repellent properties of the ammonium carboxylate of formula (1) can be enhanced using a mixture of a liquid or water soluble organic ammonium carboxylate and an active ingredient containing the chelating agent.

  In some cases, the ammonium carboxylate of formula (1) can be used to repel small vertebrates such as mice and rats, birds, and other pests.

Examples A number of examples are given below solely for the purpose of clarifying the invention.

Compositions A typical aqueous solution for termite protection of food is 0.01 to 10% by weight of said wood preservative solution (eg HEDP based on phosphonate) and ammonium carboxylate of formula (1) and 1 to Contains 45% by weight of a chelating agent-containing wood preservative component, the balance being substantially water, additives and surfactants.

  A typical aqueous solution for fire protection (and termite protection) is 5 to 35% by weight of the wood preservative solution (eg HEDP based on phosphonate) and ammonium carboxylate of formula (1) and 1 to 30% by weight. % Of a chelating agent-containing wood preservative component, with the balance being essentially water, additives and surfactants.

  Preferably, the chelating agent of the present invention is a chelating agent capable of binding iron and manganese ions and containing phosphorus (P) in the molecular structure such as HEDP.

Examples of wood protection compositions for insects, especially termites and ants.
Composition 1
Composition 1 is primarily directed to repellents against insects, especially termites.
30 wt% monoethanolammonium formate (43 wt% formic acid and 57 wt% monoethanolamine)
8.33 wt% Cublen KT600 (60 wt% HEDP)
0.5 wt% PHMG20 (20 wt% PHMG)
1% by weight of ionic surfactant, balance is water

  The composition of Example 1 is well adsorbed and absorbed by the wood and has excellent immobilization within the wood material.

Examples of compositions that protect wood from fire and are also useful against insects, especially against termites and ants Composition 2
Composition 2 is primarily intended to protect wood from fire, but also has repellent properties against insects such as termites.
10 wt% monoethanolammonium formate (43 wt% formic acid and 57 wt% monoethanolamine)
49.2 wt% Cublen KT600 (29.5 wt% HEDP)
20.6% by weight ammonia water (24.5% by weight), ie ammonia (100%)
3.6% by weight of ionic surfactant, the balance being water

The compound of Example 2 was applied to the surface of a spruce or hippo plywood. The composition was well absorbed by the wood at about 250 g / m ² when applied once. The treated wood material showed excellent fire protection properties in tests according to standard EN5660.

The composition of Example 2 is well adsorbed and absorbed by the wood and has excellent immobilization within the wood material.
Compositions 1 and 2 can be used to impregnate, apply or spray wood as described below.

  Depending on the particular application and wood treatment method, the composition of the invention can be modified very greatly in terms of ammonium carboxylate and chelating agent content compared to those prepared in Example 1 or 2. For example, if the composition of Example 2 is used and wood is impregnated with this composition, it may be possible to reduce the amount of chelating agent to about 1/20 of the concentration shown in Example 1 or 2.

  Other chelating agents such as 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP) used in compositions 1 and 2, ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriimine pentamethylenephosphonic acid (DTPMP) It can be replaced with a phosphorus-containing chelating agent.

  The following are exemplary microbicidal active ingredients that can also be used in compositions and solutions containing such chelating agents that repel invertebrates. Ammonium carboxylate carriers described with respect to these microbicidal active ingredients can also be used in preparing the above chelating agents that repel invertebrates.

Research Objectives of Microbicides A study is conducted to determine the microbicidal efficacy of a system that combines an ammonium carboxylate carrier with the active ingredients of the present invention against microorganisms that damage wood (molds, blue mold and decaying fungi).

1. Materials and Methods 1.1 Ammonium carboxylate carrier Two ammonium carboxylate carrier mixtures were selected for testing, and water-soluble mixtures were selected as shown in the accompanying table (Table 1). White spirit solvent was additionally used as a reference carrier.

2.2 Active ingredients and mixtures thereof The active ingredients studied consist of commercial and fresh solutions presented in the middle column of the following tables (2 and 3). The right column of the table corresponds to the ammonium carboxylate solution used in Table 1.

2.3 Wood Material Extraction Test Oven dried pine surface samples (15 × 15 × 5 mm) were extracted by five different extraction procedures (Procedures 1-5). A raw (unextracted) wood sample was used as a reference material for the extracted wood material.

