FI129509B - Menetelmä puun palonsuoja-aineen ja palonsuoja-ainekoostumuksen tuottamiseksi - 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 liguid or water- 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 ma- terial having flame retardant properties in wood.

In the JP-patent application 2010-240968 it has been presented a wood preserva- tive composition which is based on ammonium carboxylate and active ingredient agent having properties as a flame retardant. However, depending on the concen- tration of the active ingredient and the exact formulation of the ammonium carbox- ylate, it has now perceived, that the active ingredient agent has a tendency to crys- 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 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 liguid or water- soluble organic ammonium carboxylate in combination with an active ingredient hav- a ing flame retarding properties.

3 25 The organic ammonium carboxylate has the formula (1a) or (1b):

O > [NH3CH2CH2(OH)]*n [RXCOO),]” (1a) Or a a N [N(CH3)3(CH2CH2(OH))]*n [RH(COO)n]" (1b)

LO

N 0 in which R5 is hydrogen, a substituted hydrocarbyl having 1-6 carbon atoms or an S unsubstituted hydrocarbyl having 1-6 carbon atoms, and n is an integer between 1-6. Preferablen is 1.

Such an ammonium carboxylate is readily absorbed in very large amounts into wood and is subsequently retained in the wood.

Group R in formula (1) is preferably hy- drogen.

The terms "substituted" and "unsubstituted" refer basically to groups con- taining heteroatoms (e.g. -OH, -NH>, -COOH). The chelating agent means a chelat- 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 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 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 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), — ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaimine- © pentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof. a The chelating agent can be used in combination with ammonium carboxylate of for- <Q mula (1a) or (1b) in high concentrations without any precipitate occurring.

The con- > centration of HEDP can be for example up to 40 % w/w in liguid composition com- E 30 prising said ammonium carboxylate with formula (1a) or (1b) and an active ingredi- a ent (HEDP). 0 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 mo- lecular structure, one can use also a mixture of monoethanolaminium [NH3CH>

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 bisphosphonates) or a mixture of chelating agents which belong to two of more groups of phosphonates: 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), eth- ylenediaminetetramethylenephosphonic acid (EDTMP) diethylenetriaimine- pentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof.

The preparation of concentrated compositions, which comprise monoethanolamin- ium [NH3CH2CH2(OH)]* ion or cholineaminium [N(CH3)3(CH2CH2(OH)]* ion in com- bination with the active ingredient comprising chelating agent, which contains phos- phorus 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 structure, should be done in a specific order to avoid precipitation of active ingredi- ent.

In the first stage ammonium ion (monoethanolaminium or cholineaminium) is re- acted with an active ingredient, comprising phosphorus (P) containing chelating agent, such as an organic bisphosphate (HEDP). pH of the solution should stay between 5-8 after this stage.

In the second stage the prepared organic ammonium chelate can then be mixed with carboxylate R3(COQ), 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 surfac- tant. © o 25 In carboxylate RYCOO)n ion RS is hydrogen, a substituted hydrocarbyl having 1-6 & carbon atoms or an unsubstituted hydrocarbyl having 1-6 carbon atoms, and n is oO an integer between 1-6. Preferable n is 1. E Such an ammonium chelate, preferably ammonium phosphate/carboxylate is read- N ily absorbed in very large amounts into wood and is subsequently retained in the I 30 — wood. co > In the method for treating wood in accordance with the invention, the organic am- monium carboxylate of formula (1a) or (1b) or ammonium chelate (monoethanola- miaminium or cholineaminium chelate) with an active ingredient, comprising phosphorus (P) containing chelating agent in its molecular structure, is preferably in the form of an agueous solution. Total agueous composition is then a homogenous agueous solution (liguid) or dis- persion, consisting of ammonium carboxylate or ammonium phosphate, possible 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-hydroxyethyli- dene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentamethylenephosphonic acid (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 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 com- bination can then be later reacted with carboxylate R9(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 am- monium carboxylate stands of formula (1a) or (1b) for a salt or a complex formed of an ammonium cation and a carboxylic anion. The carboxylate ion of the salt or com- plex may be monovalent (RCOO') or polyvalent (R(COO')n>1), and in that case it may also comprise unneutralised carboxyl groups (-COOH). In the latter case, R? is © defined as being substituted with carboxyl. a 25 — Since the group R® is associated with a carboxylate group, the ammonium carbox- <Q ylate 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 E acids such as formic acid, acetic acid, propionic acid, n- and i-butyric acid, and n- N and 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.

