Treatment of wood with polyorganosiloxanes.

Abstract

The present application relates to a method for treating lignocellulosic material with at least one polyorganosiloxane compound, the polyorganosiloxane compound having a polyorganosiloxane backbone and a polyorganosiloxane compound of formula (I): JPEG2025500773000018.jpg2536 (in the above formula, R 2 , R 3 , R 4 are, independently of one another, linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, optionally containing one or more heteroatoms of O, S, N, C1-C 45 represents a hydrocarbon residue, The polyorganosiloxane includes at least one ammonium group residue (where * represents a bond site attached to the polyorganosiloxane backbone).

Description

[Technical field]

[0001] The present application relates to a method for treating lignocellulosic materials with polyorganosiloxane compounds to enhance the biological durability of the lignocellulosic materials, and further relates to lignocellulosic materials impregnated with polyorganosiloxane compounds. [Background technology]

[0002] background Finishing methods and chemicals for wood and lignocellulosic materials using preservative chemicals and agents that provide biological durability and dimensional stability are continuously being investigated in the art. Wood treatment agents known in the art often contain heavy metal components to achieve the desired finishing performance of wood and lignocellulosic materials. However, it is inevitable that such heavy metal-containing agents will migrate into the environment and thus impose a harmful burden on living organisms. Therefore, it is a general goal of the art to reduce the use of heavy metal-containing wood treatment agents in the treatment of lignocellulosic materials.

[0003] Natural wood has the problem of low biological durability and dimensional stability. When such natural wood is used in an outdoor environment, the wood alternately absorbs and releases moisture under changing weather conditions, causing the wood to shrink and expand in dimensions. Furthermore, the absorption of moisture makes the wood more susceptible to attack by wood-damaging fungi. Therefore, research has focused on wood modifiers that can enhance the biological durability and moisture resistance of wood and lignocellulosic materials.

[0004] One approach to meet the above requirements is the impregnation of wood with polyorganosiloxane compounds. Commonly known methods using these finishes require high temperature curing and reaction steps during impregnation of wood and lignocellulosic materials. Generally, temperatures above 100° C. are used to finish wood and lignocellulosic materials with said polyorganosiloxane compounds. However, from an industrial point of view, it is desirable to carry out such curing and reaction steps at lower temperatures, since impregnation plants in the wood industry are often limited to a maximum temperature of 80° C. Therefore, commonly known methods / techniques using known polyorganosiloxanes (curing and drying at temperatures above 100° C.) cannot be easily implemented with equipment available on an industrial scale and require additional investment costs in special drying equipment and specific process know-how.

[0005] DE 10 2004 036 918 A1 discloses protective agents for lignocellulosic materials which are characterized in that they contain amino-modified polymeric silicones.

[0006] WO 2012 / 143371 A1 discloses functionalized polyorganosiloxanes or silanes for the treatment of lignocellulosic materials, the polyorganosiloxanes comprising functional groups.

[0007] WO 2014 / 111514 A1 discloses a method for treating cellulosic substrates with functionalized polyorganosiloxanes containing aromatic, heteroaromatic and amino functional groups.

[0008] DE 10 2012 103 372 A1 discloses amino-functional polysiloxanes as protective agents for lignocellulosic materials.

[0009] In view of the deficiencies existing in the state of the art, there is a constant need to improve the biological durability and dimensional stability of wood and lignocellulosic materials by impregnation with heavy metal-free wood treatment agents without the need for high curing temperatures. Summary of the Invention

[0010] Summary of the Invention In one of the first aspects of the present invention, the above object is achieved by the following items.

[0011] Item 1: 1. A method for treating lignocellulosic material with at least one polyorganosiloxane compound, the polyorganosiloxane compound having a polyorganosiloxane backbone and formula (I): [ka] (In the above formula, R 2 , R 3 , R 4 are each independently a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted C1-C 45 represents a hydrocarbon residue, optionally containing one or more heteroatoms O, S, N, * represents a bond site attached to said polyorganosiloxane backbone) and at least one ammonium group residue.

[0012] Item 2: R 2 , R 3 , R 4 are, independently of one another, C1 or C2 saturated or C2 unsaturated hydrocarbon residues, and / or linear, cyclic or branched saturated or unsaturated C3-C 45 The method according to item 1, which represents a hydrocarbon.

[0013] Item 3: R 2 , R 3 , R 4 are, independently of one another, saturated C1 or C2 hydrocarbon residues and / or linear, cyclic or branched saturated C3-C 20 3. The method according to item 1 or 2, wherein the hydrocarbon is represented.

[0014] Item 4: The polyorganosiloxane compound is a C1 to C 20The method of any one of the preceding items, further comprising at least one divalent moiety -R- consisting of a saturated or unsaturated, linear or branched hydrocarbon residue, optionally containing one or more heteroatoms of O, S, N, and at least one ammonium group residue of formula (I) bonded to the siloxane portion of the polyorganosiloxane backbone via a bonding site *.

[0015] Item 5: The polyorganosiloxane compound has the formula (II): [ka] (In the above formula, R 1 and R 5 are each independently an organic aliphatic C1-C6 residue or a divalent moiety -R- as defined in claim 4, at least one ammonium group residue of formula (I) is bonded to the siloxane moiety via a bonding site *, and at least 1, preferably 2, or preferably at least 10, preferably at least 20 R 1 is R in the compound of formula (II) 5 together represent a divalent moiety -R-, m + represents m times the positive charge assigned by the polyorganosiloxane compound, mA - is a charge-balancing anion A selected from the group consisting of halides, hydroxides, 1 / 3 borates, 1 / 2 sulfates, 1 / 2 phosphates, nitrates, carboxylates, or mixtures thereof; - represents The method according to any one of the preceding items, wherein n represents a number average degree of polymerization and is 9 to 200, preferably 30 to 150, preferably 35 to 75, and preferably 40 to 60.

[0016] Item 6: R 1 represent, independently of each other, an organic aliphatic C1-C6 residue, R 5represents the divalent moiety -R- according to item 4, and at least one terminal, preferably two terminal ammonium group residues of formula (I) are bonded to the siloxane moiety via bonding site*.

[0017] Item 7: Item 11. The method according to any one of the preceding items, wherein the weight average molecular weight of the polyorganosiloxane compound is in the range of 2.000 g / mol to 12.000 g / mol.

[0018] Item 8: Treating the lignocellulosic material with at least one polyorganosiloxane compound comprises the steps of: a) optionally pre-drying the lignocellulosic material; b) impregnating the lignocellulosic material with an aqueous composition comprising the polyorganosiloxane compound according to any one of claims 1 to 6; c) drying the impregnated lignocellulosic material; 2. The method according to any one of the preceding items, comprising:

[0019] Item 9: The process according to item 8, wherein the step c) is carried out at a temperature of 20 to 120°C, 30 to 120°C, 40 to 120°C, 50 to 120°C, preferably 50 to 100°C, preferably 60 to 85°C.

[0020] Item 10: 10. The process according to item 8 or 9, wherein step b) is a vacuum pressure impregnation process carried out in the pressure range from 5 mbar to 20 bar.

[0021] Item 11: 11. The method according to any one of items 8 to 10, wherein in step a) the lignocellulosic material is pre-dried until the residual relative moisture content is less than 0.1-20%, preferably 0.1-15%.

[0022] Item 12: 12. The method according to any one of items 8 to 11, wherein the aqueous composition is free of heavy metals.

[0023] Item 13: A process for treating lignocellulosic material with at least one polyorganosiloxane compound, preferably in the form of an aqueous composition, at a temperature below 100°C.

[0024] Item 14: 15. The method according to any one of items 8 to 14, wherein the aqueous composition comprises the polyorganosiloxane compound in an amount of at least 0.1 wt% to at most 90 wt%, or at least 0.5 wt% to at most 80 wt%, or at least 1 wt% to at most 60 wt%, or at least 2 wt% to at most 40 wt%, or at least 2.5 wt% to at most 30 wt%, or at least 2.5 to at most 20 wt%, or at least 4 wt% to at most 20 wt%, or at least 5 wt% to at most 15 wt%, or at least 6 wt% to at most 15 wt%, or at least 7 wt% to at most 12 wt%, or at least 7 wt% to at most 10 wt%, based on the total weight of the aqueous composition.

[0025] In a second aspect of the present invention, the above object is achieved by the following items.

[0026] Item 15: 15. A lignocellulosic material treated by the method according to any one of items 1 to 14.

[0027] Item 16: 16. The lignocellulosic material according to item 15, characterized in that the mass % gain after drying and leaching measured according to DIN EN 84-2020-10 (formerly DIN EN 84-2018-10) is not more than 7%, preferably 5-7%, and / or the swelling coefficient measured according to the procedure described herein is not more than 14%, preferably 12-13%, and / or the mass loss due to fungal decay of brown rot pathogens measured according to EN 113-2 (2021) (formerly: CEN / TS 15083-1 (2005)) is less than 5%.

[0028] In a third aspect of the present invention, the above object is achieved by the following items.

