Use of (per) fluoropolyether compounds as additives in formulations

Abstract

Use of mono- and bifunctional (per)fluoropolyether compounds as additives in formulations for the wood treatment, said (p-er)fluoropolyether compounds having the structures:

Description

[0001] The present invention relates to the use of additives for the protective treatment of wood materials to confer improved oil- and hydro-repellence properties.

[0002] Specifically, the invention relates to the addition of additives to the formulations usually utilized for the wood treatment, such as for example impregnating, antivegetative, insecticidal formulations, etc. Said additives are effectively used at very low surface concentrations, avoiding to modify the surface aspect of the treated wood material.

[0003] Compounds able to give wood hydro-repellence properties are known in the prior art. U.S. Pat. No. 5,141,983 which describes polyurethane-acrylic copolymers dispersed in water can for example be mentioned. The drawback of these products consists in that they are not able to confer suitable oil-repellence properties.

[0004] Other compounds, for example functionalized amino-organo hydrogenated siliconates are described in U.S. Pat. No. 5,178,668. Also for these products, there is the drawback that they are unable to confer suitable oil-repellence properties.

[0005] In U.S. Pat. No. 5,855,817 compounds having more than one hydroxyl function in combination with quaternary ammonium salts to confer hydro-repellence to wood, are described. Also in this case the oil-repellence properties are not high.

[0006] There are also aqueous formulations based on siliconates, polyurethanes and silicates, described in U.S. Pat. No. 5,356,716. Also in this case no mention is made to possible conferred oil-repellence properties.

[0007] Hydrocarbon solvent-based formulations comprising mixtures of fluoropolymers, hydrogenated silanes and silicones are described in U.S. PAT. NO. 5,593,483. Also in this case no mention is made to possible conferred oil-repellence properties.

[0008] In U.S. Pat. No. 5,691,000 specific perfluoropolyether phosphor monoester compounds able to give hydro- and oil-repellence to wood are described. The solvents used for the dissolution of these compounds are CFC-113 or alcohol/water mixtures. In this patent also other perfluoropolyether compounds having different functionalities are exemplified. The Examples show that these latter derivatives have lower hydro- and oil-repellence properties in comparison with the perfluoropolyether phosphor monoesters. In particular, the hydro-repellence values of phosphor monoesters when applied on wood are unsatisfactory. In fact, the Applicant has noticed that the oil- and hydro-repellence test is not sufficiently discriminating to identify the real protection degree given to wood. For this reason, these products have found a poor commercial application for the protective wood treatment. In this patent no mention is made to the use as additives of said products in the formulations used for wood.

[0009] The technical problem that the present invention intends to solve is that to find additives showing the following property combination:

[0010] improved hydro-repellence properties;

[0011] improved oil-repellence properties;

[0012] absence of any change of the wood natural aspect;

[0013] substantial maintenance of the properties conferred by impregnating, antivegetative, insecticidal, etc., formulations also after additive addition;

[0014] good compatibility of the additive with impregnating, anti-vegetative, insecticidal, etc. formulations so as to have substantially uniform oil- and hydro-repellence properties on the surface of the treated wood;

[0015] improvement of the wetting capacities of the above mentioned formulations for wood;

[0016] improved friction coefficient, i.e. decrease of the friction coefficient values of the wood surface which implies a wear limitation.

[0017] The need was therefore felt to have available additives for formulations used in the wood treatment, able to give the combination of the above mentioned properties.

[0018] An object of the invention are therefore mono- and bifunctional (per)fluoropolyether compounds and their use as additives in formulations for the wood treatment, excluding the formulations based on paraffin waxes dissolved in hydrocarbon solvents, said perf luoropolyether compounds having the following structures:

[0019] Rf—CFY—L—W (C)

[0020] W—L—YFC—O—Rf—CFY—L—W (D)

[0021] wherein:

[0022] L is an organic group selected from —CH2—(OCH2CH2)n—,

[0023] —CO—NR′—, with R′═H or C1-C4 alkyl group;

[0024] n═0−8, preferably 1−3;

[0025] Y═F, CF3;