N Group R* of formula (1) is most advantageously hydrogen, methyl or ethyl. In for- mula (1), n is preferably 1 or 2, most advantageously 1. Conseguently, the most 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 cholin- eaminium.

The monoethanolaminium or cholineaminium carboxylate of formula (I) is selected from the group comprising a salt or a complex of formic acid and monoethanolamin- ium or cholineaminium. These agents will provide maximum absorption of the sub- stance into wood and retention in the wood. Prefereble organic ammonium carbox- ylate is a mixture of a salt of formic acid and monoethanolamine or formic acid and choline.

IS Active ingredient, which is used in combination with the above mentioned ammo- nium 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 phospho- nate or bisphosphonate (i.e. organic phosphonate i.e. organophosphate) or a mix- 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-pre- serving agent.

Chelate means herein an anion of the chelating agent. = In a case active ingredient (chelating agent) is for example HEDP, a homogenous a 25 aqueous solution (liquid) comprising combination of monoethanolaaminium or cho- S lineaminium cation and HEDP anion, with the compound of formula (3a) or (3b) can 2 be prepared: = a x[NH3CH2CH2(OH)]* + [HEDP]Y —[ HEDPJY [NH3CH2CH2(OH)]** (3a) E x[N(CH3)s(CH2CH2(OH)]* + [HEDP] Y — [(HEDP]Y [N(CH3)s(CH2CH2(OH)] ** S 30 (3b)

N 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.

Monoethanolaminium or cholineaminium phosphates are homogenous agueous solutions (liguids) 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 liguid as a solvent. Suitable surfactant is for example non-ionic surfactant.

Suitable nonionic surfactants are such as alkyl polyglucosides, fatty alcohols in- cluding 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 corro- sion. Its kalium and calcium salts can be used for lowering icing temperature of the — 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 emul- sions based on fatty acids and/or polysaccharides i.e. prevents the phase separa- — 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 so- dium 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 cetylpyri- dinium chloride.

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

o

O oO 25 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 N by preparing it first from its starting material in situ, in other words substantially in 5 contact with wood. Typical starting materials then comprise hydroxide or a salt (such D 30 as chloride) formed by an ammonium ion defined in formula (1a) or (1b) (monoeth- N anolaminium 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

1b), e.g. sodium salt or ammo, resulting mainly in the following reactions (2a) or (2b): x[NH3CH2CH2(OH)X] + (HEDPM,) + R3(COOM)m — [NH3CH2CH2(OH)]*x[HEDP-]y [RXCOO)m] (2a) or x[N(CH3)3(CH2CH2OH)X] + (HEDPM,) + R3(COOM), — [(N(CH3)3(CH2CH2OH)]'n [HEDP], [RKCOO)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, R? is identical to those of formula (1a) and (1b) and 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, 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 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 a instead of water. 2 25 — Preliminary results indicate, that when ammonium carboxylate of formula (1a) or o (1b) is for instance a fluid pair: ethylene amine — formic acid, it can under special I circumstances react and form amide when no solvent is present. Increasing tem- - perature favours amide formation. Nearly no esters are formed.

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

It has now been found that the organic ammonium carboxylate (1a) or (1b, for ex- ample ethanolamine 1-hydroxyethylidene,1,1-diphosphonate or choline 1-hydroxy- ethylidene,1,1-diphosphonate is also suitable for transferring a wood preservative active ingredient into the wood that contains phosphorous chelating agent(s) se- lected from the group comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylene- triaiminepentamethylenephosphonic 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 salt and an organic active ingredient acid.

The invention is based partly on the fact, that both polar poles of ammonium car- boxylate present in formula (1a) or (1b) or ammonium carboxylate present in the ethanolamine phosphonate / carboxylate or choline phosphonate/carboxylate are readily adsorbed and absorbed to the treated wooden material.

The small molecular IS 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, compo- nents and molecules of the wood makes the organic ammonium carboxylate ex- tremely effective in the use of wood treatment.

The wooden material can be easily treated by the organic carboxylate containing — phoshate anions and/or ethanolaminium or cholineaminium phosphate and the or- ganic 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 comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP) ethylenedia- = minetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentameth- N ylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof do not have any = tendency to form precipitates or to foam.