[0029] Item 17: Use of an aqueous composition comprising the polyorganosiloxane compound according to any one of items 1 to 7, or the polyorganosiloxane compound according to items 8 to 12 or 14, as a treatment agent for lignocellulosic materials.

[0030] Item 18: Use of an aqueous composition comprising a polyorganosiloxane compound according to any one of items 1 to 7, or a polyorganosiloxane compound according to items 8 to 12 or 14, for increasing the water absorption resistance and / or dimensional stability and / or weather resistance and / or biological resistance, in particular the resistance to wood-damaging fungi and / or marine borers and / or wood pests, of a lignocellulosic material. [Brief description of the drawings]

[0031] (No original text) DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] Description of the Invention In one aspect, the invention relates to a method of treating lignocellulosic material with a polyorganosiloxane compound, the polyorganosiloxane compound having a polyorganosiloxane backbone and a polyorganosiloxane having formula (I): [ka] (In the above formula, R 2 , R 3 , R 4 are each independently a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted C1-C 45 represents a hydrocarbon residue, optionally containing one or more heteroatoms of O, S, N, and * represents a bond site attached to the polyorganosiloxane backbone, and contains at least one ammonium group residue. 2 , R 3 , R 4represent, independently of one another, a C1 or C2 saturated or C2 unsaturated, substituted or unsubstituted hydrocarbon residue, optionally containing one or more heteroatoms of O, S, N, and / or R 2 , R 3 , R 4 are each independently a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted C3-C 45 represents a hydrocarbon residue, optionally containing one or more heteroatoms of O, S, N, and * represents a bond site attached to the polyorganosiloxane backbone.

[0033] Furthermore, the present invention relates to a method for treating lignocellulosic material with a polyorganosiloxane compound at a temperature below 100°C, preferably below 95°C, more preferably below 90°C, more preferably below 85°C.

[0034] By using the method as described, the basic requirements for carrying out the impregnation method of lignocellulosic materials in industrial plants are met. In particular, the above method allows low impregnation temperatures below 100°C so that the described method can be used in conventional wood impregnation plants. Furthermore, it has been found that a permanent increase in biological durability can be achieved when the method of the invention is applied to lignocellulosic materials. Furthermore, an improved resistance to alternating moisture and therefore improved weathering resistance under outdoor conditions has been observed.

[0035] The term "polyorganosiloxane" in the context of this application refers to an oligomeric or polymeric siloxane compound having organic residues. In general, the molecular structure of polyorganosiloxanes is characterized by silicon atoms linked in a chain through oxygen atoms to form a -Si-O- backbone, where the silicon atoms have further organic residues bonded to the silicon atoms through carbon-silicon bonds. In general, the polyorganosiloxanes envisaged in the present invention contain repeat units of type (A) or (B), i.e. organosilicone repeat units, and can be either type (A) or type (B). [ka] represents a repeat unit bonded to a linear skeletal structure or to a branched skeletal structure. The subscripts n and m represent the number of repeat units (A) and (B) in the polyorganosiloxane. The number n can be 9 to 200, or 30 to 150, or 35 to 125, or 40 to 100. The number m can be 0 to 15, or 3 to 12, or 5 to 10. The polyorganosiloxane is of type (C). [ka] The number of terminal groups in the polyorganosiloxane compound can range from 0 to 17, or 0 to 15, or 2 to 15, or 5 to 14, or 7 to 12. R in (A), (B) and (C) org represents an organic saturated or unsaturated linear, branched or cyclic aliphatic or aromatic residue; R org optionally includes heteroatoms O, S, and N, and each R org may be the same or different from each other. org At least one of the groups is a divalent residue capable of bonding to the bonding site* of the ammonium group residue of formula (I). The polyorganosiloxane can have a linear, branched or cyclic backbone structure.

[0036] The term "ammonium group residue" refers to the residue R specified above and below. 2 , R 3 , R 4 and further bonded to the polyorganosiloxane backbone via a bond site *. As outlined above, the divalent residue -R- can bond the ammonium group residue of formula (I) to the Si atom of the polyorganosiloxane backbone. R orgThe number of ammonium group residues bonded to the polyorganosiloxane skeleton via may be at least 1, or at least 2, or at least 10, or at least 20, or at least 1 to 25, or at least 1 to 20, or at least 1 to 15, or at least 1 to 10, or at least 1 to 5, or at least 2 to 4, or 2, or 3, depending on the size of the polyorganosiloxane compound. In one embodiment, the ammonium group residue is located at at least one end of the polyorganosiloxane skeleton, i.e., a terminal ammonium group residue located at one or both ends of a linear polyorganosiloxane skeleton, or at least one end, two ends, three ends, or up to 20 ends of a branched polyorganosiloxane skeleton. The size of the polyorganosiloxane compound essentially depends on the number n and / or m of repeat units (A) and / or (B), and the number of terminal groups (C). It is desirable to match the number of ammonium group residues with the number of organosilicone units (A), (B) and (C).Typically, the ratio of ammonium group residues to the sum of organosiloxane groups (A), (B) and / or (C) can range from 1:5 to 1:105, or from 1:10 to 1:90, or from 1:20 to 1:75, or from 1:30 to 1:50.

[0037] Residue R bonded to the quaternary nitrogen atom of the ammonium group residue 2 , R 3 , R 4 In one embodiment, may be independently selected from a methyl or ethyl group or an ethylene group. One or more heteroatoms O, S, N that may be bonded to the C1 or C2 residue may be structured with -OH, SH, NH2, or =O, =S, =NH groups, or in the case of the C2 residue, may have the structure -O-, -S-, -NH-.

[0038] Also, R 2 , R 3 , R 4may additionally or alternatively, independently of one another, be linear, cyclic or branched, saturated or unsaturated, C3-C 45 It can represent a hydrocarbon residue. The structures of the O, S, and N atoms can be as described above. R 2 , R 3 , R 4 A particular group of -(CH2)2-NH2, -(CH2)3NH(CH2)2-NH2, -(CH2)3N(CH3)2, -(CH2)5-NH2, -CH2-CH2-NH2, -CH2CH2-NH-CH2CH2-NH-C4H9, or -(CH2)2-OH, -(CH2)2O(CH2)2-OH, -(CH2)2O-CH3, -(CH2)5-OH, -CH2-CH2-OH, -CH2CH2-O-CH2CH2-O-C4H9, or Alkyl or alkoxy groups, in particular dihydroxyethyl, hydroxypropyl, dihydroxypropyl, trihydroxypropyl, hydroxyisopropyl, hydroxybutyl, dihydroxybutyl, trihydroxybutyl, hydroxyisobutyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy and / or isobutoxy, or Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentriacontyl, dotriacontyl, tritriacontyl, tetratriacontyl, pentatriacontyl, hexatriacontyl, heptatriacontyl, octatriacontyl, nonatriacontyl, tetracontyl, hentiracontyl, dotetracontyl, tritetracontyl, tetratetracontyl, pentatetracontyl and isomers thereof, or These include isopropyl, isobutyl or saturated or unsaturated straight chain, cyclic or branched hydrocarbons having up to 20 carbon atoms, alicyclic such as allyl or butadienyl or cyclohexyl groups, or aromatic groups such as phenyl, naphthyl or benzyl.

[0039] The positive charge of at least one ammonium group residue in the polyorganosiloxane compound is counterbalanced by an anion that can be selected from the group consisting of halides, hydroxides, borates (1 / 3), sulfates (1 / 2), phosphates (1 / 3), nitrates and carboxylates or mixtures thereof. The halides can be in the form of chlorides, bromides and iodides or mixtures thereof.

[0040] The term "lignocellulosic material" in the context of this application refers to materials such as solid wood, particle board, fiberboard, oriented strand board, wood-based composites such as veneer-based composites (e.g. plywood, LVL), or other wood-based materials such as paper, cardboard, insulation board, etc. In one embodiment according to the invention, the lignocellulosic material treated in the method according to the invention is paper, packaging material, wood or a wood-based composite.

[0041] According to a first aspect, the present invention provides a method for the preparation of a compound comprising the steps of: 2 , R 3 , R 4 are each independently a C1 or C2 saturated or C2 unsaturated hydrocarbon residue, and / or a linear, cyclic or branched saturated or unsaturated C3-C 45 R is a method for representing hydrocarbons. 2 , R 3 , R 4Particular groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentriacontyl, dotriacontyl, tritriacontyl, tetratriacontyl, pentat ... Contyl, hexatriacontyl, heptatriacontyl, octatriacontyl, nonatriacontyl, tetracontyl, hentetracontyl, dotetracontyl, tritetracontyl, tetratetracontyl, pentatetracontyl and their isomers, or isopropyl, isobutyl or saturated or unsaturated hydrocarbon straight chain, cyclic or branched, hydrocarbon having up to 20 carbon atoms, alicyclic such as allyl or butadienyl or cyclohexyl groups, or aromatic groups such as phenyl, naphthyl or benzyl.

