FI20185752A1 - A method for providing wood with a flame retardant and the flame retardant composition - Google Patents

Abstract

The invention relate to use of the composition comprising liquid or water-soluble organic ammonium carboxylate in combination with an active ingredient acid or a liquid or water soluble ammonium in combination with an active ingredient acid, wherein the active ingredient acid is based on a chelating agent, which contains phosphorus (P) in its molecular structure; as a flame retardant in a wood.

Description

A method for providing wood with a flame retardant and the flame retardant composition

The invention relates to the use of the composition comprising a liquid or water5 soluble organic ammonium ion and an active ingredient acid comprising phosphorus based material, as a flame retardant in a wood.

The invention relates also to a method for preparing a flame retardant composition comprising ammonium ion and an active ingredient comprising phosphor based material having flame retardant properties in wood.

In the JP-patent application 2010-240968 it has been presented a wood preservative composition which is based on ammonium carboxylate and active ingredient agent having properties as a flame retardant. However, depending on the concentration of the active ingredient and the exact formulation of the ammonium carboxylate, it has now perceived, that the active ingredient agent has a tendency to crys15 tallize out from the liquid. There is also problem of excessive foaming specifically when the concentration of the active ingredient agent is high.

The purpose of the invention is thus to provide a method and a composition for treating wood, which composition stays as a homogenous solution or dispersion even in a case of presence elevated concentrations of active ingredient having flame 20 retardant properties in wood. This composition should be well absorbed in wood and has good flame retention properties when absorbed or adsorbed therein.

The objectives mentioned above have now been achieved by using liquid or watersoluble organic ammonium carboxylate in combination with an active ingredient having flame retarding properties.

The organic ammonium carboxylate has the formula (1a) or (1 b):

[NH₃CH₂CH₂(OH)]⁺n [R⁵(COO)n] ⁿ (1a) or [N(CH₃)₃(CH₂CH₂(OH))]⁺n [R⁵(COO)_n]-ⁿ (1 b) in which R⁵ is hydrogen, a substituted hydrocarbyl having 1-6 carbon atoms or an unsubstituted hydrocarbyl having 1-6 carbon atoms, and n is an integer between

1-6. Preferable n is 1.

20185752 prh 10 -09- 2018

Such an ammonium carboxylate is readily absorbed in very large amounts into wood and is subsequently retained in the wood. Group R⁵ in formula (1) is preferably hydrogen. The terms substituted and unsubstituted refer basically to groups containing heteroatoms (e.g. -OH, -NH2, -COOH). The chelating agent means a chelat5 ing agent that contain phosphorus (P) in the molecular structure, with a method for treating wood

The mixture of active ingredient and the above mentioned ammonium carboxylate (1a) or (1b), where ammonium ion is based on choline or ethanolamine (that is, is cholineaminium or ethanolaminium) cation, is a homogenous solution or dispersion 10 preferable a homogenous aqueous liquid. The active ingredient contains a chelating agent that has flame retarding properties. Chelation is the formation or presence of two or more separate bindings between a polydentate (multiple bonded) 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 15 chemicals that form soluble, complex molecules with certain metal ions, inactivating the ions so that they cannot normally react with other elements or ions to produce precipitates or scale.

The chelating agent according to the invention is a chelating agent being able to 20 bind iron and manganese ions and that contain phosphorus (P) in the molecular structure. The chelating agent is selected from the group comprising phosphonates (i.e. organic phosphonate i.e. organophosphate) preferable HEDP (etidrone acid based bisphosphonates) or a mixture of chelating agents which belong to two of more groups of phosphonates: 1 -hydroxyethylidene, 1,1 -diphosphonic acid (HEDP), 25 ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenethaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof.

The chelating agent can be used in combination with ammonium carboxylate of formula (1a) or (1b) in high concentrations without any precipitate occurring. The concentration of HEDP can be for example up to 40 % w/w in liquid composition com30 prising said ammonium carboxylate with formula (1a) or (1b) and an active ingredient (HEDP).

Additionally it has now been found, that instead of mixing ammonium carboxylate of formula (1a) or (1b) with an active ingredient which is based on above mentioned active ingredient comprising chelating agent, which contains phosphorous in its mo35 lecular structure, one can use also a mixture of monoethanolaminium [NH3CH2

20185752 prh 10 -09- 2018

CH2(OH)]⁺ or choline [N(CH3)3(CH2CH2(OH)]⁺ cation with the above chelating agent (chelate) comprising active ingredient acid.

Chelating agent is selected from the group comprising phosphonates (i.e. organic bisphosphonate i.e. or ganobisphosphate) preferable HEDP (etidrone acid based 5 bisphosphonates) or a mixture of chelating agents which belong to two of more groups of phosphonates: 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof.

The preparation of concentrated compositions, which comprise monoethanolamin10 ium [NH3CH2CH2(OH)]⁺ ion or cholineaminium [N(CH3)3(CH2CH2(OH)]⁺ ion in combination with the active ingredient comprising chelating agent, which contains phosphorus in its molecular structure, or monoethanolaminium [NH3CH2(OH)CH3]⁺ or cholineaminium [N(CH3)3(CH2CH2(OH)]⁺ carboxylate in combination with the active ingredient comprising chelating agent, which contains phosphorus in its molecular 15 structure, should be done in a specific order to avoid precipitation of active ingredient.

In the first stage ammonium ion (monoethanolaminium or cholineaminium) is reacted with an active ingredient, comprising phosphorus (P) containing chelating agent, such as an organic bisphosphate (HEDP). pH of the solution should stay 20 between 5 -8 after this stage. In the second stage the prepared organic ammonium chelate can then be mixed with carboxylate R⁵(COO)ri ion or any other acid source to neutralize ammonium or choline group totally or partially. The above two-staged reaction is preferable done in the presence of surfactant such as non-ionic surfactant.

In carboxylate R⁵(COO)ri ion R⁵ is hydrogen, a substituted hydrocarbyl having 1-6 carbon atoms or an unsubstituted hydrocarbyl having 1-6 carbon atoms, and n is an integer between 1-6. Preferable n is 1.

Such an ammonium chelate, preferably ammonium phosphate/carboxylate is readily absorbed in very large amounts into wood and is subsequently retained in the 30 wood.

In the method for treating wood in accordance with the invention, the organic ammonium carboxylate of formula (1a) or (1b) or ammonium chelate (monoethanolamiaminium or cholineaminium chelate) with an active ingredient, comprising

20185752 prh 10 -09- 2018 phosphorus (P) containing chelating agent in its molecular structure, is preferably in the form of an aqueous solution.

Total aqueous composition is then a homogenous aqueous solution (liquid) or dispersion, consisting of ammonium carboxylate or ammonium phosphate, possible 5 additional active ingredients and water, ionic co-solvents, additives and surfactants.

The organic ammonium chelate has a concentration of e.g. y 15-45% w/w of the total composition and the active ingredient (preferable bisphosphate such as HEDP) has a concentration of 10 -40 % w/w preferable 30 -40 % w/w.

Said active ingredient is selected from the group comprising 1-hydroxyethyli10 dene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentamethylenephosphonicacid (DTPMP) or salt thereof or a mixture thereof.

Mixing monoethanolaminium or cholineaminium with above mentioned phosphorus (P) containing chelating active ingredient is made preferable in the presence of ionic 15 liquid and water as a solvent. Suitable non-ionic surfactant is also added to ensure forming of a homogenous mixture, such as homogenous aqueous liquid. This combination can then be later reacted with carboxylate R⁵(COO)_n' but also other acidic anion sources depending on the pH of the final solution are applicable.

Wood treating involves contacting the wood with another substance. Organic am20 monium carboxylate stands of formula (1a) or (1 b) for a salt or a complex formed of an ammonium cation and a carboxylic anion. The carboxylate ion of the salt or complex may be monovalent (RCOO) or polyvalent (R(COO’)_n>i), and in that case it may also comprise unneutralised carboxyl groups (-COOH). In the latter case, R⁵ is defined as being substituted with carboxyl.