I when wood is treated with the solution comprising ethanolaminium or cholineamin- = 30 ium chelate an/or carboxylate, active ingredient is preferable based on phosphonic O acid, selected from the group comprising 1-hydroxyethylidene,1,1-diphosphonic 0 acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethy- > lenetriaiminepentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof.

This have a flame retardant wood material becomes non-flammable or get better properties against fire (fire protection).

Wood can be treated in sufficiently large amounts with solution containing men- tioned 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 preserv- 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 mi- cro-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 am- IS 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 mix- 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 oO from the group comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), eth- > ylenediaminetetramethylenephosphonic acid (EDTMP) diethylenetriaimine- = pentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereofcon- N 30 taining sodium benzoate, sodium alkyl benzene sulphonate, cetyl pyridinium chlo- 5 ride and a salt of formic acid and ethanolamine. The latter also acts as a well ab- S sorbable organic ammonium carboxylate according to formula (1a).

The organic active ingredient acid component of the active ingredient used for pro- tecting wood from micro-organisms is preferably selected from the group comprising aromatic carboxylic and sulphonic acids, fatty acids, organic hydroxylic acids and their oligomers and chelating acids. Preferred substances comprise benzoic acid, Ce-Coo fatty acid, preferably C12-C1s fatty acid such as stearic acid, and ethylenedi- aminetetraacetic acid (EDTA). A mixture of benzoic acid and a C12-C4s fatty acid such as stearic acid is a particularly advantageous organic active ingredient com- ponent.

An advantageous combination is organic active ingredient acid and organic ingredi- ent 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 guality and guantity selected so as to protect the wood from micro-organisms. In an agueous solution, the weight ratio of organic ammonium carboxylate of formula (1) to water is then particularly in IS therange 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 em- bodiment of the invention does not reguire environmentally hazardous copper and/or zinc to be included in the agueous 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) ethanola- = mine or choline phosphate is used for transferring other substances into the wood N 25 as well. Typical such substances comprise anti-oxidants, free-radical capturers, UV <Q protective agents and wood extractives, such as tannins, described in WO 2 2009/101261 or WO 2009/101262 for Granula Ltd which WO-publications will be E incorporated therein completely.

O Wood is treated by a solution of ethanolaminium or cholineaminium carboxylate of 0 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 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 pro- cess, thus further improving the adsorption and absorption. The invention enables a convenient procedure for the treatment of wood materials in a cost effective man- 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 impreg- nating the wood with this agent or an agueous 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. 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 retention properties. When chelating agent is HEDP the organic ammonium chelate or mixture of ammonium chelate and carboxylate has the formula: x[NH3CH2CH2OH]* + [HEDP] —[ HEDP]” [NH3CH2CH2OH]** (3a) or x[N(CH3)3(CH2CH2OH)]* + [HEDP] Y — [(HEDP] [N(CH3)3(CH2CH2OH)]'* (3b); Or x[NH3CH2CH2(OH)X] + (HEDPM,) + RYCOOM)m — [NH3CH2CH2(OH)]*x [HEDP']y © [R(COO)m] (2a), or

O

N & x[N(CH3)3(CH2CH2OH)X] + (HEDPMy) + RI(COOM)n — [(N(CH3)3(CH2CH2OH]'n oO 25 [HEDP']y [RKCOO)] (2b). E in which R5 is hydrogen, a substituted hydrocarbyl having 1-6 carbon atoms or an N 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. R* is identical to those of 2 formula (1a) and (1b) and X and M are an anion respectively a cation forming a

O N 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.

Active ingredient is selected from the group comprising a phosphonate or a bisphos- phonate or salt thereof or a mixture of chelating agents selected from the group comprising 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP) ethylenedia- minetetramethylenephosphonic acid (EDTMP), diethylenetriaiminepentameth- — 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 relating to the organic ammonium carboxylate in combination with active ingredient and their composition also apply to the wood preservative composition of the inven- tion. 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 preserv- ative composition, R* is preferably hydrogen, methyl or ethyl. R is preferably hy- drogen.

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. Typi- cal chelating agents of this kind are 1-hydroxyethylidene,1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylene- triaiminepentamethylenephosphonic 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 preserva- 2 tive composition containing chelating agent protecting wood from flames.

2 The chelating agent containing wood preservative solution against flames is prefer- E ably in a form of an agueous solution or dispersion having an active ingredient con- N centration 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 2 can contain also surfactans and additives including other kind of active ingredients, S viscocity modifiers, biocides, colouring agents, UV-protecting substances, agents modifying water repellency of composition, stability enhancers etc.