[0042] According to a first aspect, the present invention provides a method for the preparation of a compound comprising the steps of: 2 , R 3 , R 4 are each independently a C1 or C2 saturated hydrocarbon residue, and / or a linear, cyclic or branched saturated C3-C 20 According to this embodiment, R 2 , R 3 , R 4 Particular groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or isopropyl, isobutyl, or a saturated or unsaturated hydrocarbon, linear, cyclic or branched, having up to 20 carbon atoms, allyl or butadienyl, or an alicyclic, such as a cyclohexyl group, or an aromatic group, such as a phenyl, naphthyl or benzyl group.

[0043] In one embodiment according to the invention, the residue R 2 , R3 , R 4 does not contain heteroatoms O, S, N, i.e., the residue R 2 , R 3 , R 4 does not include any of the heteroatoms O, S, or N. Thus, in such embodiments, these residues R 2 , R 3 , R 4 All other embodiments described above and below which require a heteroatom O, S, N are not included in this embodiment.

[0044] According to a first aspect, the present invention provides a polyorganosiloxane compound having a C1 to C 20 The present invention also relates to a method of preparing a polyorganosiloxane comprising the steps of: (a) a polyorganosiloxane having a structure in which the siloxane moiety is a siloxane moiety having at least one divalent moiety, -R-, which comprises a saturated or unsaturated, linear or branched hydrocarbon residue of the formula (I) and optionally contains one or more heteroatoms O, S, N, and which has at least one ammonium group residue of formula (I) bonded to the siloxane moiety via a bonding site *; org The group corresponds to the divalent moiety -R-. The number of divalent moieties -R- in the polyorganosiloxane compound can be at least 1, or at least 2, or at least 3, or at least 5, or at least 7, or at least 10, and can be 25 or less, or 20 or less, or 15 or less, or 13 or less, or 10 or less, or from 1 to 25, or from 1 to 20, or from 1 to 15, or from 1 to 10, or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 5, or 4, 3, or 2.

[0045] One or more heteroatoms O, S, N in at least one divalent group -R- represent -OH, -SH, -NH2 or =O, =S, =NH or -O-, -S- or -NH-. In a preferred embodiment, the divalent moiety -R- is -(CH2) 1-20 -, -(CH2) 1-10 -(CH(CH2) 1-5-(CH2) 1-10 -or-(CH2) 1-10 -(NH)-(CH2) 1-10 -or-(CH2) 1-10 -(NH)-(CH2) 1-10 -(CHNH2)-(CH2) 1-10 or -((CH2)2-NH-) 1-7 (CH2) 1-6 -, -(CH2-CH2-NH) 1-7 (CH2) 1-6 -, -(CH2) 1-10 -(NH)-(CH2) 1-10 -(NH)-(CH2) 1-10 -, -((CH2)2-O-) 1-7 (CH2) 1-6 -or-(CH2) 1-5 -(CHOH)-(CH2) 1-6 -or-(CH2) 1-8 -O-(CH2) 1-5 -(CHOH)-(CH2) 1,2 - represents.

[0046] According to a first aspect, the present invention provides a polyorganosiloxane compound having the formula (II): [ka] (In the above formula, R 1 represent, independently of each other, an organic aliphatic C1-C6 residue or a divalent moiety -R- which bonds at least one ammonium group residue of formula (I) to a siloxane moiety as specified in the present application via a bonding site *, where R in the compound of formula (II) 5 together with at least 1, or at least 5, preferably at least 10, preferably at least 15, preferably at least 20 R 1 represents the divalent moiety -R-, m + represents the m-fold positive charge assigned to the polyorganosiloxane compound, and mA - is a charge-balancing anion A selected from the group consisting of halides, hydroxides, 1 / 3 borates, 1 / 2 sulfates, 1 / 3 phosphates, nitrates, carboxylates, or mixtures thereof;- and n represents a number average degree of polymerization, which is 9 to 200, preferably 30 to 150, preferably 35 to 75, preferably 40 to 60. 1 each independently represents an organic aliphatic C1-C6 residue, R 5 represents a divalent moiety -R- as defined in this application, linking at least one terminal, and preferably two terminal ammonium group residues of formula (I) to the siloxane moiety via a linking site *.

[0047] The ammonium group residues are bonded to the polyorganosiloxane backbone via the divalent moiety -R-. Preferably, the polyorganosiloxane backbone is a linear polymer chain. In a preferred embodiment, n is at least 9, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35 and up to 200, or up to 175, or up to 150, or up to 125, or up to 100, or up to 75, or at least 9 to up to 200, or at least 10 to up to 200, or at least 15 to up to 175, or at least 15 to up to 150, or at least 20 to up to 150, or at least 25 to up to 125, or at least 30 to up to 100, or at least 35 to up to 75, or at least 40 to up to 60.

[0048] The number of divalent moieties -R- in said polyorganosiloxane compound of formula (II) is at least 1 or at least 2 or at least 3 or at least 5 or at least 7, and can be up to 25 or up to 20 or up to 15 or up to 13 or up to 10, or can range from 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 or 5 or 4 or 3 or 2.

[0049] According to a first aspect, the present invention provides a polyorganosiloxane compound having a weight average molecular weight in the range of Mw=2.000 g / mol to Mw=12.000 g / mol, where Mw is measured by gel permeation chromatography using a standard polystyrene calibration. In a preferred embodiment, the weight average molecular weight of the polyorganosiloxane compound is at least 2000 g / mol, or at least 2500 g / mol, or at least 3000 g / mol, or at least 3500 g / mol to at most 12.000 g / mol, or at most 11.000 g / mol, or at most 10.000 g / mol, or at most 9.000 g / mol, or at most 8000 g / mol, or at most 7.000 g / mol, or at most 6.000 g / mol, or at most 5.000 g / mol, or at least 2000 g / mol. mol up to 12.000 g / mol, or at least 2.000 g / mol up to 11.000 g / mol, or at least 2.000 g / mol up to 10.000 g / mol, or at least 2.5000 g / mol up to 9.000 g / mol, or at least 2.500 g / mol up to 8.000 g / mol, or at least 2.500 g / mol up to 7.000 g / mol, or at least 3.000 g / mol up to 6.000 g / mol, or at least 3.500 g / mol up to 5.500 g / mol.

[0050] According to a first aspect, the method of the invention comprises the following steps: a) optionally pre-drying the lignocellulosic material, b) impregnating said lignocellulosic material with an aqueous composition comprising a polyorganosiloxane compound as described herein, and c) drying the impregnated lignocellulosic material. In the following, the process steps are described in more detail. The variables and parameter ranges can be adjusted to optimize the results of the method of the invention, taking into account the shape / dimension and type of lignocellulosic material to be treated.

[0051] In the optional pre-drying step a), heat and / or vacuum are applied to the lignocellulosic material as necessary to reduce the moisture content of the lignocellulosic material. Adjusting the moisture content of the lignocellulosic material to a predetermined range is beneficial to increase the absorption capacity of the lignocellulosic material and to achieve optimal impregnation of the lignocellulosic material with the aqueous composition comprising the polyorganosiloxane compound as described herein. Preferably, drying is performed at reduced pressure and at ambient temperature. In certain embodiments, drying is carried out at a pressure of at least 20 mbar, or at least 25 mbar, or at least 30 mbar, or at least 35 mbar, or at least 40 mbar, or up to 100 mbar, or up to 90 mbar, or up to 80 mbar, or up to 70 mbar, or up to 60 mbar, or at least 20 mbar to 100 mbar, or at least 25 mbar to 90 mbar, or at least 30 mbar to 85 mbar, or at least 35 mbar to 80 mbar, or at least 40 mbar to 70 mbar.

[0052] Also, pre-drying can be carried out under atmospheric pressure at a temperature in the range of at least 20°C, or at least 30°C, or at least 40°C, or at least 50°C and up to 140°C, or up to 130°C, or up to 120°C, or up to 110°C, or up to 100°C, or at least 20°C and up to 140°C, or at least 30°C and up to 130°C, or at least 40°C and up to 120°C, or at least 50°C and up to 110°C, or at least 50°C and up to 100°C.

[0053] Pre-drying can be carried out within the temperature and vacuum pressure ranges specified above.