Since the group R⁵ is associated with a carboxylate group, the ammonium carboxylate of formula (1) is preferably based on a lower organic carboxylic acid and it can be prepared from such an acid or its salt. Lower organic acids include lower fatty acids such as formic acid, acetic acid, propionic acid, n- and i-butyric acid, and nand i-pentanic acid. Useful acids also include benzoic acid and oxycarboxylic acids 30 such as glycolic acid and lactic acid. Lower dicarboxylic acids such as oxalic acid, malonic acid, succinic acid and glutaric acid are also applicable.

Group R⁵ of formula (1) is most advantageously hydrogen, methyl or ethyl. In formula (1), n is preferably 1 or 2, most advantageously 1. Consequently, the most

20185752 prh 10 -09- 2018 advantageous organic ammonium carboxylate used in the method of the invention is based on lower fatty acids.

The ammonium ion is primary (RNH₃ ⁺) or tertiary (RN(CH3), and R is a substituted alkyl containing 1-6 carbon atoms. Ammonium ions containing substituted alkyls 5 have typically been formed from water-soluble amines, whose alkyl is substituted with one hydroxyl group. Organic ammonium carboxylates and organic ammonium chelates of the invention are based on ordinary monoethanolaminium or cholineaminium.

The monoethanolaminium or cholineaminium carboxylate of formula (I) is selected 10 from the group comprising a salt or a complex of formic acid and monoethanolaminium or cholineaminium. These agents will provide maximum absorption of the substance into wood and retention in the wood. Preferable organic ammonium carboxylate is a mixture of a salt of formic acid and monoethanolamine or formic acid and choline.

Active ingredient, which is used in combination with the above mentioned ammonium ion (monoethanolaminium of cholineaminium), includes a phosphor containing chelating agent and thus forms a monoethanolaminium chelate or cholineaminium chelate. Chelating agent is preferable selected from the group comprising phosphonate or bisphosphonate (i.e. organic phosphonate i.e. organophosphate) or a mix20 ture thereof. Thus, chelating agent such as phosphonate of biphosphonate used have a dual function: it serves as a flame retarding agent and also as a wood-preserving agent.

Chelate means herein an anion of the chelating agent.

In a case active ingredient (chelating agent) is for example HEDP, a homogenous 25 aqueous solution (liquid) comprising combination of monoethanolaaminium or cholineaminium cation and HEDP anion, with the compound of formula (3a) or (3b) can be prepared:

x[NH₃CH₂CH₂(OH)]⁺ + [HEDP]* -^[ HEDP]*- [NH₃CH₂CH₂(OH)]^+x (3a) x[N(CH₃)₃(CH₂CH₂(OH)]⁺ + [HEDP] *’ [(HEDP]*’ [N(CH₃)₃(CH₂CH₂(OH)] ^+x (3b) in formulas 3a and 3b, monoethanolaminium phosphate (3a) or cholineaminium phosphate (3b), y=1 - 4, x<= 4y and x, y are both integers and preferable.

20185752 prh 10 -09- 2018

Monoethanolaminium or cholineaminium phosphates are homogenous aqueous solutions (liquids) which are prepared in a presence of surfactant, more preferable in the presence of non-ionic surfactant. The compounds (3a) or (3b) are made in a presence of water and ionic liquid as a solvent. Suitable surfactant is for example 5 non-ionic surfactant.

Suitable nonionic surfactants are such as alkyl polyglucosides, fatty alcohols including cetyl alcohol and oleyl alcohol, acid or salts of octanoic acid, for example sodium or kalium salts. The latter can be used to reduce crystallization and corrosion. Its kalium and calcium salts can be used for lowering icing temperature of the 10 solution.

The use of tensides i.e. surfactants improves the distribution of monoethanolamine or choline with the mentioned active ingredient containing an anion which is based on phosphonates and facilitates the dissolving of the film forming resins and emulsions based on fatty acids and/or polysaccharides i.e. prevents the phase separa15 tion in the readymade wood preservative.

Some commonly encountered surfactants of other type include:

Anionic surfactants based on sulfate, sulfonate or carboxylate anions such as sodium dodecyl sulfate, ammonium lauryl sulfate, and other alkyl sulfate salts such as sodium laureth sulfate, alkyl benzene sulfonate or fatty acid salts.

Cationic surfactants based on quaternary ammonium cations such as cetylpyridinium chloride.

The concentration of phosphor containing active ingredient (chelating agent) in said homogenous solutions or dispersions between monoethanolamine or choline and chelating agent can be kept high without adverse effects.

The mixture of ammonium carboxylate of formula (1a) of (1b) and chelating agent or monoethanolaminium [NH3(CH2CH2OH)]⁺ or cholineaminium [N(CH3)3(CH2CH2OH)]⁺ anion and chelating agent can also be contacted with wood by preparing it first from its starting material in situ, in other words substantially in contact with wood. Typical starting materials then comprise hydroxide or a salt (such 30 as chloride) formed by an ammonium ion defined in formula (1a) or (1b) (monoethanolaminium chloride or cholineaminium chloride), and an acid or salt formed by an acid ion of chelating agent, preferable HEDP and/or carboxylate in formula (1a or

20185752 prh 10 -09- 2018

1b), e.g. sodium salt or ammo, resulting mainly in the following reactions (2a) or (2b):

x[NH₃CH₂CH₂(OH)X] + (HEDPMy) + R⁵(COOM)m [NH³CH2CH₂(OH)]⁺X [HEDP ]y [R⁵(COO)m]- (2a) or x[N(CH3)₃(CH₂CH₂OH)X] + (HEDPMy) + R⁵(COOM)n^ [(N(CH3)3(CH2CH2OH)]⁺n [HEDP-]_y [R⁵(COO)n]- (2b) in which carboxylates of formula (2a) and (2b) are stable, y, x and n are integer, y is between 1 - 4 and y+m<=5x, R⁵ is identical to those of formula (1a) and (1b) and 10 X and M are an anion respectively a cation forming a stable acid or salt. Typical anions X comprise hydroxyl and halogenides for example chloride and typical cation M comprise proton and alkali and earth alkali metals.

In the practice, formulas (2a) and (2b) are prepared e.g. by mixing an ammonium cation source and a chelating agent as a anion source in the desired molar ratio, 15 either without a medium or by using an appropriate solvent such as water or water and ionic solvent as a medium. After this carboxylate is added. When the starting material is an amine and an acid, they are simply mixed during gentle heating, if necessary. When the starting materials consist of salts, they are typically dissolved separately in water, and then the solutions are combined. If the salt or complex thus 20 formed is hydrophobic, it will separate from the water phase as an unctuous or paste-like deposit or a wax-like precipitate, and it can be separated from the water phase by any known methods. When both the starting materials and the formed product are hydrophobic, the preparation can be carried out in an organic solvent instead of water.

Preliminary results indicate, that when ammonium carboxylate of formula (1a) or (1b) is for instance a fluid pair: ethylene amine - formic acid, it can under special circumstances react and form amide when no solvent is present. Increasing temperature favours amide formation. Nearly no esters are formed.

Raw material for the organic ammonium carboxylates of formula (1a) and (1b) as 30 well as compositions and solutions obtained from these carboxylates can be got from reuse of the freezing point depressant compositions described in US patent application 12/639109 for Ahlnäs et al.

20185752 prh 10 -09- 2018

It has now been found that the organic ammonium carboxylate (1a) or (1b, for example ethanolamine 1-hydroxyethylidene,1,1-diphosphonate or choline 1-hydroxyethylidene,1,1-diphosphonate is also suitable for transferring a wood preservative active ingredient into the wood that contains phosphorous chelating agent(s) se5 lected from the group comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof which provides wood properties against flammability of wood. Said active ingredient can be also a mixture or a reaction product of an organic active ingredient 10 salt and an organic active ingredient acid.