Surfactants are wetting agents that lower the surface tension of a liguid, allowing easier spreading, and lower the interfacial tension in between two liguids. A surfac- tant can be classified by the presence of formally charged groups in its head. A non- ionic surfactant has no charge groups in its head. The head of an ionic surfactant 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 de- pending on the composition to be prepared. The use of tensides i.e. surfactants — further improves the distribution and the penetration of the organic ammonium car- boxylates 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 preserv- ative.

Some commonly encountered surfactants of each type include anionic based on sulfate, sulfonate or carboxylate anions such as sodium dodecyl sulfate , ammo- nium lauryl sulfate, and other alkyl sulfate salts such as sodium laureth sulfate, al- kyl 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 crystalliza- tion and corrosion.

The wood preservative composition according to invention can also include one or several microbisides as additives. 00 > 25 The organic ammonium carboxylate or phosphate may act alone in the composition & or together with another microbicide wood preservative compound as a microbicide, oO protecting wood additionally for microbes. E A microbicide wood preservative compound comprises preferably microbicide active N 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 2 sodium benzoate, sodium alkyl benzene sulphonate, cetyl pyridinium chloride, a salt N 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.

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 en- hance the protection against molds. Further, the drying properties of PHMG are very good which speeds up the treating process. Other polymeric guanidines or poly- 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 — 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 prepar- ing wood by impregnating the wood with this composition. It has also been surpris- 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 pre- vent 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)]* + [HEDP]Y —[ HEDPJY [NH3CH2CH2(OH)]** (3a) 00 N x[N(CH3)3(CH2CH2OH)]* + [HEDP] Y — [(HEDP] [N(CH3)3(CH2CH2OH)] ** 3 (3b)

O > 25 in which R? 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 N are both integers n is an integer between 1-6 as such has wood protecting proper- 5 ties against fire. 0 N The objectives mentioned above have now been achieved with a new method for preparing wood with liquid or water-soluble organic ammonium carboxylate of the type above, in combination with an active ingredient having flame retarding proper- ties. Also the organic ammonium carboxylate having the formula (1a) or (1b) in combi- nation with an active ingredient 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), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaimine- pentamethylenephosphonic acid (DTPMP) or salt thereof or a mixture thereof have flame retarding properties. [NH3CH2CH2(OH)]*n [R*(COO)n]” (1a) Or [N(CH3)3(CH2(CH2(OH)]*n [R(COO)n]” (1b) 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. Such an ammonium carboxylate is readily absorbed in very large amounts into wood and is subsequently retained in the wood. Group R>in formula (1) is preferably hydrogen. The terms "substituted" and "unsubstituted" refer basically to groups con- taining heteroatoms (e.g. -OH, -NH;, -COOH). Depending on the application, ammonium carboxylate or ammonium phosphate can be as a solid form or as a solution. Preferably ammonium carboxylate of formula (1a) or (1b) 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)20H)] * and acid ion [R3(COO)n]™ in formula (1a) and 81b) have been discussed extensively = above and therefore it is not our intention to repeat them in this connection.

N 2 25 Wood is treated by a solution of ammonium carboxylate of formula (1a) or (1b) in o such a way that said solution is adsorbed and absorbed to the wood to be treated I over the whole thickness thereof, or to a certain depth from the surface. The ab- = sorbing and adsorbing properties of ammonium carboxylate and also the general O 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.

If ammonium carboxylate of formula (1) is used as a solution it is prepared as de- scribed 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 com- ponent present in formula (1).

The non-flammability properties of ammonium carboxylate of formula (1a) or (1b) 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 ammo- nium carboxylate 1— 30 % by weight and possible wood preservative containing active ingredient 1 - 45 % by weight, the remainder being substantially water, addi- © tives and surfactants. & S Composition 1 2 I 25 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. O 30 wt-% monoethanolammonium formiate (43 wt-% formic acid and 57 wt-% mo- 0 noethanolamine) > 8.33 wt-% Cublen KT600 (60 wt-% HEDP) 05 wt-% PHMG 20 (20 wt-% PHMG) Cublen is neutralized with monoethanolamine in agueous environment.

1-4 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-% mo- 10 noethanolamine)

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 IS 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 car- & boxylate and chelating agent content compared to those prepared in example 1 or oO 25 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.