Extraction Procedure 1, Water Extraction Wood samples were impregnated with water (vacuum impregnation) before extraction. The water-impregnated sample was extracted by autoclave at a temperature of 121 ° C. for 20 minutes.

Extraction procedure 2, MHEA1
Wood samples were impregnated with 50% MHEA support (vacuum impregnation), and the impregnated samples were extracted by autoclave at a temperature of 121 ° C. for 20 minutes. The sample was then rinsed with cold water until the rinse water became clear (at least 3-4 rinses, one rinse with water = overnight in water under pressure).

Extraction procedure 3, MHEA2
Wood samples were impregnated with 50% MHEA support (vacuum impregnation), and the impregnated samples were extracted by autoclave at a temperature of 121 ° C. for 20 minutes. The sample was then rinsed with cold water overnight under pressure (one rinse).

Extraction Procedure 4, Solvent Extraction Wood samples were extracted with acetone in a Soxhlet apparatus for 4 hours. After this, the sample was further extracted with distilled water for 4 hours in a Soxhlet apparatus. The sample was not dried between extractions.

Extraction Procedure 5, Solvent-MHEA Extraction Wood samples were extracted with acetone in a Soxhlet apparatus for 4 hours. The sample was then further extracted with distilled water for 4 hours in a Soxhlet apparatus. The sample was not dried between extractions. After water extraction, the sample was air dried and impregnated with 50% MHEA support (vacuum impregnation). After impregnation, the sample was rinsed with water overnight under pressure.

2.4. Biological effects of the active ingredient and ancat mixture and extracted wood 2.4.1 Rot test Small pine surface samples (15 mm x 15 mm x 5 mm) were vacuum impregnated with the active ingredient carrier mixture of the study (Table 2). Untreated samples and samples treated with simply ancat carrier or white spirit solvent were used as standards. Brown rot fungi, Coniophoraputeana , BAM Ebw were selected as test fungi. The fungal strain is from the VTT Technical Research Center of Finland, Building, Built Environment.

The amount of active ingredient-carrier mixture absorbed (retained kg / m ³ ) absorbed in the sample was determined by means of calculation and weighing based on drying (dry weight of sample before and after impregnation and rinsing). Part of the sample was rinsed with water before starting the rot test. Rinsing was performed by impregnating the specimen with water and rinsing the sample in water for 4 days. The rinse water was changed four times during the rinse operation. Rinsing was performed according to a modified EN84 standard. The amount of active ingredient-carrier absorbed in the sample was also determined after rinsing.

  The spoilage test was performed according to the EN113 standard, which was quickly modified. The reference sample, as well as the unrinsed and rinsed test samples, were rotted for 5 weeks. The effect of the impregnation treatment was determined based on the weight loss caused by the fungus.

2.4.2 Mold and Blue Discoloration Test In the mold and blue discoloration test, a pine surface wood sample (25 × 50 × 5 mm) was vacuum impregnated with a mixture of active ingredient and carrier (Table 3). The sample was not rinsed.

  The mixture of active ingredient and carrier, and the antifungal and anti-blue blight effects of these standards were examined in the laboratory by the suspension method. Test samples and reference samples were suspended in random order in the exposure chamber. The relative humidity of the chamber was adjusted with water in the range of 95-100% at 20 ° C. (+/− 2 ° C.) of the test temperature.

Blue discoloration and mold fungal suspensions were injected into the test box prior to the start of the test. Mold suspensions consist of three mold species that grow in wood: Aspergillus versicolor (E1), Gladosporium sphaerospermum (R7) and Penicillium sp. (Penicillium sp.). 1017). The blue discoloration disease suspension was made up of the following species: Aureobasidium pullulans (T1), Sclerophoma enteroxylina (Z17), and Ceratocystislifera (Zerato) composition (11). The fungal strain is from the VTT Technical Research Center of Finland, Building, Built Environment. Molding of the test samples was monitored visually on a 0-5 scale at 2, 4, 6, 8 and 10 weeks from the start of the test.
0 = No growth s1 = Trace of growth start (observation with a microscope)
2 = 1-10% area covered by microbial growth (microscopic observation)
3 = 10-30% area is covered with microbial growth (visual observation)
4 = 30-70% area is covered with microbial growth (visual observation)
5 = 100% area covered with microbial growth (visual observation)

3. Results 3.1 Anti-rot effect and extraction procedure of active ingredient and carrier mixture Idambo (C. puteana) is a brown rot fungus that causes weight loss of wood material and reduces strength. The metabolism of brown rot fungi utilizes the components of the wood's hydrocarbon structure (hemicellulose and cellulose) and also changes the lignin structure. When brown rot progresses for a long time, only fragile lignin remains, and even light pressure breaks down into dust.