The invention is based partly on the fact, that both polar poles of ammonium carboxylate present in formula (1a) or (1b) or ammonium carboxylate present in the ethanolamine phosphonate I carboxylate or choline phosphonate/carboxylate are readily adsorbed and absorbed to the treated wooden material. The small molecular 15 size of the both polar molecules, the low surface tension and the special feature of both polar molecules to fasten in the hydrofobic and hydrofilic materials, components and molecules of the wood makes the organic ammonium carboxylate extremely effective in the use of wood treatment.

The wooden material can be easily treated by the organic carboxylate containing 20 phoshate anions and/or ethanolaminium or cholineaminium phosphate and the organic carboxylate phosphate anions will stay inside the wooden material without leaching out. In the same time solutions comprising organic ammonium carboxylate of formula (1a) and (1b) or ammonium cation (ethanolaminium or cholineaminium) and an active ingredient anion based on phosphonic acid, selected from the group 25 comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenethaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof do not have any tendency to form precipitates or to foam.

When wood is treated with the solution comprising ethanolaminium or cholineamin30 ium chelate an/or carboxylate, active ingredient is preferable based on phosphonic acid, selected from the group comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenethaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof. This have a flame retardant wood material becomes non-flammable or get 35 better properties against fire (fire protection).

20185752 prh 10 -09- 2018

Wood can be treated in sufficiently large amounts with solution containing mentioned chelating agents because these chelating agents are not toxic. Additionally using the concentrated solutions of phosphor containing chelating agents and wood preservative solutions one can achieve fire protective properties and wood preserv5 ative on wood material.

Since the organic ammonium carboxylate and corresponding ammonium chelate is well absorbed into wood, it can, in another embodiment, be used as a further carrier of other active ingredients, such as active ingredients protecting the wood from micro-organisms.

Since the ethanolamine or choline carboxylate and/or chelate is well absorbed into wood, it can, in another embodiment, be used as a carrier of other kind of active ingredients, such as active ingredients protecting the wood from micro-organisms. The carrier then dissolves the active ingredient, transfers it in large amounts into the wood, and retains it in the wood. Consequently, the quality and quantity of the am15 monium carboxylate under consideration can be selected so that it transfers the wood-preservative agent to the wood.

It has been found that the organic ammonium carboxylate of formula (1a) or (1b) is particularly suitable for transferring wood preservative into wood comprising also a microbicide wood preservative. Microbicide wood preservative is preferable a mix20 ture or a reaction product of an organic active ingredient salt and an organic active ingredient acid.

The microbicide organic active ingredient salt component of the active ingredient is preferably selected from the group comprising alkali metal, earth alkali metal and ammonium salts of aromatic acids, alkali metal, earth alkali metal and ammonium 25 salts of aliphatic and aromatic sulphonic acids and acid salts of amines. Particularly advantageous organic active ingredient salts comprise chelating agent selected from the group comprising 1 -hydroxyethylidene, 1,1 -diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereofcon30 taining sodium benzoate, sodium alkyl benzene sulphonate, cetyl pyridinium chloride and a salt of formic acid and ethanolamine. The latter also acts as a well absorbable organic ammonium carboxylate according to formula (1a).

The organic active ingredient acid component of the active ingredient used for protecting wood from micro-organisms is preferably selected from the group comprising

20185752 prh 10 -09- 2018 aromatic carboxylic and sulphonic acids, fatty acids, organic hydroxylic acids and their oligomers and chelating acids. Preferred substances comprise benzoic acid, C6-C20 fatty acid, preferably C12-C18 fatty acid such as stearic acid, and ethylenediaminetetraacetic acid (EDTA). A mixture of benzoic acid and a C12-C18 fatty acid 5 such as stearic acid is a particularly advantageous organic active ingredient component.

An advantageous combination is organic active ingredient acid and organic ingredient salt/ammonium carboxylate HEDP + salt of ethanolaminium together with formic acid and/or propionic acid.

In one embodiment of the invention, wood is treated with a view to protect it also from micro-organisms. In that case, the organic ammonium carboxylate of formula (1) may act as such as a wood preservative, with its quality and quantity selected so as to protect the wood from micro-organisms. In an aqueous solution, the weight ratio of organic ammonium carboxylate of formula (1) to water is then particularly in the range of 1:6-1:1. In this embodiment, the wood preservative contains typically 15-45% by weight of the agent of formula (1a) or (1b).

Given the exceptionally good absorption into wood and retention in wood, one embodiment of the invention does not require environmentally hazardous copper and/or zinc to be included in the aqueous solution.

Some microbicide organic active ingredients mentioned above can be used in other purposes also. For example they can be used as surfactants (sodium alkyl benzene sulphonate and benzalkonium chloride).

In one embodiment, the ammonium carboxylate of formula (1a) or (1b) ethanolamine or choline phosphate is used for transferring other substances into the wood 25 as well. Typical such substances comprise anti-oxidants, free-radical capturers, UV protective agents and wood extractives, such as tannins, described in WO 2009/101261 or WO 2009/101262 for Granula Ltd which WO-publications will be incorporated therein completely.

Wood is treated by a solution of ethanolaminium or cholineaminium carboxylate of 30 formula (1a) or (1b) or ethanolaminium or cholineaminium phosphate in combination with organic active ingredient as mentioned above in such a way that said solution is adsorbed and absorbed to the wood to be treated over the whole thickness thereof, or to a certain depth from the surface. Since various alternatives exists, the treatment may be carried out during processing of wood at suitable point, for

20185752 prh 10 -09- 2018 instance during the final drying of the wood. The wood treatment solution of the invention may be heated and/or an elevated temperature may be used in the process, thus further improving the adsorption and absorption. The invention enables a convenient procedure for the treatment of wood materials in a cost effective man5 ner, said procedure being easily incorporated into other common processes as one stage in the process line comprising successive steps for the treatment of wood product or articles for example first step using the pressure impregnation and the second step using spraying, painting or other surface treatment process by impregnating the wood with this agent or an aqueous solution of it under vacuum. The 10 typical impregnating period is 1-120 minutes and the typical treatment temperature is 80-160°C. After impregnation the wood is usually rinsed.

The invention also relates to a wood preservative composition which provides also fire protection to wood. The composition contains organic ammonium carboxylate and an organic active ingredient containing a chelating agent that gives wood fire 15 retention properties. When chelating agent is HEDP the organic ammonium chelate or mixture of ammonium chelate and carboxylate has the formula:

x[NH₃CH₂CH₂OH]⁺ + [HEDPp -4 HEDPfy [NH₃CH₂CH₂OH]^+x (3a) or x[N(CH3)₃(CH₂CH₂OH)]⁺ + [HEDP] r [(HEDPfy [N(CH3)₃(CH₂CH₂OH)]^+x 20 (3b);

or x[NH₃CH₂CH₂(OH)X] + (HEDPMy) + R⁵(COOM)m [NH³CH2CH₂(OH)]⁺ _x[HEDP ]_y [R⁵(C00)m]' (2a), or x[N(CH3)₃(CH₂CH₂OH)X] + (HEDPMy) + R⁵(COOM)n [(N(CH3)3(CH2CH2OH]⁺n 25 [HEDP-]_y [R⁵(COO)n]’ (2b).

in which R⁵ is hydrogen, a substituted hydrocarbyl having 1-6 carbon atoms or an unsubstituted hydrocarbyl having 1-6 carbon atoms, and y, x and n are integer, y is between 1 -4 and y+m<=5x, n and m are between 1-6. R⁵ is identical to those of formula (1a) and (1b) and X and M are an anion respectively a cation forming a 30 stable acid or salt. Typical anions X comprise hydroxyl and halogenides for example choloride and typical cations M comprise proton and alkali and earth alkali metals.

20185752 prh 10 -09- 2018

Active ingredient is selected from the group comprising a phosphonate or a bisphosphonate or salt thereof or a mixture of chelating agents selected from the group comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenethaiminepentameth5 ylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof.