N = The chelating agent 1- hydroxyethylidene,1,1-diphosphonic acid (HEDP) used in 2 compositions 1 and 2 can be replaced by other phosphor containing chelating

O N 30 agents such as ethylenediaminetetramethylenephosphonic acid (EDTMP) or dieth- ylenetriaiminepentamethylenephosphonic acid (DTPMP).

Composition 3 Concentrated homogenous solution 53 % HEDP acid (60 %) = 31.8 % w/w calculated from the total weight of the com- position 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. 50 % 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 mo- IS noethanolamine ammonia water: 53.9 % w/w calculated from the total weight of the composition 4. Examples 2-6 © In the following, practical examples will be given of methods how compositions ac- N 20 cording to invention can be used for the treatment of wood and how the treatment S can be integrated in a wood material processing line in mills for wood processing.

O > 2) Pressure impregnation Ao a N A conventional method for entering great amounts of impregnation substance in = wood, and thereby providing the most effective treatment by means of different 2 25 steps (negative pressure and overpressure, elevated temperature). By this method,

O N 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 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 the speed of the line, relatively good penetrability and thereby a reasonable re- sistance to weather and fire can be achieved by this method. © 6) Drying of the wood and the control of final moisture content

O N In the processing of timber in sawmills, it is more and more important that the final <Q 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. E In connection with the drying, the tree often dries to a moisture content that is lower N than desired. At the end, the moisture content can be adjusted, for example, by a = technigue based on spraying with water. In this step, it is very easy to add the com- 2 position according to the invention into the wood, wherein it is possible to eliminate

O N 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 short- term 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. Bythe solution of the invention, it possible to facilitate the treatment of wood under winter conditions where the processing of frozen wood (for example, melting, im- pregnation, planning, painting, etc.) is problematic and constitutes an extra cost item. Usually ammonium carboxylate of formula (1) as mentioned above is absorbed into 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 IS 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 pre- paring above mentioned chelating agents.

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

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. IS Table 1 Ammonium carboxylate carriers selected for the tests. Ammonium carboxylate carrier Proportion of total carrier, % MHEA/PHEA 70/30 00

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O - MH = formic acid (actually its anion, i.e. formiate) a a N EA = ethanolamine (actually its cation, i.e. ethanolammonium) = PH = propionic acid (actually its anion, i.e. propionate) 0 S 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 accord- ance with table 1. Table 2 Active ingredient and carrier mixtures used in decay tests 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% 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 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 N 15 (ref.) - 100% of White Spirit <Q 2 5 E EDTA = ethylenediaminetetraacetic acid N CEBE2 = 43% of MHEA + 43% of cetyl pyridinium benzoate + 9% Pre- = ventol MP100 + 526 EDTA 2 CEOS = 13% of stearic acid + 33% of lactic acid-oligomer + 6% of N 10 cetyl pyridium chloride + 48% of MHEA BHTEB = 5% of Preventol A8 + 5% of benzoic acid + 90% of MHEA BEPRE 100 = 4% of Preventol MP100 +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 00

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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 00 IBPC = 3-iodine-2-propynylbutylcarbonate

O 3 2.3 Extraction tests of the wood material 2 Oven-dry pine surface samples (15 x 15 x 5 mm) were extracted under five different E 5 extraction schedules (schedules 1 - 5). Unprocessed (unextracted) wood samples N were used as reference material for the extracted wood material.

LO 3 Extraction schedule 1, Water extraction

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

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 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 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 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 extrac- 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.

O N 2.4. Biological effectiveness of mixtures of active ingredient and ancat and extracted <Q wood

O I 25 2.4.1 Decay tests a N Small pine surface samples (15 mm x 15 mm x 5 mm) were vacuum impregnated 5 with the active ingredient carrier mixture under study (table 2). Untreated samples D and samples treated merely with ancat carriers or a White Spirit solvent were used N as a reference. The brown-rot fungus Coniophoraputeana, BAM Ebw was selected as the test fungus. The fungus strain is derived from the strain collections of VTT Technical Research Centre of Finland, Building, Built Environment.

The amounts of mixtures of active ingredient-carrier absorbed into the samples (re- tention kg/m?) were determined by calculatory means and dry basis weighing (dry weights of the samples before and after impregnation and rinsing). Part of the sam- ples was rinsed with water before the decay tests were started. The rinsing was 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 opera- tion. 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 IS 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.