[0054] In the impregnation step b), the lignocellulosic material is brought to ambient temperature (i.e. 20-25°C) and treated with an aqueous composition of polyorganosiloxane compounds as described above. In the context of the present invention, the term "impregnation" means that the air inclusions present in the lignocellulosic material are replaced by the penetrating aqueous composition comprising the polyorganosiloxane compounds. This allows the penetrating aqueous composition comprising the polyorganosiloxane compounds to enter the luminal and cell wall domains of the cell-like structures of the lignocellulosic material. Preferably, a vacuum pressure treatment procedure is applied to the lignocellulosic material to aid and enhance the absorption of the aqueous composition comprising the polyorganosiloxane compounds into the structural parts of the material. In certain embodiments, it is preferred to apply successive vacuum pressure treatment cycles. In one embodiment, the impregnation comprises 1 cycle, at least 2 cycles, or at least 3 cycles, or at least 4 cycles, or at least 5 cycles and up to 10 cycles, or up to 9 cycles, or up to 8 cycles, or up to 7 cycles, or at least 1 to up to 10 cycles, or at least 2 to up to 8 cycles, or at least 3 to up to 7 cycles. The term "cycle" in this context means that a vacuum is applied for a period of time followed by pressure for a period of time. The vacuum can be applied for at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes, up to 10 hours, or up to 8 hours, or up to 6 hours, or up to 5 hours, or up to 3 hours, or at least 15 minutes to up to 10 hours, or at least 30 minutes to up to 8 hours, or at least 45 minutes to up to 6 hours, or at least 60 minutes to up to 5 hours, or at least 15 minutes to up to 3 hours. The pressure can be applied for at least 30 minutes, or at least 45 minutes, or at least 60 minutes, or at least 2 hours, or at least 3 hours, up to 36 hours, or up to 24 hours, or up to 18 hours, or up to 12 hours, or up to 6 hours, or at least 30 minutes to up to 36 hours, or at least 45 minutes to up to 24 hours, or 60 minutes to up to 18 hours, or at least 2 hours to up to 12 hours, or at least 30 minutes to up to 18 hours.The duration of application of the vacuum and pressure will depend on the material and specific dimensions of the treated lignocellulosic material and the dimensions of the products made from said lignocellulosic material. During the pressure step, the lignocellulosic material is immersed in the aqueous composition comprising the polyorganosiloxane compound. During the vacuum step, the lignocellulosic material is removed from the aqueous composition comprising the polyorganosiloxane.

[0055] In drying step c), the impregnated lignocellulosic material is dried. The water portion of the aqueous composition comprising the polyorganosiloxane compound is removed from the lignocellulosic material by evaporation, and the polyorganosiloxane compound remains in the cell wall structure and / or cell cavities of the lignocellulosic material. Drying is carried out under heating conditions. The heating temperature is selected to result in a heat-induced hardening of the polyorganosiloxane compound remaining in the lignocellulosic material.

[0056] Step c) can be carried out at a temperature of 20-120° C., preferably 30-120° C., or preferably 40-120° C., or preferably 50-100° C., or preferably 55-90° C., preferably 60-85° C. Preferably, drying is carried out at at least 20° C., or at least 30° C., or at least 40° C., or at least 50° C., or at least 55° C., or at least 60° C., or at least 65° C., or at least 70° C., or up to 120° C., or up to 110° C., or up to 103° C., preferably up to 100° C., or up to 95° C., or up to 90° C., or up to 85° C., or up to 80° C., or at least 50° C. and up to 100° C., or at least 55° C. and up to 95° C., or at least 60° C. and up to 90° C., or at least 65° C. and up to 85° C., or at least 70° C. and up to 80° C. The treatment time of the drying step c) is at least 24 hours, or at least 36 hours, or at least 48 hours, or at least 60 hours, or at least 72 hours, or at least 84 hours and up to 216 hours, or up to 204 hours, or up to 192 hours, or up to 180 hours, or up to 168 hours, or up to 156 hours, or in the range of at least 24 hours to up to 216 hours, or at least 36 hours to up to 204 hours, or at least 48 hours to up to 192 hours, or at least 48 hours to up to 180 hours, or at least 60 hours to up to 168 hours.

[0057] Preferably, the drying step c) comprises a pre-drying step c1) and at least one drying step c2). The pre-drying step c1) can be applied to the impregnated lignocellulosic material immediately after the impregnation step and before the drying step c2). By employing the pre-drying step c1), the occurrence of severe cracks or other drying defects in the impregnated material can be avoided. In certain embodiments, such defects are expected to occur when the lignocellulosic material is exposed to a temperature of more than 50° C. immediately after the impregnation step. This is because such lignocellulosic materials may have very high moisture content levels (more than 100% relative moisture content) immediately after impregnation with the aqueous composition. Thus, the pre-drying allows the lignocellulosic material to be smoothly dried before being treated at higher temperatures in the drying chamber. In the pre-drying step c1), the impregnated lignocellulosic material is dried at a lower temperature compared to the drying step c2). In an embodiment, the pre-drying step c1) is carried out at a temperature of at least 15°C, or at least 20°C, or at least 25°C, or at least 30°C, or at least 35°C, up to 80°C, or up to 75°C, or up to 70°C, or up to 65°C, or up to 60°C, or up to 55°C, or at least 15°C to up to 80°C, or at least 20°C to up to 75°C, or at least 25°C to up to 70°C, or at least 30°C to up to 65°C, or at least 35°C to up to 60°C, or at least 40°C to up to 55°C.The treatment time of the pre-drying step c1) is at least 12 hours, or at least 36 hours, or at least 60 hours, or at least 84 hours, or at least 108 hours, or at least 132 hours, or at least 156 hours and up to 504 hours, or up to 456 hours, or up to 408 hours, or up to 360 hours, or up to 412 hours, or up to 364 hours, or up to 316 hours, or up to 268 hours, or up to 220 hours, or from at least 12 hours to up to 504 hours, or from at least 36 hours to up to 456 hours, or from at least 60 hours to up to 408 hours, or from at least 84 hours to up to 364 hours, or from at least 108 hours to up to 316 hours, or from at least 132 hours to up to 268 hours, or from at least 156 hours to up to 220 hours.

[0058] Furthermore, the final step c) may comprise a series of drying steps starting from a pre-drying step c1) followed by a drying step c2).

[0059] According to a first aspect, the method of the invention is characterized in that step b) is a vacuum pressure impregnation process carried out in the pressure range from 5 mbar to 20 bar. Preferably, the vacuum pressure impregnation process is divided into a vacuum stage and an overpressure stage. In a preferred embodiment, only one vacuum pressure cycle is applied. The vacuum step is carried out at a pressure of at least 5mbar, or at least 10mbar, or at least 15mbar, or at least 20mbar, or at least 25mbar, or at least 30mbar, or at least 40mbar, or at least 50mbar and up to 800mbar, or up to 700mbar, or up to 600mbar, or up to 500mbar, or up to 400mbar, or up to 300mbar, or at least 5mbar and up to 800mbar, or at least 10mbar and up to 700mbar, or at least 15mbar and up to 600mbar, or at least 20mbar and up to 500mbar, or at least 25mbar and up to 500mbar, or at least 30mbar and up to 400mbar, or at least 40mbar and up to 300mbar, or at least 50mbar and up to 100mbar. The vacuum can be applied for at least 5 minutes, or at least 10 minutes, or at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes and up to 4 hours, or up to 3.5 hours, or up to 3 hours, or up to 2 hours, or up to 1.5 hours, or at least 5 minutes and up to 4 hours, or at least 10 minutes and up to 3.5 hours, or at least 15 minutes and up to 3 hours.The subsequent overpressurization steps are carried out in a pressure range of at least 1 bar, or at least 2 bar, or at least 3 bar, or at least 4 bar, at least 5 bar, or at least 6 bar, or at least 7 bar, or at least 8 bar, or at least 9 bar and up to 20 bar, or up to 18 bar, or up to 16 bar, or up to 14 bar, or up to 13 bar, or up to 12 bar, or at least 1 bar and up to 20 bar, or at least 2 bar and up to 18 bar, or at least 3 bar and up to 16 bar, or at least 4 bar and up to 14 bar, or at least 5 bar and up to 12 bar, or at least 6 bar and up to 10 bar. The pressure may be applied for at least 10 minutes, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes, or at least 2 hours, or at least 3 hours, or at least 4 hours, or at least 5 hours, or at least 6 hours, or at least 7 hours, or at least 8 hours and up to 19 hours, or up to 18 hours, or up to 17 hours, or up to 16 hours, or up to 15 hours, or up to 14 hours, or up to 13 hours, or up to 12 hours, or up to 10 hours, or at least 10 minutes and up to 19 hours, or at least 30 minutes and up to 18 hours, or at least 1 minute and up to 10 hours.

[0060] The method according to the invention is characterized in that a step a) is included in the method, in which the lignocellulosic material is pre-dried to a residual moisture content of 0.1-20%. In the context of the present application, the residual moisture content percentage shall refer to the relative moisture content of the lignocellulosic material. The definition and determination of the relative moisture content of lignocellulosic materials, such as wood, is known in the art. The relative moisture content percentage is obtained by multiplying by 100 the ratio of the moisture content (in weight) and the dry mass (in weight) of the lignocellulosic material under investigation. The moisture content influences the effectiveness of the impregnation. The higher the moisture content, the less effective the impregnation and therefore fewer chemical molecules are able to penetrate the wood cell walls of the lignocellulosic material. As a rough estimate, at a relative moisture content above 25-30%, the wood cell walls are almost completely filled with water. Thus, in one embodiment, before treating the lignocellulosic material according to the invention, the relative moisture content of the lignocellulose should be in the range of 0-20%. Preferably, the moisture content of the lignocellulosic material in step a) is adjusted to a residual moisture content of at least 0.1%, or at least 1%, or at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15% and up to 20%, or up to 19%, or up to 18%, or up to 17%, or in the range of at least 0.1% to 20%, or at least 1% to up to 19%, or at least 2% to up to 18%, or at least 5% to up to 17%, or at least 10% to up to 17%, or at least 12% to at least 16%, or preferably 15%±1%.