The wood preservative composition in accordance with the invention thus contains the same organic ammonium carboxylate of formula (1a) and (1b) and/or the same active ingredient that gives wood fire protection and which are used in the wood preparation method described above. Hence the technical special features above 10 relating to the organic ammonium carboxylate in combination with active ingredient and their composition also apply to the wood preservative composition of the invention. For this reason, only a number of crucial features of the composition will be repeated below.

In the organic ammonium carboxylate of formula (1a) and (1b) in the wood preserv15 ative composition, R⁵ is preferably hydrogen, methyl or ethyl. R¹ is preferably hydrogen.

The active ingredient gives flame retarding properties to ammonium carboxylate of formula (1a) or (1b). Preferably active ingredient is chelating agent which binds iron and manganese ions and contains phosphorus (P) in the molecular structure. Typi20 cal chelating agents of this kind are 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriaiminepentamethylenephosphonic acid (DTPMP) or a mixture thereof.

The organic ammonium carboxylate of formula (1a) or (1b) is typically in the form of an aqueous solution having typically a concentration of 5-95% by weight from total 25 composition comprising ammonium carboxylate of formula (1) and wood preservative composition containing chelating agent protecting wood from flames.

The chelating agent containing wood preservative solution against flames is preferably in a form of an aqueous solution or dispersion having an active ingredient concentration of 10-45 %, preferable 30 -45 % by weigh and ammonium carboxylate 30 concentration of 1 -50 % by weight. This kind of aqueous wood preservative solution can contain also surfactans and additives including other kind of active ingredients, viscocity modifiers, biocides, colouring agents, UV-protecting substances, agents modifying water repellency of composition, stability enhancers etc.

20185752 prh 10 -09- 2018

Surfactants are wetting agents that lower the surface tension of a liquid, allowing easier spreading, and lower the interfacial tension in between two liquids. A surfactant can be classified by the presence of formally charged groups in its head. A nonionic surfactant has no charge groups in its head. The head of an ionic surfactant 5 carries a net charge. If the charge is negative, the surfactant is more specifically called anionic; if the charge is positive, it is called cationic. If a surfactant contains a head with two oppositely charged groups, it is termed zwitterionic.

Instead of sodium alkyl benzene sulphonate can be used other surfactants also depending on the composition to be prepared. The use of tensides i.e. surfactants 10 further improves the distribution and the penetration of the organic ammonium carboxylates of formula (1) and the wood preservative active ingredients and facilitates the dissolving of the film forming resins and emulsions based on fatty acids and/or polysaccharides i.e. prevents the phase separation in the readymade wood preservative.

Some commonly encountered surfactants of each type include anionic based on sulfate, sulfonate or carboxylate anions such as sodium dodecyl sulfate , ammonium lauryl sulfate, and other alkyl sulfate salts such as sodium laureth sulfate, alkyl benzene sulfonate or fatty acid salts; cationic based on quaternary ammonium cations such as cetylpyridinium chloride; nonionic such as alkyl polyglucosides, fatty alcohols including cetyl alcohol and oleyl alcohol,acid or salts of octanoic acid , for example sodium or kalium salts. The latter can be used to reduce crystallization and corrosion.

The wood preservative composition according to invention can also include one or several microbisides as additives.

The organic ammonium carboxylate or phosphate may act alone in the composition or together with another microbicide wood preservative compound as a microbicide, protecting wood additionally for microbes.

A microbicide wood preservative compound comprises preferably microbicide active ingredient that is a mixture or a reaction product of an organic active ingredient salt 30 and an organic active ingredient acid. The organic active ingredient salt is typically sodium benzoate, sodium alkyl benzene sulphonate, cetyl pyridinium chloride, a salt of formic acid and ethanolamine, or a mixture of these. The organic active ingredient acid is typically benzoic acid, stearic acid, ethylenediaminetetraacetic acid (EDTA) or a mixture of these.

20185752 prh 10 -09- 2018

From biocides we wish especially mention PHMG, which can be added preferably 0.001 -5 wt-% to the wood preservative composition according to invention for enhance the protection against molds. Further, the drying properties of PHMG are very good which speeds up the treating process. Other polymeric guanidines or poly5 meric compounds can also be included into wood preservative composition.

Paint type resins such as fatty acids and/or polysaccharides may be added into wood preservative compositions of invention to further improve the water-repellency of wood material.

0.005 - 7 wt-% of tensides may be added to the wood preservative compositions to 10 further improve stability thereof or to further facilitate adsorption and absorption of a wood preservative composition into wood.

The invention also relates to the use of the composition described above for preparing wood by impregnating the wood with this composition. It has also been surpris15 ingly found that the ammonium carboxylate or phosphate of the invention can be used either as such or together with known anti-corrosive agents for making wood corrosion-free, less corrosive or anti-corrosive. After preparation, the wood will prevent or reduce corrosion of metal bodies such as nails, screws or the like getting into contact with the wood.

The inventors have found that the ammonium phosphate of formula (3a) or (3b) [x[NH₃CH₂CH₂(OH)]⁺ + [HEDPty -^[ HEDPty [NH₃CH₂CH₂(OH)]^+x (3a) x[N(CH3)₃(CH₂CH₂OH)]⁺ + [HEDP] r [(HEDPty [N(CH3)₃(CH₂CH₂OH)] ^+x (3b) in which R⁵ is hydrogen, a substituted hydrocarbyl having 1-6 carbon atoms or an unsubstituted hydrocarbyl having 1-6 carbon atoms, and y=1 -4, x<= 4y when x, y are both integers n is an integer between 1-6 as such has wood protecting properties against fire.

The objectives mentioned above have now been achieved with a new method for 30 preparing wood with liquid or water-soluble organic ammonium carboxylate of the

20185752 prh 10 -09- 2018 type above, in combination with an active ingredient having flame retarding properties.

Also the organic ammonium carboxylate having the formula (1a) or (1b) in combination with an active ingredient selected from the group comprising phosphonates 5 (i.e. organic phosphonate i.e. organophosphate) preferable HEDP (etidrone acid based bisphosphonates) or a mixture of chelating agents which belong to two of more groups of phosphonates: 1 -hydroxyethylidene, 1,1 -diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof have 10 flame retarding properties.

[NH₃CH₂CH₂(OH)]⁺n [R⁵(COO)n] ⁿ (1a) or [N(CH₃)₃(CH₂(CH₂(OH)]⁺n [R⁵(COO)n]’ⁿ (1 b) in which R⁵ is hydrogen, a substituted hydrocarbyl having 1-6 carbon atoms or an unsubstituted hydrocarbyl having 1-6 carbon atoms, and n is an integer between 15 1-6. Such an ammonium carboxylate is readily absorbed in very large amounts into wood and is subsequently retained in the wood. Group R⁵ in formula (1) is preferably hydrogen. The terms substituted and unsubstituted refer basically to groups containing heteroatoms (e.g. -OH, -NH₂, -COOH).

Depending on the application, ammonium carboxylate or ammonium phosphate can 20 be as a solid form or as a solution. Preferably ammonium carboxylate of formula (1a) or (1 b) is used as a solution for treating wood material. The preferable structure and properties of ammonium ion [NH₃CH₂CH₂(OH)]⁺n or [N(CH3)3 (CH2)2OH)]⁺ and acid ion [R⁵(COO)n]'ⁿ in formula (1a) and 81b) have been discussed extensively above and therefore it is not our intention to repeat them in this connection.

Wood is treated by a solution of ammonium carboxylate of formula (1a) or (1b) in such a way that said solution is adsorbed and absorbed to the wood to be treated over the whole thickness thereof, or to a certain depth from the surface. The absorbing and adsorbing properties of ammonium carboxylate and also the general methods for preparing ammonium carboxylate solutions has discussed extensively 30 above. Under the heading “Examples” we will give thereinafter some established methods for impregnating, spraying and painting wood material with solutions which is also applicable when used ammonium carboxylate containing solutions as such.

20185752 prh 10 -09- 2018

If ammonium carboxylate of formula (1) is used as a solution it is prepared as described above that is, by mixing an ammonium cation source and a carboxyl anion source in the desired molar ratio, either without a medium or by using an appropriate solvent such as water as a medium.