  The results of the rot test are illustrated in FIGS. The results show that all of the tested active ingredient and carrier mixtures and the ancat carrier are not sooted in the accelerated spoilage test. Indicates that only the corruption caused by Puteana was prevented. In all cases, the weight loss of the samples was less than the weight loss of the preservative limit set by the EN113 standard (≦ 3%).

  A weight loss of less than 3% was achieved in the rinse samples when the preservative contained Tebuconazole-MHEA, Tebuconazole-MHEA + PREA, CEBE2-MHEA, CEOS-MHEA or BHTEB-MHEA. A weight loss limit of approximately 3% was achieved with rinse samples containing benzoic acid-MHEA + PREA (4.2% weight loss) or the acidic form of EDTA-MHEA + PREA (5.2% weight loss). Rinsing clearly reduced the anti-corruption effect of benzoic acid-MHEA (7.3% weight loss) and the acidic form of EDTA-MHEA (12.7% weight loss).

  In the absence of soot, both ancat carriers efficiently prevented weight loss caused by decaying fungi in the test samples. The effect of MHEA + PREA decreased after rinsing and a 9% weight loss was noted in the test sample. White spirit did not prevent weight loss caused by rotting fungi. In contrast, a mixture of SBBW30 and white spirit proved to have a high anti-corrosion effect both in the absence of rinse and in the rinse.

  The purpose of the extraction test was to determine, for example, whether removal of soluble sugars or structural components in the carrier increases the rot resistance of the wood. The ancat support proved to extract hydrocarbons, especially hemicellulose xylan, from wood material (see results of extraction test). The results of the rot test show that water extraction (extraction procedure 1), MHEA1 (extraction procedure 2) and solvent extraction (extraction procedure 4) did not increase the rot resistance of the extracted wood material (weight loss> 30%). Indicated. In contrast, in samples treated with extraction procedures 3 (MHEA2) and 5 (solvent-MHEA extraction), the weight loss caused by the rot fungus was below the 3% limit defined by the standard.

FIG. Effect of extraction procedure on anti-corrosion properties of wood materials.
Table 4 shows the content of active ingredient-support absorbed in the sample during impregnation. The content was relatively high and varied in the range of 190-240 kg / m ³ . Rinsing had no significant effect on absorption.

3.2 Anti-fungal and anti-blue discoloration effect of active ingredient / carrier mixture and extraction procedure Blue discoloration fungus penetrates the structure of the wood material and causes discoloration by staining the material. The moisture behavior of the material (the material has a higher moisture absorption). The metabolism of blue-rotting fungi primarily utilizes soluble nutrients and usually does not result in wood weight loss or strength reduction. In contrast, fungi grow only on the surface of wood material. Mold does not penetrate into the material structure and therefore does not cause weight loss or strength reduction. Molds survive by soluble nutrients present on the material surface. The damage caused by mold relates to discoloration and odor and possible health hazards.

  The blue discoloration test did not produce any results. No blue discoloration was observed in the treated or untreated samples during the 10 week exposure period. In the case of an untreated standard, this zero result may also be due in part to excess moisture in the sample caused by the hygroscopic nature of the active ingredient and carrier mixture, the susceptibility of the blue mold to the test compound, and / or the carrier. It can also be attributed to the transfer of the active ingredient to the untreated reference sample due to its high mobility.

  The results of the mildew test are shown in FIGS. A corresponding example is shown in Table 3. Mold growth is determined by mixing samples of the following active ingredients and carriers: benzoic acid-MHEA- (Example 18), benzoic acid-MHEA + PREA (Example 19), acidic form EDTA-MHEA (Example 20), acidic form EDTA- When treated with MHEA-PREA (Example 21), SBB-MHEA (Example 22), CEBE2-MHEA (Example 23) and BEPRE100-MHEA (Example 26), and SBBW30-White Spirit, completely in the 10-week exposure study Prevented. In the untreated control sample and the test sample treated with white spirit, mold generation reached a mold index of 5 after 6 weeks of exposure (100% of the sample surface was covered by mold growth). Moderate mold growth was observed in two samples treated with ancat carrier. The mold index reached a value of 2 upon exposure (mold growth was still not visible). Moderate mold growth (mold index 2) was also observed in test samples treated with the active ingredient mixture of CEBE2-MHEA (Example 23) and CEOS-MHEA (Example 24).