[0061] As mentioned above, in step b), an aqueous composition is used that contains a polyorganosiloxane compound in an amount of at least 0.1 wt% to at most 90 wt%, at least 0.5 wt% to at most 80 wt%, or at least 1 wt% to at most 60 wt%, or at least 2 wt% to at most 40 wt%, or at least 2.5 wt% to at most 30 wt%, or at least 2.5 wt% to at most 20 wt%, or at least 4 wt% to at most 20 wt%, or at least 5 wt% to at most 15 wt%, or at least 6 wt% to at most 15 wt%, or at least 7 wt% to at most 12 wt%, or at least 7 wt% to at most 10 wt%, based on the total weight of the aqueous composition. Thus, the amount of polyorganosiloxane compound present in the aqueous composition is at least 0.1 wt%, or at least 0.5 wt%, or at least 1 wt%, or at least 2.5 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 6 wt%, or at least 8 wt%, up to 90 wt%, or up to 80 wt%, or up to 60 wt%, or up to 50 wt%, or up to 40 wt%, or up to 20 wt%, or up to 15 wt%, or up to 12 wt%, or up to 10 wt%, or ... The amount of polyorganosiloxane is at least 0.1 wt% up to 90 wt%, or at least 0.5 wt% up to 80 wt%, or at least 1 wt% up to 60 wt%, or at least 2 wt% up to 40 wt%, or at least 2.5 wt% up to 30 wt%, or at least 2.5 up to 20 wt%, or at least 4 wt% up to 20 wt%, or at least 5 wt% up to 15 wt%, or at least 6 wt% up to 15 wt%, or at least 7 wt% up to 12 wt%, or at least 7 wt% up to 10 wt%, where wt% is based on the total weight of the aqueous composition. The aqueous composition may also include emulsifiers and solubilizers. Preferably, the remainder of the aqueous composition to 100 wt% is water. The concentration of polyorganosiloxane in the aqueous composition depends on the respective application for which the impregnated lignocellulosic material is intended. The higher concentration range is applicable when the lignocellulosic material is intended for high performance requirements, for example, outdoors or in high humidity environments.

[0062] The aqueous composition containing the polyorganosiloxane compound is adjusted to a pH in the range of 3 to 6.5, or 3.5 to 6, or 4 to 5.5. The predetermined pH value within the ranges specified herein ensures the stability of the aqueous composition containing the polyorganosiloxane compound and its uniform distribution on the lignocellulosic material.

[0063] The aqueous composition comprising the polysiloxane compound further has the feature that the aqueous composition is free of heavy metals. In the context of this application, "free of heavy metals" means a composition having a density of 5 g / cm3 in pure form. 3 "Free" means that no more than about 100% of a heavy metal is present in the aqueous composition. The term "metal" includes metals in ion, complex, compound and pure form. The term "free" means that no heavy metals have been added to the aqueous composition. The term "free" does not include unavoidable traces of heavy metals that may always be present as unavoidable contaminants.

[0064] A commercially available polyorganosiloxane compound, or an aqueous composition comprising the respective polyorganosiloxane compound, is Siligen® MIH liq.

[0065] In a second aspect, the present invention relates to a lignocellulosic material treated with a method according to the first aspect of the invention. Thus, all the features described above with reference to the first aspect of the invention also apply to the second aspect of the invention. The lignocellulosic material can be any processed state of engineered wood, such as particle board, medium density fiberboard, oriented strand board (OSB), paper, cardboard, lignocellulosic insulation board, plywood, veneer and packaging materials. The lignocellulosic material according to the invention can have any dimensions and volume. Particularly advantageously, the lignocellulosic material is in the form of wood processed products, such as wooden boards, beams, laths, panels, timber, rafters, furniture, flooring, etc.

[0066] The present invention further relates to a method for treating lignocellulosic material with at least one polyorganosiloxane compound at a temperature below 100° C. All the above disclosed explanations regarding the individual method steps also apply to this embodiment of the additional method, except that the treatment is carried out at a temperature below 100° C., preferably below 95° C., preferably below 90° C., preferably below 85° C., preferably below 80° C., and the method is not limited to polyorganosiloxane compounds according to the first aspect of the invention.

[0067] In one embodiment, the method is carried out by treating the lignocellulosic material with an aqueous composition comprising a polyorganosiloxane compound, including but not limited to a polyorganosiloxane compound according to the first aspect of the present invention, in an amount of at least 0.5 wt% to up to 80 wt%, or at least 1 wt% to up to 60 wt%, or at least 2 wt% to up to 40 wt%, or at least 2.5 wt% to up to 30 wt%, or at least 2.5 wt% to up to 20 wt%, or at least 4 wt% to up to 20 wt%, or at least 5 wt% to up to 15 wt%, or at least 6 wt% to up to 15 wt%, or at least 7 wt% to up to 12 wt%, or at least 7 wt% to up to 10 wt%, based on the total weight of the aqueous composition. The amount of polyorganosiloxane compound in the aqueous composition is at least 0.1 wt%, or at least 0.5 wt%, or at least 1 wt%, or at least 2 wt%, or at least 2.5%, or at least 4 wt%, or at least 5 wt%, or at least 6 wt%, or at least 8 wt% and up to 90 wt%, or up to 80 wt%, or up to 60 wt%, or up to 40 wt%, or up to 20 wt%, or up to 15 wt%, or up to 12 wt%, or up to 10 wt%, or the polyorganosiloxane is The polyorganosiloxane is present in the composition in an amount of at least 0.1 wt% to up to 90 wt%, or at least 0.5 wt% to up to 80 wt%, or at least 1 wt% to up to 60 wt%, or at least 2 wt% to up to 40 wt%, or at least 2.5 wt% to up to 30 wt%, or at least 4 wt% to up to 20 wt%, or at least 5 wt% to up to 15 wt%, or at least 6 wt% to up to 15 wt%, or at least 7 wt% to up to 12 wt%, or at least 7 wt% to up to 10 wt%, where wt% is based on the total weight of the aqueous composition. The aqueous composition may also include emulsifiers and solubilizers. Preferably, the remainder of the aqueous composition to 100 wt% is water. The concentration of polyorganosiloxane in the aqueous composition depends on the respective application for which the impregnated lignocellulosic material is intended.

[0068] Advantageous improved capabilities of lignocellulosic materials treated by the method according to the invention are dimensional stability and / or weathering resistance (weathering resistance) and / or biological durability and / or hydrophobicity. The term "weathering" as used herein refers to optical (e.g. surface greying) and / or physical (e.g. moisture content) changes in lignocellulosic materials as a result of the influence of environmental conditions, such as UV light (which causes UV degradation) or wood-damaging fungi. The term "wood-damaging fungi" as used herein refers to fungi that grow on the wood surface and thereby cause wood damage, i.e. change or deteriorate the original properties in some way, for example by promoting decay processes (e.g. brown rot (C. puteana) or white rot (T. versicolor)) or optical appearance (e.g. mold or staining fungi). Thus, a board sample (50x25x500 mm 3 and 80x20x400mm 3 ) were treated with the method according to any of the above embodiments. Impregnation and drying at a temperature of 70 ° C improved the results. The treated wood samples show only minor optical changes compared to the untreated reference samples (see Fig. 2a) and b). However, no detrimental drying defects such as cracks, deformations or cell collapse are observed. The board samples also show improved biological durability in the respective durability tests. The material performance with regard to biological durability (resistance to biological deterioration) can be verified on test specimens according to DIN EN 252 (2015) and DIN EN 350 (2016). The verification of biological durability is carried out under conditions of use classes (UC) 3, 4 and 5 (DIN EN 335, 2013). An exemplary test setup for UC 3, 4 and 5 conditions is shown in Fig. 1. Lignocellulosic materials, such as boards, treated with the method according to the invention show less tendency to graying of the surface, i.e. improved weather resistance. Furthermore, lignocellulosic materials treated with the method according to the invention show improved adherence to dimensional accuracy after 15 months of outdoor environmental exposure. Qualitative results are shown in FIG.

[0069] The biological durability of the lignocellulosic material treated with the method according to the invention is tested in an outdoor underground test according to EN 252 (2015). The evaluation can be carried out in a pick test according to EN 252 (2015). Untreated control samples show signs of decay after one year of exposure, while all samples treated with the method according to the invention remain healthy. In particular, the biological durability against wood pests is improved. The term "wood pests" in this specification refers to insects that are harmful to wood or that directly damage it, such as subterranean termites, Cerambycidae, Anobiidae and Lyctidae. Whereas the untreated controls were almost completely decayed after 8 months, the samples treated with the method according to the invention surprisingly showed only little attack by wood pests or wood-damaging fungi. Furthermore, the biological durability of the lignocellulosic material treated by the method according to the invention in a marine environment is tested according to EN 275 (1992). Whereas the untreated control samples completely decayed after less than one year of exposure, the samples treated by the method according to the invention surprisingly showed only little attack by marine borers. The term "marine borers" in this application refers to marine organisms that are harmful to wood or directly damage it, such as, for example, Teredinidae or Limnoriidae. As with other tests carried out, after one year of exposure to the marine environment, the fouling organisms were removed and X-ray measurements were carried out to detect internal attack by marine borers, such as, for example, Teredo navalis (shipworm). The treated samples suffered "light attack" (decay rating 1), whereas the untreated control samples showed extensive attack by marine borers and were destroyed after only one year (decay rating 4, "damaged", EN 275, 1992). It has thus been found that the lignocellulosic material treated with the method of the invention meets the requirements of industrial practice in many technical fields of application, in particular outdoor applications, such as terrace decking, facade cladding, garden furniture manufacturing, carpentry, house building, wood construction, gardening and agriculture, shipbuilding and model making.