When ammonium carboxylate of formula (1) is used as a solid it is preferably a mixture of salt comprising a suitable molar ratio of salt of an ammonium component present in formula (1) mixed with suitable amount of moles of salt of an acid component present in formula (1).

The non-flammability properties of ammonium carboxylate of formula (1a) or (1b) 10 can be enhanced by using a mixture of liquid or water-soluble organic ammonium carboxylate and an active ingredient comprising chelating agents mentioned above.

Examples

A number of examples are given below with the sole purpose of illuminating the invention.

Example 1

Compositions and their usage

A typical aqueous solution contains 10 -35 % by weight preferable 25 -35 by weight of chelating agent being able to bind iron and manganese ions and that contain phosphorus (P) in its molecular structure. This solution contains additionally ammo20 nium carboxylate 1- 30 % by weight and possible wood preservative containing active ingredient 1 - 45 % by weight, the remainder being substantially water, additives and surfactants.

Composition 1

Composition 1 is targeted to fire-protection of wood. Composition 1 protects wood against fire and it makes wood non-flammable for a certain time.

wt-% monoethanolammonium formiate (43 wt-% formic acid and 57 wt-% monoethanolamine)

8.33 wt-% Cublen KT600 (60 wt-% HEDP)

0.5 wt-% PHMG 20 (20 wt-% PHMG)

Cublen is neutralized with monoethanolamine in aqueous environment.

20185752 prh 10 -09- 2018

-4 wt-% non- ionic tenside rest is water

The composition of example 1 was well absorbed and adsorbed into wood and has excellent fixation into wood material.

Composition 2

Composition 2 is also intended for protecting wood against fire and makes wood non-flammable for a certain time.

wt- % monoethanolammonium formiate (43 wt-% formic acid and 57 wt-% monoethanolamine)

49.2 wt -% Cublen KT 600 (29.5 wt-% HEDP)

20.6 wt-% ammonia water (24.5 wt%) i.e. ammonia (100%)

3.6 wt-% ionic tenside rest is water

The composition 2 was applied onto surface of plywood board made of spruce or birch. The composition was absorbed well into wood, about 250 g/m2 when applied once. Treated wood material showed excellent fire-protecting properties in a test according to standard EN5660.

The composition of example 2 was well absorbed and adsorbed into wood and has excellent fixation into wood material. The compositions 1 and 2 can be used for impregnating, painting or spraying wood as described below.

Depending on the specific application and wood treating method the compositions according to invention can be modified very extensively as to their ammonium carboxylate and chelating agent content compared to those prepared in example 1 or 2. For example, if one uses composition according to example 2 and impregnates wood with this composition, it may be possible to lower then amount of chelating agent to about 1/20 from concentration shown in example 1 or 2.

The chelating agent 1- hydroxyethylidene,1,1-diphosphonic acid (HEDP) used in compositions 1 and 2 can be replaced by other phosphor containing chelating agents such as ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriaiminepentamethylenephosphonic acid (DTPMP).

Composition 3

Concentrated homogenous solution % HEDP acid (60 %) = 31.8 % w/w calculated from the total weight of the composition 3.

25 % of ammonia water (24.5 %) = 6.1 % w/w NH₃

Total weight of HEDP and ammonia water: 37.9 % w/w calculated from the total weight of the composition 3.

Composition 4

Concentrated homogenous dispersion

50 % HEDP (70 %) = 37.9 % w/w calculated from the total weight of the composition

4.

% complex of formic acid and monoethanolaminium + non-ionic surfactant (37.9 % w/w)

Total weight of HEDP and dispersion containing complex of formic acid and mo15 noethanolamine ammonia water: 53.9 % w/w calculated from the total weight of the composition 4.

Examples 2-6

20185752 prh 10 -09- 2018

In the following, practical examples will be given of methods how compositions ac20 cording to invention can be used for the treatment of wood and how the treatment can be integrated in a wood material processing line in mills for wood processing.

2) Pressure impregnation

A conventional method for entering great amounts of impregnation substance in wood, and thereby providing the most effective treatment by means of different 25 steps (negative pressure and overpressure, elevated temperature). By this method, the best penetrability of compositions is obtained, and the wood can normally be impregnated to the core. The composition according to the invention has a very good penetrability, wherein it is possible to reduce the negative

20185752 prh 10 -09- 2018 pressures/overpressures used in conventional CCA impregnation and thereby to improve the cost-effectiveness of the process. Also, a tighter-grained type of wood, such as spruce, can be pressure impregnated with the composition according to the invention, which has not been possible with conventionally used substances.

3) Immersion impregnation

The penetrability of the composition according to the invention is good, and in some cases, mere immersion impregnation is also possible. This method is simple but it requires separate immersion basins and is carried out in batch processes, like the pressure impregnation.

4) Spraying

The composition according to the invention can be sprayed onto the surface of wood, for example, in connection with the planning of sawn timber. In this way, preservation against microorganisms can be achieved during storage and delivery before a surface treatment (painting etc.) later on.

5) Painting or other surface treatment line

The composition according to the invention may also be added into the wood in connection with a painting or another surface treatment line. From a paint dosing tank, a wooden board can be impregnated with the solution under overpressure or negative pressure through a separate painting unit. Depending on the pressure and 20 the speed of the line, relatively good penetrability and thereby a reasonable resistance to weather and fire can be achieved by this method.

6) Drying of the wood and the control of final moisture content

In the processing of timber in sawmills, it is more and more important that the final moisture content of the wood is suitable to prevent cracking and dimensional 25 changes, as well as to prevent too good a substrate from forming for biological life.

In connection with the drying, the tree often dries to a moisture content that is lower than desired. At the end, the moisture content can be adjusted, for example, by a technique based on spraying with water. In this step, it is very easy to add the composition according to the invention into the wood, wherein it is possible to eliminate 30 cracking and dimensional changes due to the drying of wood. Furthermore, this method can be used to improve the fire resistance and to provide at least a shortterm preservation against micro-organisms.

In connection with the treatment methods according to points 1 to 4, however, it is important to dry the wood well (for example, at a temperature from 40 to 80 °C), wherein the extra water absorbed in the wood during the process can be removed and the moisture content can be stabilized to a desired final level.

By the solution of the invention, it possible to facilitate the treatment of wood under winter conditions where the processing of frozen wood (for example, melting, impregnation, planning, painting, etc.) is problematic and constitutes an extra cost item.

Usually ammonium carboxylate of formula (1) as mentioned above is absorbed into 10 wood by impregnating the wood with this agent or an aqueous solution of it under vacuum. The typical impregnating period is 1-120 minutes and the typical treatment temperature is 80-160°C. After impregnation the wood is usually rinsed.

Example 7

In the following are given exemplary microbiside active ingredients which can be also used in compositions and solutions containing above mentioned chelating agents which repels invertebrates. The ammonium carboxylate carriers mentioned in connection of those microbicide active ingredients may also be used when preparing above mentioned chelating agents.

20185752 prh 10 -09- 2018

Microbicide studies

Objective

Studies are made in order to determine the microbicide effect of the system com5 bining an ammonium carboxylate carrier and an active ingredient of the invention against micro-organisms that damage wood (mildews and blue stain and rot fungus).

1. Materials and methods

1.1 Ammonium carboxylate carriers

Two ammonium carboxylate carrier mixtures were selected for the tests, with the water-soluble mixtures selected as shown in the accompanying table (table 1). A White Spirit solvent was additionally used as a reference carrier.

Table 1 Ammonium carboxylate carriers selected for the tests.

20185752 prh 10 -09- 2018

Ammonium carboxylate carrier	Proportion of total carrier, %
MHEA	100
MHEA/PHEA	70/30

MH = formic acid (actually its anion, i.e. formiate)

EA = ethanolamine (actually its cation, i.e. ethanolammonium)

PH = propionic acid (actually its anion, i.e. propionate)

2.2 Active ingredients and their mixtures

The active ingredients under study consisted of the commercial and new solutions listed in the central column of the following tables (2 and 3). The right-hand column of the tables corresponds to the ammonium carboxylate solutions used in accordance with table 1.