  The purpose of the extraction test was to determine, for example, whether removal of soluble sugars or structural components in the carrier increases the mold resistance of the wood. The mold test results showed that water extraction (extraction procedure 1), MHEA2 (extraction procedure 3) and solvent extraction (extraction procedure 4) did not increase the mold resistance of the extracted wood material, and the mold index In some cases it differs from 3-5 (visible to abundant growth). In contrast, mold generation was moderate (less than 1 mold index) in samples treated with extraction procedures 2 and 5 (MHEAI and solvent-MHEA extraction).

4). Conclusions of the microbicidal study It was observed whether the mixture of active ingredient and carrier had a specific preventive ability with respect to both spoilage and mold formation. The spoilage test shows the anti-corruption effect of MH / EA and MH / EA + PR / EA carriers and active ingredients mixed with them (benzoic acid, acidic form of EDTA, Tebuconazole, CEBE2, BHTEB, BEPRE, 100-MHEA, CEOS). Were determined. The spoilage test also determined the effect of SBB dissolved in white spirit solvent. Wood samples extracted with five different extraction procedures were also included in this decay test.

  The mixture of active ingredient and carrier is a C.I. It effectively prevented corruption caused by Puteana. The test results showed that the mixture of active ingredient and carrier efficiently prevented weight loss caused by decaying fungi in the treated wood sample even after rinsing. The most efficient active ingredient mixture with the highest anti-rot ability occurred in the formulation produced by Granula Oy.

  Next, the mold and blueprint disease test consists of MH / EA and MH / EA + PR / EA carriers and active ingredients mixed with these carriers (benzoic acid, EDTA, IBPC, SBB, CEBE2, CEOS, BHTEB, acidic form BEPRE100 -The antifungal and anti-blue blight effects of SBB dissolved in MHEA) and white spirit solvent were determined. The test results showed that the active ingredient and carrier mixture actively prevented mold growth on the surface of the treated wood samples during the 10 week exposure test. Blue discoloration was not observed. This result indicates that the active ingredient is transferred to an untreated reference sample due to excess moisture in the sample caused by the hygroscopic nature of the active ingredient and carrier mixture, the susceptibility of blue mold to test compounds, and / or the high mobility of the carrier. It can also be attributed to.

  The effect of wood material solubility and structural component extraction on spoilage and mold formation was determined by treating the wood material with five different extraction procedures. Water and solvent extraction had no effect on the rotting and mold resistance of the wood material. C. The spoilage caused by puteana was suppressed when the wood sample contained a carrier after extraction.

  In the following, the examples describe how the composition of the invention can be used in the treatment of wood and how the treatment of wood can be incorporated into the wood processing line of a wood processing sawmill. The method is shown.

1) Pressure impregnation The traditional method of putting a large amount of impregnation material into wood, thereby resulting in the most effective treatment by different steps (negative and overpressure, high temperature). This method gives the best penetration of the composition and allows the wood to be impregnated, usually up to the core. The composition of the present invention has very good permeability and can reduce the negative / overpressure used for conventional CCA impregnation, thereby improving the cost effectiveness of this method It is possible. Also, wood of a closer grain type, such as spruce, could be pressure impregnated with the composition of the present invention, which was not possible with previously used materials.

2) Immersion impregnation The composition of the present invention has good permeability, and in some cases, simple immersion impregnation is possible. This method is simple but requires a separate dip container and is performed in a batch process similar to pressure impregnation.

3) Spraying The composition of the invention can be sprayed onto the surface of wood, for example when a sawn timber is planned. In this way, preservation against microorganisms can be achieved during storage and delivery before subsequent surface treatment (such as application).

4) Coating or other surface treatment line The composition of the present invention can also be added to wood in connection with a coating or other surface treatment line. From the paint dosing tank, the wood board can be impregnated via a separate application unit with the solution under over or under pressure. Depending on the pressure and speed of the line, relatively good permeability and thus reasonable weathering and fire resistance can be achieved with this method.