[0070] According to a second aspect of the invention, there is also provided lignocellulosic material treated by a method according to the (first aspect of) the invention. The above-mentioned embodiments, advantages etc. relating to the first aspect of the invention also apply to the second aspect.

[0071] The lignocellulosic material according to the invention is characterized by a weight percentage increase after drying and leaching, measured according to DIN EN 84-2020-10 (formerly DIN EN 84-2018-10), of not more than 15%, or not more than 10%, or not more than 7%, preferably between 4 and 8%, or between 5 and 7%. In certain embodiments, the weight percentage increase is at least 1%, or at least 2%, or at least 4%, or at least 5% and up to 7%, or up to 6.5%, or at least 2% to up to 7%, or at least 3% to up to 7%, or at least 4% to up to 7%, or at least 5% to up to 7%, or at least 5% to up to 6.5%. The weight percentage increase brought about by the absorption of the cationic polyorganosiloxane compound is preferably in the narrow range of 5% to 7%. Too much absorption and too high values ​​of weight percentage increase may lead to loss of dimensional accuracy of the lignocellulosic material object. Thus, manufacturing processes using lignocellulosic materials that absorb too much cationic polyorganosiloxane compound may be compromised. It has been found that a weight percent increase of 5-7% optimizes the need for dimensional stability while improving weather resistance and resistance to wood-damaging organisms such as wood-damaging fungi and / or marine borers and / or wood pests (biological durability). In certain embodiments, a weight percent increase of more than 7% may be desirable if the dimensional stability of the lignocellulosic product is maintained. This depends on the lignocellulosic material and the concentration of polyorganosiloxane compound used in the treatment according to the invention.

[0072] According to a second aspect of the invention, the lignocellulosic material is characterized by a swelling coefficient of 14% or less, preferably 13.5% or less, as determined by the procedure described herein. In certain embodiments, the swelling coefficient is 13.0% or less, or 12.5% ​​or less. The swelling coefficient is a measure of the swelling / shrinkage properties of the lignocellulosic material observed in an environment of varying moisture conditions, such as outdoor weathering. A low swelling coefficient is preferred and indicates a low swelling / shrinkage behavior of the lignocellulosic material. In particular, in construction applications, low swelling / shrinkage properties of the lignocellulosic material are important to ensure dimensional stability and durability of constructions using the lignocellulosic material. The swelling / shrinkage behavior in an environment of alternating moisture conditions is a common property of all lignocellulosic materials. The swelling coefficient is determined according to the following procedure: A treated lignocellulosic sample, e.g. a block of wood, that has been dried in an oven is immersed in water and saturated with moisture. The absorption of moisture is facilitated by applying a vacuum. A vacuum is applied for 30 minutes and the sample is then stored in water at atmospheric pressure for a further 24 hours. The sample is saturated with water as specified. The swelling factor is then calculated by comparing the dimensions of the sample in the oven-dried state (relative moisture content equal to 0%) with those in the water-saturated state (after 30 minutes of vacuum and 24 hours of storage in water). In particular, the percent swelling factor is calculated by multiplying the ratio of the dimensions in the oven-dried state to the swollen state by 100. However, it has been found that the cationic polyorganosiloxane compounds used in the method according to the invention have an ionic activity and therefore an affinity for water, which gives the lignocellulosic material a swelling factor lower than that of untreated lignocellulosic materials. The lignocellulosic materials according to the invention therefore combine the relevant needs of moisture resistance and dimensional stability with the desired weather resistance and resistance to wood-damaging fungi, wood pests or marine borers.

[0073] In a further embodiment of the second aspect, the lignocellulosic material is characterized by a mass loss due to fungal decay of brown rot pathogens of less than 5% measured according to EN 113-2 (2021) (formerly CEN / TS 15083-1 (2005)). In certain embodiments, the mass loss due to fungal decay of brown rot pathogens is less than 4.5%, or less than 4.0%, or less than 3.5%, or less than 3.0%, or less than 2.5%, or less than 2.0%, or less than 1.5%. Although fungal decay of brown rot pathogens is to some extent endemic to all lignocellulosic materials, the lignocellulosic materials of the present invention show a significantly reduced mass loss due to brown rot decay compared to untreated lignocellulosic materials or lignocellulosic materials impregnated with alternative non-cationic polyorganosiloxanes. It is therefore clear that the biological resistance of lignocellulosic materials treated with the method of the present invention is significantly improved. This makes the lignocellulosic material of the invention particularly suitable for applications in which the lignocellulosic material is exposed to climatic conditions conducive to fungal growth, i.e. damp rooms or outdoor applications.

[0074] According to a second aspect of the invention, the lignocellulosic material is characterized as having a cell wall swelling of at least 0.10%. In certain embodiments, the cell wall swelling of the lignocellulosic material is at least 0.15%, or at least 0.20%, or at least 0.25%, or at least 0.30%, or at least 0.35%, or at least 0.40%, or at least 0.45%, or at least 0.50%, or at least 0.55%, or at least 0.60%, or at least 0.65%, or at least 0.70%, or at least 0.75%, or at least 0.80%, or at least 0.85%, or at least 0.90%, or at least 0.95%, or at least 1.00%, or at least 1.05%, or at least 1.10%, or at least 1.15%, or at least 1.20%, or at least 1.30%, or at least 1.40%, or at least 1.50%, or at least 1.60%, or at least 1.70%, or at least 1.80%, or at least 1.90%, or at least 1.95%, or at least 1.00%, or at least 1.05%, or at least 1.10%, or at least 1.15%, or at least 1.20%, or at least 1.40%, or at least 1.50%, or at least 1.6 ... In the above embodiment, the range is 1.25%, or at least 1.30%, or at least 1.35%, or at least 1.40%, or at least 1.40%, or at least 1.50%, or at least 1.55%, or at least 1.60%, and is up to 5.00%, or up to 4.50%, or up to 4.00%, or up to 3.50%, or up to 3.00%, or up to 2.50%, or up to 2.00%, or up to 1.75%, or up to 1.70%, or at least 0.10% to 5.00%, or at least 0.50% to 4.00%, or at least 1.00% to 2.50%, or at least 1.40% to 2.00%, or at least 1.50% to 1.75%, or at least 1.55% to 1.70%. Cell wall swelling represents the dimensional deviation of a lignocellulosic material object treated by swelling in the method according to the invention. Cell wall swelling provides a measure of the amount of polyorganosiloxane compound inserted into the lignocellulosic material during the process conditions of the method according to the invention.

[0075] It can be seen that the cell wall swelling of the lignocellulosic material treated with the described cationic polyorganosiloxane compound is higher than that of the comparative example in which a non-cationic polyorganosiloxane is used. Thus, the absorption of the cationic polyorganosiloxane is improved over the techniques using the same process parameters. However, the swelling induced by the absorption of the cationic polyorganosiloxane remains in a low percentage range.

[0076] In a further embodiment of the second aspect, the lignocellulosic material is characterized in that the polyorganosiloxane compounds according to the invention are deposited in the capillaries / cell cavities and inside the cell walls of the lignocellulosic material, resulting in a significantly reduced ability of the capillaries to absorb liquid water compared to a comparative lignocellulosic material using non-cationic polyorganosiloxanes. The term "capillaries / cell cavities" in this specification refers to the natural complex system of pathways for their water supply (cell spaces), e.g. tracheids or vessels. It is therefore clear that the resistance of the lignocellulosic material treated by the method of the invention to liquid water and / or moisture exposure is significantly improved.

[0077] According to a second aspect, the lignocellulosic material is characterized by having a silky feel on its impregnated surface. The term "silky feel" refers to the feel of the surface when touched and depends on the hydrophobicity (surface wettability) of the treated surface. The lignocellulosic material treated according to the method of the invention is more hydrophobic and therefore less hydrophilic compared to native lignocellulosic material, resulting in this silky feel. To characterize the increased hydrophobicity of the treated lignocellulosic material, contact angle measurements of polar liquids (water) can be performed. The contact angle of the lignocellulosic material treated according to the first aspect of the invention is up to 5°, or up to 7°, or up to 10°, or up to 12°, or up to 15°, or up to 20°, or up to 22°, or up to 25°, or up to 30°, or even more than 30° after weathering (e.g. 15 months) than the untreated surface of the lignocellulosic material, thus demonstrating the increased hydrophobicity of the lignocellulosic material treated according to the first aspect of the invention.