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 N 25 thrive in wood: Aspergillus versicolor (E1), Gladosporium sphaerospermum (R7) <Q and Penicillium sp. (1017). The blue stain suspension consisted of the following 2 species: Aureobasidium pullulans (T1), Sclerophoma entoxylina (Z17) and Cerato- E cystispilifera (Z11). The fungus strains are derived from the strain collections of VTT N 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.

N 0= nogrowth s1 = marks of starting growth (microscopically observable) 2= 1-10% of the area covered by microbial growth (microscopically observable)

3= 10-30% of the area covered by microbial growth (visually observable) 4 = 30-70% of the area covered by microbial growth (visually observable) = 100% of the area covered by microbial growth (visually observable) 5 3. Results

3.1 Anti-decay effect of the mixtures of active ingredient and carrier and the extrac- tion 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 —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, when notrinsed, 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 pre- servative contained tebuconazole-MHEA, tebuconazole-MHEA+PREA, CEBE2- 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).

N 2 25 Whenunrinsed, both the ancat carriers prevented efficiently the weight loss caused o by rot fungus in the test samples. The effectiveness of MHEA+PREA decreased I 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 O and WhiteSpirit proved to have a high anti-decay effect both when rinsed and not o 30 rinsed.

N The objective of the extraction tests was to determine whether removal of e.g. sol- uble sugars or structural components soluble in the carrier increases the decay re- sistance 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 ma- terial. 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 (weight losses > 30 %). By contrast, in samples treated under extraction schedules 3 (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/m?. Rinsing had no notable effect on the absorption. Table 4. Active ingredient contents in the test samples after impregnation and rins- ing. Example Mixture active ingredient-carrier Retention kg/m? Not rinsed Rinsed 13 MHEA 201 194 14 MHEA+PREA 182 182 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 o - 7 CEBE2-MHEA 205 208 = 8 CEOS-MHEA 231 233 N 30 9 BHTEB-MHEA 235 235 5 10 BEPRE100-MHEA 236 228 3

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

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 ma- terial 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 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 pre- sent on the material surface. The damages caused by mildews relate to discolour- ation 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 mix- tures of active ingredient and carrier, to the susceptibility of blue stain fungi to the compounds under study and/or to transfer of the active ingredients also to the un- treated 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 exam- ples are given in table 3. Mildew growth was prevented completely in an exposure test of 10 weeks when the samples were treated with the following mixtures of active ingredient and carrier: benzoic acid-MHEA- (example 18), benzoic acid- MHEA+PREA (example 19), EDTA-MHEA in acid form (example 20), EDTA-MHEA- PREA in acid form (example 21), SBB-MHEA (example 22), CEBE2-MHEA (exam- ple 23) and BEPRE100-MHEA (example 26) and SBBW30-WhiteSpirit. In untreated 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 expo- oO sure (mildew growth not yet visible). Moderate mildew growth (mildew index 2) was > 30 also observed in test samples treated with active ingredient mixtures of CEBE2- = MHEA (example 23) and CEOS-MHEA (example 24).

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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 (ex- 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 un- der 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 pre- ventive 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, CEBE2, BHTEB, BEPRE 100-MHEA, CEOS). The decay tests also determined the effect of SBB dissolved in a WhiteSpirit 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 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 pro- duced by the company Granula Oy. © The mildew and blue stain tests, in turn, determined the anti-mildew effect and anti- > 25 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, oO BEPRE 100-MHEA in acid form) and SBB dissolved in a WhiteSpirit solvent.

The > test results showed that the mixtures of active ingredient and carrier actively pre- = vented mildew growth on the surface of the treated wood samples during an expo- N 30 sure period of 10 weeks.

No blue staining was observed.

This result may be due to 5 excessive moisture of the samples, which in turn was caused by the hydroscopicity D of the mixtures of active ingredient and carrier, to the susceptibility of blue stain fungi N 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 was inhibited in the cases where the wood material contained a carrier after the extraction. 00

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Claims (21)

Patenttivaatimukset

1. Koostumuksen, joka käsittää nestemäistä tai vesiliukoista ammoniumia yhdistel- mänä tehoainehapon kanssa, jolloin ammonium perustuu monoetanoliaminium- tai — koliiniaminiumkationiin, ja tehoainehappo perustuu kelatointiaineeseen (kelaatti), joka sisältää molekyylirakenteessaan fosforia (P), ja joka koostumus on läsnä vesi- pitoisessa liuoksessa, dispersiossa tai emulsiossa, joka koostumus käsittää lisäksi tehoainetta, joka on puuta säilyttävä liuos, joka sisältää mikrobisidisen tehoaineen lisäaineena, joka mikrobisidinen tehoaine on orgaanisen tehoainesuolan ja orgaa- — nisen tehoainehapon seos tai reaktiotuote, ja joka koostumus voi lisäksi sisältää lisäkomponentin, joka on valittu muista tehoai- neista, mahdollisista ionisista lisäliuottimista, lisäaineista ja pinta-aktiivisista aineista koostuvasta ryhmästä, koostumuksen loppuosan ollessa vettä, — käyttö puun palamista hidastavana ja mikrobisidisenä aineena.