Table 2 Active ingredient and carrier mixtures used in decay tests

20185752 prh 10 -09- 2018

Example	Active ingredient and its	Carrier and its concen-
	concentration	tration
	Commercial active ingre-
	dient:
1	5% of Tebuconazole	30% of MHEA
2	5% of Tebuconazole	30% of MHEA/PHEA
	New active ingredient:
3	5% of benzoic acid	30% of MHEA
4	5% of benzoic acid	30% of MHEA/PHEA
5	5% of EDTA in acid form	30% of MHEA
6	5% of EDTA in acid form	30% of MHEA/PHEA
7	5% of CEBE 2	30% of MHEA
8	5% of CEOS	30% of MHEA
9	5% of BHTEB	30% of MHEA
10	5% of BEPRE	30% of MHEA
11	5% of SBBW-30	100% of White Spirit
Comparisons:
Untreated wood
12 (ref.)	-	-
Wood treated with carrier
alone
13 (ref.)	-	30% of MHEA
14	-	30% of MHEA/PREA
15 (ref.)	-	100% of White Spirit
5
EDTA	ethylenediaminetetraacetic acid
CEBE2	= 43% of MHEA + 43% of cetyl pyridinium benzoate + 9% Pre-
	ventol MP100 + 5% EDTA
CEOS	= 13% of stearic acid + 33% of lactic acid-oligomer + 6% of
10	cetyl pyridium chloride + 48% of MHEA
BHTEB	= 5% of Preventol A8 + 5% of benzoic acid + 90% of MHEA
BEPRE 100	= 4% of Preventol MP 100 +92% of MHEA

SBBW-30 = 30% (25% of stearic acid + 12% benzoic acid + 65% of alkylbenzyldimethylammonium chlorides of various alkyl chain lengths) + 70 % White Spirit

Preventol A8 = Tebuconazole

Preventol MP 100 = IBPC = 3-iodine-2-propynyl butyl carbonate

20185752 prh 10 -09- 2018

Table 3 Active ingredient mixtures used in mildew and blue stain tests

Example	Active ingredient and its	Carrier and its concen-
	concentration	tration
	Commercial active ingredi-
	ent
16	5% of IBPC	30% of MHEA
17	5% of IBPC	30% of MHEA/PREA
	New active ingredient
18	5% of benzoic acid	30% of MHEA
19	5% of benzoic acid	30% of MHEA/PREA
20	5% of EDTA in acid form	30% of MHEA
21	5% of EDTA in acid form	30% of MHEA/PREA
22	5% of SBB	30% of MHEA
23	5% of CEBE2	30% of MHEA
24	5% of CEOS	30% of MHEA
25	5% of BHTEB	30% of MHEA
26	5% of BEPRE 100	30% of MHEA
27	5% of SBBW-30	100% of White Spirit
Comparisons:
Untreated wood
28 (ref.)	-	-
Wood treated with
carrier alone
29 (ref.)	-	30% of MHEA
30	-	30% of MHEA/PREA
31 (ref.)	-	100% of White Spirit

IBPC = 3-iodine-2-propynylbutylcarbonate

20185752 prh 10 -09- 2018

2.3 Extraction tests of the wood material

Oven-dry pine surface samples (15x15x5 mm) were extracted under five different 5 extraction schedules (schedules 1 - 5). Unprocessed (unextracted) wood samples were used as reference material for the extracted wood material.

Extraction schedule 1, Water extraction

The wood samples were impregnated (vacuum impregnated) with water before extraction. The water-impregnated samples were extracted in an autoclave for 20 10 minutes at a temperature of 121 °C.

20185752 prh 10 -09- 2018

Extraction schedule 2, MHEA1

Wood samples were impregnated (vacuum impregnation) with a 50% MHEA carrier and the impregnated samples were extracted in an autoclave for 20 minutes at a temperature of 121 °C. Then the samples were rinsed with cold water until the rinsing 5 water was limpid (at least 3-4 rinses, one water rinse = in water over night under press).

Extraction schedule 3, MHEA2

Wood samples were impregnated (vacuum impregnation) with a 50% MHEA carrier and the impregnated samples were extracted in an autoclave for 20 minutes at a 10 temperature of 121 °C. Then the samples were rinsed with cold water under press over night (one rinse).

Extraction schedule 4, Solvent extraction

Wood samples were extracted with acetone in a Soxhlet apparatus for 4 hours. After this the samples were further extracted with distilled water in a Soxhlet apparatus 15 for 4 hours. The samples were not dried between the extractions.

Extraction schedule 5, Solvent-MHEA-extraction

Wood samples were extracted with acetone in a Soxhlet apparatus for 4 hours. Then the samples were further extracted with distilled water in a Soxhlet apparatus for 4 hours. The samples were not dried between the extractions. After the water extrac20 tion, the samples were air dried and impregnated (vacuum impregnation) with a 50% MHEA carrier. After they had been impregnated, the samples were rinsed with water under press over night.

2.4. Biological effectiveness of mixtures of active ingredient and a neat and extracted wood

2.4.1 Decay tests

Small pine surface samples (15 mm x 15 mm x 5 mm) were vacuum impregnated with the active ingredient carrier mixture under study (table 2). Untreated samples and samples treated merely with ancat carriers or a White Spirit solvent were used as a reference. The brown-rot fungus Coniophoraputeana, BAM Ebw was selected 30 as the test fungus. The fungus strain is derived from the strain collections of VTT

Technical Research Centre of Finland, Building, Built Environment.

20185752 prh 10 -09- 2018

The amounts of mixtures of active ingredient-carrier absorbed into the samples (retention kg/m³) were determined by calculatory means and dry basis weighing (dry weights of the samples before and after impregnation and rinsing). Part of the samples was rinsed with water before the decay tests were started. The rinsing was 5 performed by impregnating the pieces with water and rinsing the samples under water for 4 days. The rinse water was renewed four times during the rinsing operation. The rinsing was performed under modified EN 84 standard. The amounts of active ingredient-carrier absorbed into the samples were determined also after the rinse.

The decay tests were conducted under accelerated and modified EN 113 standard. The reference samples and both unrinsed and rinsed test samples were allowed to decay over a period of 5 weeks. The effectiveness of the impregnation treatments was determined on the basis of the weight loss caused by the fungus.

2.4.2 Mildew and blue stain tests

In mildew and blue stain tests, pine surface wood samples (25 x 50 x 5 mm) were vacuum impregnated with mixtures of active ingredient and carrier (table 3). The samples were not rinsed.

The anti-mildew and anti-blue stain effect of the mixtures of active ingredient and carrier and their references were examined in a laboratory by a suspending method. 20 The test samples and the reference samples were suspended in random order in exposure chambers. The relative humidity in the chambers was regulated by means of water in the range 95 - 100% at a test temperature of 20 °C (+/-2 °C).

Blue stain and mildew fungus suspensions were injected into the test boxes before the test was started. The mildew suspension contained three mildew species that 25 thrive in wood: Aspergillus versicolor (E1), Gladosporium sphaerospermum (R7) and Penicillium sp. (1017). The blue stain suspension consisted of the following species: Aureobasidium pullulans (T1), Sclerophoma entoxylina (Z17) and Ceratocystispilifera (Z11). The fungus strains are derived from the strain collections of VTT Technical Research Centre of Finland, Building, Built Environment. The moulding 30 of the test samples was monitored visually at the end of 2, 4, 6, 8 and 10 weeks from the start of the test on a scale 0-5.