[0078] According to the present invention, there is also provided the use of a polyorganosiloxane compound as described above or the use of an aqueous composition as described above for the treatment of lignocellulosic material. Preferably, the use according to the present invention is the use of a polyorganosiloxane compound as described above as a treatment agent for lignocellulosic material and / or the use of a polyorganosiloxane compound as defined with reference to the first and second aspects of the present invention for increasing the water absorption resistance (hydrophobicity) and / or the dimensional stability and / or the weather resistance and / or the biological resistance, in particular the resistance against wood-damaging fungi and / or marine borers and / or wood pests, of lignocellulosic material. EXAMPLES

[0079] example Example 1. Working Example: Impregnation of Lignocellulosic Specimens 1, 2.5, 5, 7.5 and 10% aqueous compositions were used, containing Siligen® MIH liq (active agent content in Siligen® MIH liq.: 18.5%) and water. For the 1% aqueous composition, 54 g of Siligen® MIH liq was mixed with 946 g of water (total solution: 1000 g). For the 2.5% aqueous composition, 135 g of Siligen® MIH liq was mixed with 865 g of water (total solution: 1000 g). For the 5% aqueous composition, 270 g of Siligen® MIH liq was mixed with 730 g of water (total solution: 1000 g). For the 7.5% aqueous composition, 405 g of Siligen® MIH liq was mixed with 595 g of water (total solution: 1000 g). For the 10% aqueous composition, 540 g of Siligen® MIH liq was mixed with 460 g of water (total solution: 1000 g). 3 Scots pine sapwood (Pinus sylvestris L.) specimens were impregnated with the aqueous composition solution by vacuum pressure impregnation. Vacuum was applied at a pressure of 50 mbar for 1.0 hour at ambient temperature. Then an overpressure of 10 bar was applied for 2.0 hours at ambient temperature. The impregnated specimens were dried in a first drying step at 20° C. for 72 hours. A second drying step was applied to the specimens at 80° C. for 48 hours.

[0080] Example 2. Comparative Example: Impregnation of Lignocellulosic Specimens The impregnation of comparative specimens CE1 and CE2 was carried out according to the procedure described in Example 1, except that for CE1, a 10% aqueous composition containing Solusoft SEID (active agent content of Solusoft SEID: 24%) and water (417 g of Solusoft SEID mixed with 583 g of water (total solution: 1000 g)) was used, and for CE2, a 10% aqueous composition containing Solusoft NMW (active agent content of Solusoft NMW: 27%) and water (370 g of Solusoft NMW and 630 g of water (total solution: 1000 g)) was used. Solusoft SEID is a polydimethylsiloxane compound with no functional end groups and with amino-functional side groups that are isoalkyl polyglycol ether amino-functionalized. Solusoft NMW is a polydimethylsiloxane compound with no functional end groups and with amino-functional side groups that are acetylamino-functionalized.

[0081] Example 3. Leaching and immobilization 20x20x10mm 3 Test specimens were impregnated according to the procedure described in Example 1 (10% sample). The test specimens were dried at different drying temperatures. The second drying step described in Example 1 varied between 70 and 120 °C. The procedure was carried out according to standard DIN EN 84-2020-10 (formerly DIN EN 84-2018-10). The test specimens were vacuum impregnated with demineralized water for 20 min up to maximum water absorption and subjected to a washing test of 14 days. The washing test included 9 water exchanges under permanent water impregnation. After the completion of the washing test, the test specimens were dried to absolute dry mass. The absolute dry mass was recorded. The residual amount of cationic polyorganosiloxane used according to Example 1 in the test specimens after washing (10% sample) was calculated from the weight difference between the test specimen at the start and the test specimen obtained after the washing test and is expressed as weight percent gain (WPG). The results are shown in Table 1. [Table 1]

[0082] As can be seen from Table 1, drying temperatures of 103, 110, and 120° C. result in the highest weight percent gains. However, it was surprisingly found that the lower drying temperatures of 70 and 80° C. also resulted in acceptable weight percent gains, which were surprisingly higher than the WPG at a drying temperature of 90° C. Thus, the method of the present invention allows for lower drying temperatures in industrial lignocellulosic material processing. Lower drying temperatures save energy and result in less heat stress on the processed lignocellulosic products, respectively.

[0083] Example 4. Determination of swelling coefficient 20x20x10mm impregnated according to the procedure in Example 1 (10% sample) and dried at different drying temperatures as outlined in Example 3 3 Test specimens of 10 ... The dimensions of the test specimens and the natural control sample were measured. The measured reduction in dimensional change due to moisture was expressed as the expansion coefficient. The results are shown in Table 2. [Table 2]

[0084] The test pieces obtained after impregnation treatment according to the method of the present invention show a higher expansion / shrinkage recovery rate, i.e. a lower expansion coefficient, when the drying temperature is lower.

[0085] Example 5: Mass loss due to fungal spoilage The biological resistance to wood-damaging fungi is evaluated in terms of mass loss due to fungal decay. The test specimens produced according to the procedure described in Example 1 were subjected to a cleaning procedure according to DIN EN 84-2020-10 (formerly DIN EN 84-2018-10). The test specimens were then inoculated with pure cultures of wood-damaging basidiomycetes according to standard EN 113-2 (2021) (formerly: CEN / TS 15083-1 (2005)). In the incubation vessels, the white rot pathogen "Trametes versicolor" and the brown rot pathogen "Coniophora puteana" were each cultivated for 16 weeks. After 16 weeks, the test specimens were removed from the incubation vessels and the mass loss due to fungal decomposition was calculated. For comparison, natural control test samples not treated according to Example 1 were treated with the same incubation procedure.

[0086] Further comparative specimens CE1 and CE2 produced according to Example 2 were used, which were treated with the same cleaning procedure according to DIN EN 84-2020-10 (formerly DIN EN 84-2018-10) and inoculated with pure cultures of the same wood-rotting basidiomycetes according to standard EN 113-2 (2021) (formerly CEN / TS 15083-1 (2005)). Similarly, the white-rot pathogen "Trametes versicolor" and the brown-rot pathogen "Coniophora puteana", respectively, were cultivated in the cultivation vessels for 16 weeks. After 16 weeks, the comparative specimens CE1 and CE2 were removed from the cultivation vessels and the mass loss due to decomposition by the fungi was calculated.

[0087] The results are shown in Table 3. [Table 3]

[0088] The mass loss (ML) of the 2.5%, 5%, 7.5% and 10% inventive samples (according to example 1) is less than 5% for both brown and white rot fungi. A significantly improved resistance to fungal decay is observed even for the 1% inventive sample (compared to the natural control sample and to CE1 and CE2, which contain a much higher amount (10%) of active agent). The mass loss to white rot fungi of CE1 and CE2 is the same as for the 5%, 7.5% and 10% inventive samples, which contain a lower or equivalent amount of active agent. However, the mass loss to brown rot fungi of all inventive samples is significantly lower than the mass loss measured for the natural control and the CE1 and CE2 samples. Accordingly, the treatment of the samples according to the invention significantly improves the resistance to wood-damaging fungi. In summary of the experimental data outlined above, it was surprising to observe that the use of drying temperatures below 90°C did not result in a significant decrease in immobilization of the polyorganosiloxane compound as one skilled in the art would expect from the prior art and from the experiments performed at higher drying temperatures above 90°C listed in Table 1. The antifungal properties against white rot fungi were then excellent, even though the polysiloxane concentration in the water was only 10 wt% and the weight percent increase in WPG was only 6-8%.

[0089] Example 6: Cell wall expansion Test specimens according to Example 1 (2.5%, 5% and 10% samples) were produced. Additionally, untreated natural test specimens for comparison and comparative test specimens produced according to CE1 and CE2 (according to Example 2) were prepared. The test specimens were dried to complete dryness (i.e. wood moisture content - 0%). The permanent swelling was then determined in terms of "cell wall swelling". By "cell wall swelling" is meant the increase in the test specimen dimensions in the dry state after treatment according to Example 1 (2.5%, 5% and 10% samples) / Example 2. The cell wall swelling is calculated by multiplying the ratio of the dimensions before / after treatment by 100. The swelling of the test specimens was compared with the dimensions of the untreated natural test specimens in the absolutely dry state. The swelling value is expressed as "cell wall swelling (CWB)". The cell wall swelling indicates that the molecules introduced by impregnation were not only incorporated into the cell cavities but also into the wood cell walls themselves. The results are shown in Table 4. The CWB indicates the deposition of the polysiloxane compound in the cell walls. The higher the CWB, the greater the expected improvement in material properties. [Table 4] As can be seen, the CWB values ​​of the inventive test specimens (2.5%, 5% and 10% samples) produced according to Example 1 show better CWB values ​​than the comparative example. It is therefore evident that the absorption of the finish used in the method according to the invention is higher than the comparative example, which indeed improves the performance of the material.