2. Patenttivaatimuksessa 1 määritelty käyttö, tunnettu siitä, että vesipitoisen liuok- sen, dispersion tai emulsion kiintoainepitoisuus on yli 30 painoprosenttia, laskettuna koostumuksen kokonaispainosta.

3. Patenttivaatimuksessa 1 tai 2 määritelty käyttö, tunnettu siitä, että koostumus — sisältää kelatointiainetta, jolla on palamista hidastavia ominaisuuksia, 10-45 paino- prosenttia, edullisesti 30-45 painoprosenttia koostumuksen kokonaispainosta. N 4. Patenttivaatimuksessa 1 määritelty käyttö, tunnettu siitä, että mikrobisidisen te- N hoaineen orgaaninen tehoainehappo on bentsoehappo, C6-C20 -rasvahappo, edul- N lisesti steariinihappo, etyleenidiamiinitetraetikkahappo (EDTA), tai näiden sekoitus. 00

O I 25 5 Patenttivaatimuksessa 1 määritelty käyttö, tunnettu siitä, että mikrobisidinen te- = hoaine on bentsalkoniumkloridi (alkyyliketjujen alkyylibentsyylidimetyyliammonium- O kloridieita, joissa alkyyliketjun pituus vaihtelee) tai polyheksametyleeniguanidini co (PHMG).

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6. Patenttivaatimuksessa 1 tai 5 määritelty käyttö, tunnettu siitä, että orgaaninen —tehoainesuola on valittu ryhmästä, joka käsittää alkalimetallin alkalimetalli- ja maa-

alkalimetallisuolat, alifaattisten ja aromaattisten sulfonihappojen maa-alkali - ja am- moniumsuolatja amiinien happosuolat.

7. Patenttivaatimuksessa 7 määritelty käyttö, tunnettu siitä, että orgaaninen te- hoainesuola on valittu ryhmästä, joka käsittää natriumbentsoaattia, natriumalkyyli- bentseenisulfonaattia, setyylipyridiniumikloridia.

8. Jossakin edellisessä patenttivaatimuksessa määritelty käyttö, tunnettu siitä, että fosforia (P) sisältävä kelatointiaine on 1-hydroksietyylideeni, 1,1-difosfoni- happo (HEDP), etyleenidiamiinitetrametyleenifosfonihappo (EDTMP) tai dietyleenit- riamiinipentametyleenifosfonihappo (DTPMP), tai näiden suola, tai näiden seos.

9. Patenttivaatimuksessa 1 määritelty käyttö, tunnettu siitä, että koostumus si- sältää lisäksi ionitonta pinta-aktiivisuusainetta, joka valitaan ryhmästä, joka koostuu oktaanihaposta, alkyylipolyglukosidista, rasva-alkoholista mukaan lukien setyylial- koholi ja oleyylialkoholi.

10. Patenttivaatimuksessa 9 määritelty käyttö, tunnettu siitä, että ioniton pinta- — aktiivisuusaine käsittää myös alkalimetalli- ja maa-alkalimetallisuolat.

11. Patenttivaatimuksessa 1 määritelty käyttö, tunnettu siitä, että koostumus si- sältää lisäksi lisäaineita, kuten MgCO3, AI(OH)3, silikayhdisteitä ja vaahtoutumista ehkäiseviä aineita.

12. Jossakin edellisessä patenttivaatimuksessa määritelty käyttö, tunnettu siitä, — että mainittu käyttö käsittää puun käsittelyn vähintään kerran kyllästämällä, suihkut- tamalla tai maalaamalla yhdisteellä, joka käsittää neste- tai vesiliukoista monoeta- noliaminiumkarboksylaattia/-kelaattia ja/tai koliiniaminiumkarboksylaatilla/-kelaatilla N ja/tai monoetanoliaminiumkelaatilla ja/tai koliiniaminiumkelaatilla, joka kelaatti on N peräisin kelatointiaineesta, joka sisältää molekyylirakenteessaan fosforia (P).