= no growth s1 = marks of starting growth (microscopically observable) = 1 -10% of the area covered by microbial growth (microscopically observable)

20185752 prh 10 -09- 2018 = 10 - 30% of the area covered by microbial growth (visually observable) = 30 - 70% of the area covered by microbial growth (visually observable) = 100% of the area covered by microbial growth (visually observable)

3. Results

3.1 Anti-decay effect of the mixtures of active ingredient and carrier and the extraction schedules

The cellar fungus (C. puteana) is a brown-rot fungus that causes weight loss and reduces the strength of wood material. The metabolism of brown-rot fungi utilises 10 the hydrocarbon structural components of wood (hemi-cellulose and cellulose) and also modifies the lignin structure. If brown rot proceeds over a long period, there will remain only brittle lignin, which decomposes into dust even under light stress.

The results of the decay tests are illustrated in figures 1 - 3. The results indicate that all of the mixtures of active ingredient and carrier and ancat carriers under study, 15 when not rinsed, prevented alone the decay caused by C. puteana in an accelerated decay test. In all the cases, the weight loss of the samples was smaller than the weight loss set as the preservative effect limit under the EN 113 standard (<3 %).

A weight loss of less than 3% was achieved in the rinsed samples when the preservative contained tebuconazole-MHEA, tebuconazole-MHEA+PREA, CEBE220 MHEA, CEOS-MHEA or BHTEB-MHEA. A weight loss limit of almost 3% was achieved with rinsed samples containing benzoic acid-MHEA+PREA (4.2 % by weight weight loss) or EDTA-MHEA+PREA in acid form (5.2% weight loss). The rinse clearly reduced the anti-decay effect of benzoic acid-MHEA (7.3% by weight loss) and of EDTA-MHEA in acid form (12.7% weight loss).

When unrinsed, both the ancat carriers prevented efficiently the weight loss caused by rot fungus in the test samples. The effectiveness of MHEA+PREA decreased after rinsing, and a weight loss of 9% was stated in the test samples. WhiteSpirit did not prevent the weight loss caused by rot fungus. By contrast, a mixture of SBBW30 and WhiteSpirit proved to have a high anti-decay effect both when rinsed and not 30 rinsed.

The objective of the extraction tests was to determine whether removal of e.g. soluble sugars or structural components soluble in the carrier increases the decay resistance of wood. Ancat carriers have proved (cf. the results of the extraction tests) to extract hydrocarbons and particularly xylane of hemi-cellulose from the wood material. The results of the decay tests indicated that water extraction (extraction schedule 1), MHEA1 (extraction schedule 2) and solvent extraction (extraction schedule 4) did not increase the decay resistance of extracted wood material 5 (weight losses > 30 %). By contrast, in samples treated under extraction schedules (MHEA2) and 5 (solvent-MHEA extraction) the weight loss caused by rot fungus was under the 3% limit prescribed by the standard.

Figure 3. Effect of the extraction schedules on the anti-decay properties of wood material.

Table 4 presents the active ingredient-carrier contents absorbed into the samples during impregnation. The contents were relatively high, with variations in the range 190 - 240 kg/m³ Rinsing had no notable effect on the absorption.

Table 4. Active ingredient contents in the test samples after impregnation and rins20185752 prh 10 -09- 2018

	ing.
15	Example	Mixture active ingredient-carrier	Retention kg/m
			Not rinsed	Rinsed
	13	MHEA	201	194
	14	MHEA+PREA	182	182
20	3	Benzoic acid-MHEA	213	225
	4	Benzoic acid-MHEA/PREA	204	214
	5	EDTA-MHEA in acid form	222	217
	6	EDTA-MHEA/PREA in acid
		form	209	203
25	1	Tebuconazole-MHEA	222	222
	2	Tebuconazole-MHEA/PREA	194	193
	7	CEBE2-MHEA	205	208
	8	CEOS-MHEA	231	233
30	9	BHTEB-MHEA	235	235
	10	BEPRE100-MHEA	236	228

3.2 Anti-mildew and anti-blue stain effect of mixtures of active ingredient/carrier and extraction schedules

20185752 prh 10 -09- 2018

Blue stain fungi penetrate into the wood material structure, and by staining the wood, they entail discolouration and alter the moisture behaviour of the material (the material will have higher water absorption). The metabolism of blue stain fungi utilises mainly soluble nutrients, and they do not usually produce weight losses or decrease 5 the strength of the wood. By contrast, mildew fungi grow only on the surface of the wood material. Mildews do not penetrate into the material structure and thus do not cause weight losses or decreased strength. Mildews live on the soluble nutrient present on the material surface. The damages caused by mildews relate to discolouration and malodour and possible health hazards.

The blue stain tests did not yield any results. Blue stain was not observed in one single treated or untreated sample during an exposure period of 10 weeks. In the case of the untreated reference, this zero result may also be partly due to excessive moisture of the samples, which in turn is caused by the hygroscopicity of the mixtures of active ingredient and carrier, to the susceptibility of blue stain fungi to the 15 compounds under study and/or to transfer of the active ingredients also to the untreated reference sample, owing to the high transfer potential of the carrier.

The results of the mildew tests are shown in figures 4-6. The corresponding examples are given in table 3. Mildew growth was prevented completely in an exposure 20 test of 10 weeks when the samples were treated with the following mixtures of active ingredient and carrier benzoic acid-MHEA- (example 18), benzoic acidMHEA+PREA (example 19), EDTA-MHEA in acid form (example 20), EDTA-MHEAPREA in acid form (example 21), SBB-MHEA (example 22), CEBE2-MHEA (example 23) and BEPRE100-MHEA (example 26) and SBBW30-WhiteSpiht. In untreated 25 control samples and test samples treated with WhiteSpirit, moulding reached the mildew index 5 (100% of the sample surface was covered by mildew growth) after 6 weeks' exposure. Moderate mildew growth was observed in the two samples treated with ancat carriers. The mildew index reached the value 2 during the exposure (mildew growth not yet visible). Moderate mildew growth (mildew index 2) was 30 also observed in test samples treated with active ingredient mixtures of CEBE2MHEA (example 23) and CEOS-MHEA (example 24).

20185752 prh 10 -09- 2018

The objective of the extraction tests was to determine whether the removal of e.g. soluble sugars or structural components soluble in the carrier increases the mildew resistance of the wood. The results of the mildew tests show that water extraction (extraction schedule 1), MHEA2 (extraction schedule 3) and solvent extraction (ex5 traction schedule 4) did not increase the mildew resistance of the extracted wood material, with a mildew index variation between 3 and 5 in these cases (visible and abundant growth). On the contrary, moulding was moderate in samples treated under extraction schedules 2 and 5 (MHEAI and solvent-MHEA extraction) (mildew index 1 or less).

4. Conclusions of mibrobicide studies

The mixtures of active ingredient and carrier were observed to have a distinct preventive potential both with respect to decay and to mildew formation. The decay tests determined the anti-decay effect of MH/EA and MH/EA+PR/EA carriers and of active ingredients mixed in these (benzoic acid, EDTA in acid form, tebuconazole, 15 CEBE2, BHTEB, BEPRE 100-MHEA, CEOS). The decay tests also determined the effect of SBB dissolved in a WhiteSpiht solvent. Wood samples extracted under five different extraction schedules were also included in the decay tests.

The mixtures of active ingredient and carrier efficiently prevented decay caused by C. puteana in an accelerated decay test. The test results indicated that the mixtures 20 of active ingredient and carrier efficiently prevented weight loss caused by rot fungus in the treated wood samples also after rinsing. The most efficient active ingredient mixtures with the highest anti-decay potential occurred among the formulations produced by the company Granula Oy.

The mildew and blue stain tests, in turn, determined the anti-mildew effect and anti25 blue stain effect of MH/EA and MH/EA+PR/EA carriers and of active ingredients mixed in these carriers (benzoic acid, EDTA, IBPC, SBB, CEBE2, CEOS, BHTEB, BEPRE 100-MHEA in acid form) and SBB dissolved in a WhiteSpiht solvent. The test results showed that the mixtures of active ingredient and carrier actively prevented mildew growth on the surface of the treated wood samples during an expo30 sure period of 10 weeks. No blue staining was observed. This result may be due to excessive moisture of the samples, which in turn was caused by the hydroscopicity of the mixtures of active ingredient and carrier, to the susceptibility of blue stain fungi to the compounds under study and/or to transfer of active ingredients also to the untreated reference sample, owing to the high transfer potential of the carrier.