5) Drying of wood and control of the final moisture content In the processing of lumber timber, the final moisture content of the wood prevents cracking and shape change and prevents the substrate from becoming too good for the production of organisms. It is becoming increasingly important to be suitable for. With respect to drying, wood is often dried to a lower moisture content than desired. Finally, the water content can be adjusted by techniques based on, for example, water spraying. In this step, it is very easy to add the composition of the present invention to wood, and it is possible to eliminate cracks and shape changes due to drying of the wood. Furthermore, this method can be used to improve fire resistance and to provide at least a short term preservative for microorganisms.

  However, for processing methods 1 to 4, it is important that the wood is sufficiently dried (eg, at a temperature of 40 to 80 ° C.) to remove excess moisture absorbed by the wood during the method. And the water content can be stabilized to the desired final level.

  The processing of frozen wood (eg melting, impregnation, design, application, etc.) is problematic and constitutes an additional expense, so the solution of the present invention can facilitate the treatment of wood under winter weather conditions It is.

  Usually, the ammonium carboxylate of the above formula (1) is absorbed by the wood by impregnating the wood with this active substance or its aqueous solution under vacuum. Typical impregnation times are 1-120 minutes and typical processing temperatures are 80-160 ° C. After impregnation, the wood is usually rinsed.

Claims (63)