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13. Patenttivaatimuksessa 12 määritelty käyttö, tunnettu siitä, että puu käsitel- 7 lään kerran tai kaksi kertaa samalla tai eri yhdisteellä.

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14. Menetelmä konsentroidun paloa hidastavan koostumuksen valmistamiseksi, kä- S sittäen neste- tai vesiliukoista orgaanista ammoniumyhdistettä yhdessä tehoaineen 2 vaikuttavan aineen , joka sopii puun syttymisen tai palamisen ehkäisemiseen, tun-

O N 30 — nettu siitä, että monoetanoliaminium [NH3CHCH2OH]* -ioni tai koliiniaminium [N(CH3),CH2CH2(OH)]* -ioni saatetaan reagoimaan tehoainehapon kanssa, joka käsittää kelatointiainetta, joka sisältää molekyylirakenteessaan fosforia, ja jossa vesipitoisen liuoksen pH on 5-8, sen jälkeen, kun monoetanoliaminium [NH3CH2CH2OH]* -ioni tai koliiniaminium [N(CH3)sCH2CH2(OH)]* -ioni on saatettu reagoimaan tehoainehapon kanssa, jolloin mainittu menetelmä käsittää lisäksi lisä- aineen, joka on mikrobisidinen tehoainene, lisäämisen, joka mikrobisidinen teho- aine on orgaanisen tehoaineen suolan ja orgaanisen tehoaineen hapon seos tai reaktiotuote.

15. Patenttivaatimuksessa 14 määritelty menetelmä, tunnettu siitä, että mikro- bisidisen tehoaineen orgaaninen tehoainehappo on bentsoehappo, C6-C20 -rasva- happo, edullisesti steariinihappo, etyleenidiamiinitetraetikkahappo (EDTA), tai näi- den seos.

16. Patenttivaatimuksessa 14 määritelty menetelmä, tunnettu siitä, että mikrobisidi- nen tehoaine on bentsalkoniumkloridi (alkyylibentsyylidimetyyliammoniumklori- dieita, joissa alkyyliketjun pituus vaihtelee) tai polyheksametyleeniguanidini (PHMG).

17. Patenttivaatimuksessa 14 määritelty menetelmä, tunnettu siitä, että orgaani- nen tehoainesuola on valittu ryhmästä, joka käsittää alkalimetallin alkalimetalli- ja maa-alkalimetallisuolat, alifaattisten ja aromaattisten sulfonihappojen maa-alkali- ja ammoniumsuolat ja amiinien happosuolat.

18. Patenttivaatimuksessa 14 määritelty menetelmä, tunnettu siitä, että orgaani- — nentehoainesuola on valittu ryhmästä, joka käsittää natriumbentsoaattia, natriumal- kyylibentseenisulfonaattia, setyylipyridiniumikloridia.

19. Patenttivaatimuksessa 14 määritelty menetelmä, tunnettu siitä, että reaktio suoritetaan veden ja mahdollisen ionisen lisäliuottimen läsnäollessa.

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20. Patenttivaatimuksessa 14 määritelty menetelmä, tunnettu siitä, että orgaanisen = 25 ammoniumyhdisteen kuivakiintoainepitoisuus on 15-45 painoprosenttia kokonais- © koostumuksesta, ja tehoaineen, joka käsittää molekyylirakenteessaan fosforia I (edullisesti fosfonaattia kuten HEDP) sisältävää kelatointiainetta, kuivakiintoainepi- = toisuus on 10-40 painoprosenttia, edullisesti 30-40 painoprosenttia kokonaiskoos- o tumuksesta. = 30

21. Patenttivaatimuksessa 14 määritelty menetelmä, tunnettu siitä, että reaktio N suoritetaan veden ja mahdollisen ionisen lisäliuottimen läsnä ollessa saattamalla vesiliukoinen monoetanoliaminium [NH3CH2CH2OH]* -ioni tai koliiniaminium [N(CH3)3CH2CH>2(OH)]* — -ioni — reagoimaan tehoaineen, joka = käsittää molekyylirakenteessaan fosforia sisältävää kelatointiainetta pinta-aktiivisen aineen, edullisesti ionittoman pinta-aktiivisen aineen läsnäollessa.

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