The effect of extraction of the soluble and structural components of wood material on decay and mildew formation was determined by treating the wood material under five different extraction schedules. Water and solvent extractions had no effect on the decay and mildew resistance of the wood material. Decay caused by C. puteana 5 was inhibited in the cases where the wood material contained a carrier after the extraction.

Claims (27)

1. Claims

   20185752 prh 10 -09- 2018

   1. The use of the composition comprising liquid or water-soluble organic ammonium carboxylate in combination with an active ingredient acid, wherein the organic

   5 ammonium carboxylate has the formula (1 a) or (1 b):

   [NH₃CH₂CH₂(OH)]⁺n [R⁵(COO)n] ⁿ (1a) or [N(CH₃)₃(CH₂CH₂OH)]⁺n [R⁵(COO)n]-ⁿ (1 b) in which R⁵ is hydrogen, an unsubstituted hydrocarbyl having 1-6 carbon atoms or a substituted hydrocarbyl having 1-6 carbon atoms and wherein substituted hydro10 carbyl refers to groups containing heteroatoms (e.g. -OH, -NH₂, -COOH); and n is an integer between 1-6; and wherein active ingredient acid is based on a chelating agent, which contains phosphorus (P) in its molecular structure; as a flame retardant in a wood.
2. 2. The use of the composition comprising a liquid or water soluble ammonium in 15 combination with an active ingredient acid wherein ammonium is based on mo- noethanolaminium or cholineaminium cation and the active ingredient acid is based on a chelating agent (chelate), which contains phosphorus (P) in its molecular structure, as a flame retardant in a wood.
3. 3. The use defined in claim 1 or 2, characterized in, that the composition comprising 20 monoethanolaminium or cholineaminium carboxylate of formula (1 a) or (1 b) in combination with a chelating agent or the composition comprising monoethanolaminium or cholineaminium ion in combination with the chelating agent, are present in an aqueous solution, dispersion or emulsion.
4. 4. The use defined in claim 3, characterized in, that the composition is emulsion 25 and it is used as a fire retarding agent of the wood adhesive agent.
5. 5. The use defined in claim 1, characterized in that the organic ammonium carboxylate of formula (1) is a salt of formic acid and monoethanolaminium.

   20185752 prh 10 -09- 2018
6. 6. The use defined in any of the previous claims, characterized in, that the composition present in aqueous solution, dispersion or emulsion further consists of possible additional active ingredients, possible ionic co-solvents, additives and surfactants, the rest being water.

   5
7. 7. The use defined in claim 6, characterized in, that the solid content of the aqueous solution, dispersion or emulsion is over 30 % w/w calculated from the total weight of the composition.
8. 8. The use defined in claim 6 or 7, characterized in, that the composition contains chelating agent having fire-retarding properties, in the range of 10- 45 % w/w pref-

   10 erable in the range of 30 -45 % w/w.
9. 9. The use defined in claim 6, characterized in that the composition further comprises an additional active ingredient, which is a wood preservative solution, which includes a microbicide active ingredient as an additive which microbicide active ingredient is a mixture or a reaction product of an organic active ingredient salt and

   15 an organic active ingredient acid.
10. 10. The use defined in claim 9, characterized in that the microbicide active ingredient is, botulin, benzalkonium chloride (alkylbenzyldimethylammonium chlorides of various alkyl chain lengths) or polyhexamethyleneguanidine (PHMG).
11. 11. The use defined in claim 9 or 10, characterized in that the organic active in20 gradient salt is selected from the group comprising alkali metal and earth alkali metal salts of alkali metal, earth alkali metal and ammonium salts of aliphatic and aromatic sulphonic acids and acid salts of amines.
12. 12. The use defined in claim 11, characterized in that the organic active ingredient salt is selected from the group comprising sodium benzoate, sodium alkyl benzene

    25 sulphonate, cetyl pyridinium chloride.
13. 13. The use defined in any of the previous claims, characterized in that chelating agent is a phosphorus (P) containing chelating agent such as 1- hydroxyethyl idene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentamethylenephosphonicacid (DTPMP) or salt

    30 thereof or a mixture thereof.
14. 14. The use defined in any of the previous claims, characterized in that R⁵ is hydrogen or unsubstituted alkyl containing 1-4 carbon atoms, and n is 1.

    20185752 prh 10 -09- 2018
15. 15. The use defined in claim 14, characterized in that R⁵ is hydrogen, methyl or ethyl.
16. 16. The use defined in claim 6, characterized in that it composition contains also a non-ionic surfactant, which is selected from the group comprising: octanoic acid,

    5 alkyl polyglucoside, fatty alcohol including cetyl alcohol and oleyl alcohol.
17. 17. The use defined in claim 16, characterized in that non-ionic surfactant comprises also alkali metal and earth alkali metal salts.
18. 18. The use defined in claim 6, characterized in that the composition contains also additives such as MgCOs, AI(OH)3, silica compounds and foaming preventing

    10 substances.
19. 19. The use defined in any of the previous claims, characterized in that said use comprises treating wood at least once by impregnating, spraying or painting with the compound comprising liquid or water-soluble monoethanolaminium carboxylate/chelate and/or with cholineaminium carboxylate/chelate and/or with monoeth-

    15 anolaminium chelate an/or with cholineaminium chelate, which chelate originates to the chelating agent, which contains phosphorus (P) in its molecular structure.
20. 20. The use defined in claim 19, characterized in that the wood is treated once or twice with the same or different compound.
21. 21. The method of preparing a concentrated flame retardant composition comprising 20 liquid or water-soluble organic ammonium compound in combination with an active ingredient agent suitable for preventing ignition or combustion of the wood, characterized in that monoethanolaminium [NH3CH2CH2OH]⁺ ion or cholineaminium [N(CH3)3CH2CH2(OH)]⁺ ion is reacted with the active ingredient acid comprising chelating agent, which contains phosphorus in its molecular structure.

    25
22. 22. The method defined in claim 21, characterized in that the reaction is done in the presence of water and a possible ionic co-solvent.
23. 23. The method defined in claim 22, characterized in that pH of the aqueous solution is between 5 -8 after monoethanolaminium [NH3CH2CH2OH]⁺ ion or cholineaminium [N(CH3)3CH2CH2(OH)]⁺ ion have been reacted with the active ingredient

    30 acid.
24. 24. The method defined in any of the claims 21-23, characterized in that the organic ammonium compound or organic ammonium carboxylate has a dry solid content of

    15-45% w/w from the total composition and the active ingredient comprising chelating agent, which contains phosphorus in its molecular structure (preferable phosphonate such as HEDP) has a dry solid content of 10 -40 % w/w preferable 30 -40 % w/w of the total composition.

    5
25. 25. The method defined in claim 21, characterized in that the prepared organic ammonium chelate is mixed with carboxylate R⁵(COO)ri ion or other acid source to neutralize monoethanolaminium or cholineaminium ions, in which which R⁵ is hydrogen, an unsubstituted hydrocarbyl having 1-6 carbon atoms ora substituted hydrocarbyl having 1-6 carbon atoms and wherein substituted hydrocarbyl refers to 10 groups containing heteroatoms (e.g. -OH, -NH2, -COOH).
26. 26. The method defined in claim 25, characterized in that R⁵ is hydrogen or unsubstituted alkyl containing 1-4 carbon atoms, and n is 1.
27. 27. The method defined in any of the claims, characterized in that the reaction is done in the presence of water and possible ionic co-solvent by reacting water-solu-

    15 ble monoethanolaminium [NH3CH2CH2OH]⁺ ion or cholineaminium [N(CH3)3CH2CH2(OH)]⁺ ion with the active ingredient acid comprising chelating agent, which contains phosphorus in its molecular structure in the presence of surface-active agent, preferable non-ionic surface active agent.