[0090] Example 7 - Absorption of liquid water Test specimens (10% sample) were prepared according to Example 1. Comparative test specimens CE2 and CE1 were prepared according to Example 2. 10x5x100mm 3 The specimens were oven dried at 103°C until constant weight (oven-dried weight at 0% moisture content). The oven-dried weight was measured. The dried specimens were immersed in water for 24 hours at atmospheric pressure and ambient temperature. After 24 hours, the mass of the immersed specimens was measured and the amount of liquid water absorbed was calculated from the weight of the untreated starting specimen. Additionally, an untreated natural specimen was provided for comparison. The results are shown in Table 5. [Table 5] A comparison of the inventive example (10% sample) with the comparative examples CE1 and CE2 shows that the water absorption is significantly lower in the case of the inventive example (10% sample). It is therefore clear that the specimens treated with the method according to the invention are more resistant to water absorption and therefore also to the alternating humidity conditions prevailing in outdoor conditions.

[0091] Example 8 - Contact angle measurement Test piece (80x25x40(ax.)mm 3 ) were produced according to the procedure of Example 1 (10% sample). Additionally, untreated natural specimens were provided. Contact angle (°) measurements of polar liquids (water) were carried out after 15 months of weathering. The weathering location was Germany (Göttingen). The specimens were exposed at a distance of 1 m from the ground at an inclination of 45°. A 1 μL water drop was administered and the angle was analyzed with software support (tangen-1 fit) (Kruss Mobile Surface Analyzer, Kruss GmbH, Hamburg, Germany). Six specimens were investigated with three drops each and the angle was analyzed at 1 s intervals over a period of 10 s. The average angles (°) are given in Table 6. [Table 6] Measurements after 15 months of weathering show that the samples of the invention have higher contact angles, which means they are more hydrophobic.

[0092] Example 9 - Underground durability against wood pests Test piece (20x8x200(ax.)mm 3 ) was prepared according to the procedure described in Example 1 (10% sample). In addition, an untreated natural sample (20x8x200 (ax.) mm 3) was provided. The test location was Indonesia (Bogor) and the resistance to wood pests (such as subterranean termites) was tested (see FIG. 1d). For this purpose, the test was carried out as an in-ground stake test according to AWPA E7-21. The specimens were sunk in soil and the decay status was evaluated after 4 and 8 months. Even after 4 months, more than 80% of the specimens were defective in the untreated control group. Tables 7 and 8 show the results of the control groups (untreated and comparative specimens) and the specimens according to the invention treated with Siligen® MIH. [Table 7] [Table 8] A corrosion rating of 10 means no corrosion, while a corrosion rating of 0 means complete failure. A comparison of the untreated sample with the sample of the invention shows that the impregnation with Siligen® MIH provides a significant protection against subterranean termites. It is therefore clear that, despite the surprisingly low temperatures required for the curing process, a significant increase in resistance to wood pests is achieved. The above ground test (UC3) test facility consisted of three segments:

Claims

1. 1. A method for treating lignocellulosic material with at least one polyorganosiloxane compound, the polyorganosiloxane compound having a polyorganosiloxane backbone and a polyorganosiloxane having formula (I): 【Chemistry 1】 (In the above formula, R ２ , R ３ , R ４ are, independently of one another, linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted C １ ~C ４５ represents a hydrocarbon residue, optionally containing one or more heteroatoms of O, S, N, * represents a bond site attached to the polyorganosiloxane backbone),

2. R ２ , R ３ , R ４ are, independently of each other, C １ or C ２ Saturated or C ２ Unsaturated hydrocarbon residues and / or linear, cyclic or branched saturated or unsaturated C ３ ~C ４５ The method of claim 1 , wherein the hydrocarbon is

3. R ２ , R ３ , R ４ are, independently of each other, C １ or C ２ saturated hydrocarbon residues and / or linear, cyclic or branched saturated C ３ ~C ２０ The method of claim 1 , wherein the hydrocarbon is

4. The polyorganosiloxane compound is C １ ~C ２０ 2. The method of claim 1, further comprising at least one divalent moiety -R- consisting of a saturated or unsaturated, linear or branched hydrocarbon residue of formula (I) optionally containing one or more heteroatoms of O, S, N, wherein at least one ammonium group residue of formula (I) is bonded to the siloxane portion of the polyorganosiloxane backbone via a bonding site *.

5. The polyorganosiloxane compound has the formula (II): 【Chemistry 2】 (In the above formula, R １ and R ５ are, independently of each other, organic aliphatic C １ ~C ６ residue, or a divalent moiety -R- according to claim 4, wherein at least one ammonium group residue of formula (I) is attached to the siloxane moiety via a bonding site *, and at least 1, preferably 2, or preferably at least 10, preferably at least 20 R １ is R in the compound of formula (II) ５ together represent the divalent moiety -R-, m ＋ represents m times the positive charge assigned by the polyorganosiloxane compound; mA － is a charge balancing anion A selected from the group consisting of halide, hydroxide, 1 / 3 borate, 1 / 2 sulfate, 1 / 2 phosphate, nitrate, carboxylate, or mixtures thereof; － represents The method according to claim 4, wherein n represents the number average degree of polymerization, which is from 9 to 200, preferably from 30 to 150, preferably from 35 to 75, preferably from 40 to 60.

6. R １ are, independently of each other, organic aliphatic C １ ~C ６ represents a residue, and R ５ represents the divalent moiety -R- of claim 5, wherein at least one, preferably two, terminal ammonium group residues of formula (I) are bonded to the siloxane moiety via bonding sites *.

7. 10. The method of claim 1, wherein the weight average molecular weight of the polyorganosiloxane compound ranges from 2.000 g / mol to 12.000 g / mol.

8. Treating the lignocellulosic material with at least one polyorganosiloxane compound comprises the steps of: a) optionally pre-drying the lignocellulosic material; b) impregnating the lignocellulosic material with an aqueous composition comprising the polyorganosiloxane compound of claim 1; c) drying the impregnated lignocellulosic material; 10. The method of claim 1, comprising:

9. 9. The process of claim 8, wherein step c) is carried out at a temperature of 20 to 120°C, 30 to 120°C, 40 to 120°C, 50 to 120°C, preferably 50 to 100°C, preferably 60 to 85°C.

10. 9. The method of claim 8, wherein step b) is a vacuum pressure impregnation process carried out in the pressure range of 5 mbar to 20 bar.

11. 9. The method according to claim 8, comprising step a), in which the lignocellulosic material is pre-dried to a residual relative moisture content of less than 0.1-20%, preferably 0.1-15%.

12. The method of claim 8, wherein the aqueous composition is free of heavy metal compounds.

13. A process for treating lignocellulosic material with at least one polyorganosiloxane compound, preferably in the form of an aqueous composition, at a temperature below 100°C, preferably below 80°C.

14. 9. The method of claim 8, wherein the lignocellulosic material is treated with an aqueous composition comprising the polyorganosiloxane compound in an amount of at least 0.1 wt % to a maximum of 90 wt %, or at least 0.5 wt % to a maximum of 80 wt %, or at least 1 wt % to a maximum of 60 wt %, or at least 1 wt % to a maximum of 15 wt %, or at most 1 wt % to a maximum of 12 wt %, or at least 1 wt % to a maximum of 10 wt %, or at least 2 wt % to a maximum of 40 wt %, or at least 2.5 wt % to a maximum of 30 wt %, or at least 2.5 to a maximum of 20 wt %, or at least 4 wt % to a maximum of 20 wt %, or at least 5 wt % to a maximum of 15 wt %, or at least 6 wt % to a maximum of 15 wt %, or at least 7 wt % to a maximum of 12 wt %, or at least 7 wt % to a maximum of 10 wt %, based on the total weight of the aqueous composition.

15. A lignocellulosic material treated by the method of any one of claims 1 to 14.

16. 16. The lignocellulosic material according to claim 15, characterized in that it has a weight percentage gain after drying and leaching of not more than 15%, or not more than 10%, or between 4 and 85%, or between 5 and 7%, determined according to DIN EN 84-2020-10 (formerly DIN EN 84-2018-10), and / or a swelling coefficient of not more than 14%, preferably between 12 and 13%, determined according to the procedure described herein, and / or a mass loss due to fungal decay of brown rot pathogens of less than 5%, determined according to EN 113-2 (2021).

17. 16. The lignocellulosic material of claim 15, wherein the treated lignocellulosic material is paper, packaging material, wood, or wood composites.

18. Use of an aqueous composition comprising the polyorganosiloxane compound according to any one of claims 1 to 7, or the polyorganosiloxane compound according to any one of claims 8 to 12 and 14, as a treatment agent for lignocellulose material.

19. The polyorganosiloxane compound according to any one of claims 1 to 7, or an aqueous composition comprising the polyorganosiloxane compound according to any one of claims 8 to 12 and 14, is used to increase the water absorption resistance and / or dimensional stability and / or weather resistance and / or biological resistance of lignocellulosic materials, in particular the resistance to wood-damaging fungi and / or marine borers and / or wood pests. Use of the polyorganosiloxane compound according to any one of claims 1 to 7, or an aqueous composition comprising the polyorganosiloxane compound according to any one of claims 8 to 12 and 14, for increasing the water absorption resistance and / or dimensional stability and / or weather resistance and / or biological resistance of lignocellulosic materials, in particular the resistance to wood-damaging fungi and / or marine borers and / or wood pests.

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