A method of treating wood, wherein the wood is contacted with a mixture of a liquid or water-soluble ammonium organic carboxylate and an active ingredient that repels invertebrates, the organic ammonium carboxylate having the following formula (1): And the wood preservative active ingredient contains a chelating agent that repels invertebrates, and the chelating agent is an aminopolycarboxylic acid or a salt thereof, a hydroxy acid or a salt thereof, a phosphonate or a salt thereof, or two or more of these groups. The above process characterized in that it is selected from the group comprising a mixture of chelating agents belonging to:
^{[NR 1 R 2 R 3 R} 4] + n [R 5 (COO) n] -n (1)
Wherein R ¹ , R ² and R ³ are selected from the group comprising hydrogen, substituted alkyl containing 1 to 6 carbon atoms and unsubstituted alkyl, and R ⁴ represents 1 to 6 carbon atoms. Is substituted alkyl or unsubstituted alkyl, R ⁵ is hydrogen, a substituted or unsubstituted hydrocarbon containing 1-6 carbon atoms, and n is an integer of 1-6.   The process according to claim 1, characterized in that the active ingredient containing a chelating agent is a mixture or reaction product of an organic active ingredient salt and an organic active ingredient acid.   Chelating agents are ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), n-hydroxyethyl-ethylenediainine triacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediamine-di-o-hydroxyphenylacetic acid (EDDHDA) ), Diethanolglycine (DEG), ethanoldiglycine (EDG) or a salt thereof, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriimine pentamethylenephosphonic acid (DTPMP) ) Or a salt thereof, or a group comprising a mixture thereof.   The chelating agent is a phosphorus-containing chelating agent such as 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriiminepentamethylenephosphonic acid (DTPMP) or a salt thereof, or a mixture thereof. The method according to claim 3, wherein: R ⁵ is hydrogen, substituted alkyl or unsubstituted alkyl containing 1 to 6 carbon atoms, and wherein n is 1 or 2, Process according to claim 1. R ⁵ is a substituted alkyl or unsubstituted alkyl containing 1 to 4 carbon atoms, and wherein n is 1, The method of claim 5. R ⁵ is hydrogen, characterized in that it is a methyl or ethyl A process according to claim 5. R ¹ is hydrogen, R ² and R ³ are selected from the group comprising C ₁ -C ₆ alkyl substituted with hydrogen and hydroxyl groups, and R ⁴ is C ₁ -substituted with hydroxyl groups characterized in that it is a C ₆ alkyl, the method of claim 1. R ¹ is hydrogen, R ² and R ^3, are groups or al selection including ethyl substituted with hydrogen and hydroxy groups, the R ⁴ is ethyl Le substituted with a hydroxyl group 9. A method according to claim 8, characterized in that R ¹ Is hydrogen and R ² And R ³ Is selected from the group comprising hydrogen and 2-hydroxyethyl, R ⁴ The method according to claim 8, characterized in that is 2-hydroxyethyl.   The process according to claim 1, characterized in that the ammonium organic carboxylate of formula (1) is a salt of formic acid and monoethanolamine or a salt of propionic acid and monoethanolamine.   The process according to claim 1, characterized in that the organic carboxylate of formula (1) is a mixture of a salt of formic acid and monoethanolamine and a salt of propionic acid and monoethanolamine.   2. A method according to claim 1, characterized in that the wood is treated by impregnation, spraying or coating with a liquid or water-soluble ammonium organic carboxylate and any active ingredients. 14. A method according to claim 13 , characterized in that the wood is dried before being treated with the method according to claim 13 . A wood preservative composition comprising an organic ammonium carboxylate and an organic active ingredient that repels invertebrates, wherein the organic ammonium carboxylate has the following formula (1), and the composition is an invertebrate active component containing a chelating agent allowed to repel the a containing the active ingredient, aminopolycarboxylic acid or a salt thereof, hydroxy acid or a salt thereof, a phosphonate or a mixture of its salt or more than one belonging chelating agents of this group Wherein said wood preservative composition is selected from the group comprising:
^{[NR 1 R 2 R 3 R} 4] + n [R 5 (COO) n] -n (1)
Wherein R ¹ , R ² and R ³ are selected from the group comprising hydrogen, substituted alkyl containing 1 to 6 carbon atoms and unsubstituted alkyl, and R ⁴ represents 1 to 6 carbon atoms. Is substituted alkyl or unsubstituted alkyl, R ⁵ is hydrogen, a substituted or unsubstituted hydrocarbon containing 1-6 carbon atoms, and n is an integer of 1-6. 16. The composition according to claim 15 , wherein the active ingredient containing a chelating agent is a mixture or reaction product of an organic active ingredient salt and an organic active ingredient acid. Chelating agents are ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), n-hydroxyethyl-ethylenediainine triacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediamine-di-o-hydroxyphenylacetic acid (EDDHDA) ), Diethanolglycine (DEG), ethanoldiglycine (EDG) or a salt thereof, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriimine pentamethylenephosphonic acid (DTPMP) The composition according to claim 16 , characterized in that it is selected from the group comprising) or a salt thereof or a mixture thereof. The chelating agent is a phosphorus-containing chelating agent such as 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriiminepentamethylenephosphonic acid (DTPMP) or a salt thereof, or a mixture thereof. The composition according to claim 15 , wherein 16. A composition according to claim 15 , characterized in that the chelating agent repels insects such as termites or ants. R ⁵ is hydrogen, substituted alkyl or unsubstituted alkyl containing 1 to 6 carbon atoms, n, characterized in that it is 1 or 2 A composition according to claim 15. R ⁵ 16. The composition according to claim 15, wherein is hydrogen, substituted alkyl or unsubstituted alkyl containing 1 to 4 carbon atoms, and n is 1. R ⁵ is hydrogen, characterized in that it is a methyl or ethyl, A composition according to claim 20. R ¹ is hydrogen, ^{R 2} and ^{R 3,} are groups or we choose comprising _C 1 -C ₆ alkyl substituted with hydrogen and hydroxy groups, _{C 1} ^{to R 4} is substituted with a hydroxyl group characterized in that ~C is ₆ alkyl Le a composition according to claim 15. R ¹ Is hydrogen and R ² And R ³ Are substituted with hydrogen and hydroxyl groups ₁ ~ C ₄ Selected from the group comprising alkyl, R ⁴ Is substituted with a hydroxyl group ₁ ~ C ₄ 16. Composition according to claim 15, characterized in that it is alkyl. R ¹ is hydrogen, R ² and R ^3, are groups or al selection including ethyl substituted with hydrogen and hydroxy groups, the R ⁴ is ethyl Le substituted with a hydroxyl group 24. The composition of claim 23, characterized. R ¹ Is hydrogen and R ² And R ³ Is selected from the group comprising hydrogen and 2-hydroxyethyl, R ⁴ The composition according to claim 23, characterized in that is 2-hydroxyethyl. 16. Composition according to claim 15 , characterized in that the ammonium organic carboxylate of the formula (1) is a salt of formic acid and monoethanolamine or a salt of propionic acid and monoethanolamine or a mixture thereof. Chelating agent intended for termites is in the form of an aqueous solution or dispersion having an active ingredient concentration of 0.01 to 95 % by weight and an ammonium carboxylate concentration of 1 to 50% by weight. Item 16. The composition according to Item 15 . Chelating agent intended for termites is in the form of an aqueous solution or dispersion having an active ingredient concentration of 0.01 to 45% by weight and an ammonium carboxylate concentration of 1 to 50% by weight. Item 16. The composition according to Item 15. It contains 0.01 to 10% by weight of a chelating agent based on phosphorus, 1 to 45% by weight of ammonium carboxylate of formula (1), and the balance is substantially water, additives and surfactants. 29. The composition of claim 28 for protecting wood from termites. 5 to 35% by weight of chelating agent based on phosphorus, 1 to 30% by weight of ammonium carboxylate of formula (1), the balance being substantially water, additives and surfactants 31. The composition of claim 30 , for protecting wood from fire. 29. Composition according to claim 28 , characterized in that the wood preservative solution also contains additives comprising other types of active ingredients besides surfactants and / or invertebrate repellent active ingredients. The composition according to claim 32 , characterized in that the wood preservative solution contains a microbicidal active ingredient as an additive. The composition according to claim 33 , characterized in that the microbicidal active ingredient is a mixture or reaction product of an organic active ingredient salt and an organic active ingredient acid. Organic active ingredient salt selected from the group comprising alkali metal, alkaline earth metal and ammonium salts of aromatic acids, alkali metal, alkaline earth metal and ammonium salts of aliphatic and aromatic sulfonic acids, and amine acid salts 35. The composition of claim 34 , wherein: 36. Composition according to claim 35 , characterized in that the organic active ingredient salt is selected from the group comprising sodium benzoate, sodium alkylbenzenesulfonate, cetylpyridinium chloride and a salt of formic acid and ethanolamine. Microbicidal active ingredient is acidic copper chromate, ammoniacal copper zinc arsenate, chromium-containing copper arsenate, ammoniacal copper quaternary salt, copper bis (dimethyldithiocarbamate), ammoniacal copper citrate, copper azole A or 34. Composition according to claim 33 , characterized in that it is a borate compound. 0 . 38. Composition according to claim 37 , characterized in that it contains from 01 to 1.5% by weight of a microbicide. 34. Composition according to claim 33 , characterized in that the microbicidal active ingredient is botulin, benzalkonium chloride (alkylbenzyldimethylammonium chlorides of various alkyl chain lengths) or polyhexamethyleneguanidine (PHMG). Sulfates such as sodium alkylbenzene sulfonate, sodium dodecyl sulfate, ammonium lauryl sulfate, sulfonate or carboxylate-containing surfactants, anionic surfactants such as alkyl sulfates such as sodium laureth sulfate, alkylbenzene sulfonate or fatty acid salts Agents; cationic surfactants based on quaternary ammonium cations such as cetylpyridinium chloride; an interface selected from the group consisting of nonionic surfactants such as fatty alcohols including alkylpolyglucosides, cetyl alcohol and oleyl alcohol 40. Composition according to claim 39 , characterized in that it also contains an active agent. Viscosity Doaratame modifiers, antioxidants, free radical scavengers, characterized by containing also other additives selected from the group comprising UV protection agents or wood extract composition of claim 39 . A composition for an invertebrate comprising an organic ammonium carboxylate and an invertebrate repellent organic active ingredient, wherein the organic ammonium carboxylate has the following formula (1), and the composition is an invertebrate: active component containing a chelating agent allowed to repel the a containing the active ingredient, aminopolycarboxylic acid or a salt thereof, hydroxy acid or a salt thereof, a phosphonate or a mixture of its salt or more than one belonging chelating agents of this group Wherein the composition is selected from the group comprising:
^{[NR 1 R 2 R 3 R} 4] + n [R 5 (COO) n] -n (1)
Wherein R ¹ , R ² and R ³ are selected from the group comprising hydrogen, substituted alkyl containing 1 to 6 carbon atoms and unsubstituted alkyl, and R ⁴ represents 1 to 6 carbon atoms. Is substituted alkyl or unsubstituted alkyl, R ⁵ is hydrogen, a substituted or unsubstituted hydrocarbon containing 1-6 carbon atoms, and n is an integer of 1-6. Chelating agents are ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), n-hydroxyethyl-ethylenediainine triacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediamine-di-o-hydroxyphenylacetic acid (EDDHDA) ), Diethanolglycine (DEG), ethanoldiglycine (EDG) or a salt thereof, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriimine pentamethylenephosphonic acid (DTPMP) 43) The composition according to claim 42 , characterized in that it is selected from the group comprising) or a salt thereof or a mixture thereof. The chelating agent is a phosphorus-containing chelating agent such as 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriiminepentamethylenephosphonic acid (DTPMP) or a salt thereof, or a mixture thereof. 44. The composition of claim 43 , wherein: R ⁵ is hydrogen, substituted alkyl or unsubstituted alkyl containing 1 to 6 carbon atoms, n is 1 or characterized in that it is a 2, The composition of claim 42. R ⁵ 43. The composition of claim 42, wherein is hydrogen, substituted alkyl or unsubstituted alkyl containing 1 to 4 carbon atoms, and n is 1. R ⁵ is hydrogen, characterized in that it is a methyl or ethyl, A composition according to claim 45. R ¹ is hydrogen, R ² and R ^3, are groups or al selection comprising C ₁ -C ₆ alkyl substituted with hydrogen and hydroxyl groups, R ⁴ is substituted with a hydroxyl group C characterized in that ₁ -C ₆ is alkyl Le a composition according to claim 47. R ¹ Is hydrogen and R ² And R ³ Is substituted with hydrogen and 2-hydroxyethyl ₁ ~ C ₄ Selected from the group comprising alkyl, R ⁴ Is substituted with a hydroxyl group ₁ ~ C ₄ 48. Composition according to claim 47, characterized in that it is alkyl. R ¹ is hydrogen, R ² and R ^3, are groups or al selection including ethyl substituted with hydrogen and hydroxy groups, the R ⁴ is ethyl Le substituted with a hydroxyl group 49. The composition of claim 48 , characterized. R ¹ Is hydrogen and R ² And R ³ Are selected from the group comprising hydrogen and ethyl substituted with 2-hydroxyethyl; ⁴ 49. The composition according to claim 48, wherein is 2-hydroxyethyl. Interfacial active agent, as well as microbicides, antioxidants, free radical scavengers, characterized by containing also additives selected from the group comprising UV protection agents or wood extract according to claim 42 Composition. How the repelling of invertebrates, with an organic carboxylic acid ammonium of the formula (1), allowed to repel invertebrates:
^{[NR 1 R 2 R 3 R} 4] + n [R 5 (COO) n] -n (1)
Wherein R ¹ , R ² and R ³ are selected from the group comprising hydrogen, substituted alkyl containing 1 to 6 carbon atoms and unsubstituted alkyl, and R ⁴ represents 1 to 6 carbon atoms. Is substituted alkyl or unsubstituted alkyl, R ⁵ is hydrogen, a substituted or unsubstituted hydrocarbon containing 1-6 carbon atoms, and n is an integer of 1-6. R ⁵ is hydrogen, substituted alkyl or unsubstituted alkyl containing 1 to 6 carbon atoms, and wherein n is 1 or 2, The method of claim 53. R ⁵ is a substituted alkyl or unsubstituted alkyl containing 1 to 4 carbon atoms, and wherein n is 1, The method of claim 54. R ⁵ is hydrogen, characterized in that it is a methyl or ethyl A process according to claim 53. R ¹ is hydrogen, R ² and R ³ are selected from the group comprising C ₁ -C ₆ alkyl substituted with hydrogen and hydroxyl groups, and R ⁴ is C ₁ -substituted with hydroxyl groups characterized in that it is a C ₆ alkyl, the method of claim 53. R ¹ is hydrogen, R ² and R ^3, are groups or al selection including ethyl substituted with hydrogen and hydroxy groups, the R ⁴ is ethyl Le substituted with a hydroxyl group 58. A method according to claim 57 , characterized. R ¹ Is hydrogen and R ² And R ³ Is selected from the group comprising hydrogen and 2-hydroxyethyl, R ⁴ 58. The method according to claim 57, characterized in that is 2-hydroxyethyl. 54. The process according to claim 53 , characterized in that the ammonium organic carboxylate of formula (1) is a salt of formic acid and monoethanolamine or a salt of propionic acid and monoethanolamine. 54. Process according to claim 53 , characterized in that the ammonium organic carboxylate of formula (1) is a mixture of a salt of formic acid and monoethanolamine and a salt of propionic acid and monoethanolamine. Insects are subjected to an organic ammonium carboxylate of formula (1) impregnated in the wood by contacting the wood with a liquid of formula (1) or a mixture of water-soluble ammonium organic carboxylates. 54. The method according to item 53 . 64. The method of claim 62 , wherein the invertebrate is an insect such as a termite.