[0026] W is selected from C1-C50 alkyl groups, preferably C8-C25, optionally containing one or more ether O, C6-C50 aryl groups, C7-C50 alkyl-aryl or aryl-alkyl groups; Rf has a number average molecular weight in the range 350-8,000, preferably 500-3,000 and it comprises repeating units having at least one of the following structures, statistically placed along the chain: (CFXO) , (CF2CF2O), (CF2CF2CF2O), (CF2CF2CF2CF2O), (CR4R5,CF2CF2O) , (CF(CF3)CF2O), (CF2CF (CF3)O),

[0027] wherein

[0028] X═F, CF3;

[0029] R4 and R5, equal to or different from each other, are selected from H, Cl, or perfluoroalkyl from 1 to 4 carbon atoms.

[0030] In particular Rf can have one of the following structures:

[0031] 1) —(CF2O) (CF2CF2O)b′—with a′/b′ in the range 0.5-2, extremes included, a′ and b′ being integers such as to give the above mentioned molecular weight;

[0032] 2) —(C3F6O)r—(C2F4O)b—(CFXO)t—with r/b═0.5-2.0; (r+b)/t is in the range 10-30, b, r and t being integers such as to give the above mentioned molecular weight, X has the above mentioned meaning;

[0033] 3) —(C3F6O)r′—(CFXO)t′—t′ can be O; when t′ is different from O then r′/t′═10-30, r′ and t′ being integers such as to give the above mentioned molecular weight; X has the above indicated meaning;

[0034] 4) —(OCF2CF(CF3) )z—OCF2(R′f)y—CF2O—(CF(CF3)CF2O)z—wherein z is an integer such that the molecular weight is the above mentioned one; y is an integer between 0 and 1 and R′f is a fluoroalkylene group having for example 1-4 carbon atoms;

[0035] 5) —(OCF2CF2CR4R5)q—OCF2(R═f)y—CF2O—(CR4R5CF2CF2O)s—

[0036] wherein: q and s are integers such that the molecular weight is the above mentioned one; R4, R5, R′f, y have the above mentioned meaning;

[0037] 6) —(C3F6O)r′″(CFXO)t′″—OCF2(R′f)y—CF2O(CF(CF3)CF2O)x″′(CFXO)t′″—wherein r′″/t′″═10-30, r′″ and t′″ being integers such as to give the above mentioned molecular weight; R′f and y having the above mentioned meaning.

[0038] In the above indicated formulas:

[0039] —(C3F6O)—can represent units of formula

[0040] —(CF(CF3)CF2O)—and/or —(CF2—CF(CF3)O)—

[0041] In the structure (C) wherein Rf is monofunctional, the other end group is of the T—O—type, wherein T is a (per) fluoroalkyl group selected from: —CF3, —CF5, —C3F7, —CF2Cl, —C2F4Cl, —C3F6Cl; optionally one or two F atoms, preferably one, can be replaced by H.

[0042] The mentioned fluoropolyethers are obtainable by the well known processes in the prior art, see for example the followwing patents herein incorporated by reference: U.S. Pat. Nos. 3,665,041, 2,242,218, 3,715,378, and EP 239,123. The functionalized fluoropolyethers are for example obtained according to EP 148482, U.S. Pat. No. 3,810,874.

[0043] The compounds of structure (C) are obtained by reacting a monofunctional perfluoropolyether ester derivative with an alkylamine. The alkylamine, generally under waxy form, is melted at a temperature in the range 40°-60° C. The perfluoropolyether ester derivative is dropped in the amine in an equimolar amount under stirring and maintaining the reactor at the desired temperature. At the end of the addition the alcohol which has formed from the condensation reaction is evaporated.

[0044] The compounds of structure (D) are obtained by reacting a bifunctional perfluoropolyether ester derivative with an alkylamine. The alkylamine, generally under waxy form, is melted at a temperature in the range 40°-60° C. The bifunctional perfluoropolyether ester derivative is dropped in the amine in molar amount 0.5 with respect to the amine under stirring and maintaining the reactor at the desired temperature. At the end of the addition the alcohol which has formed from the condensation reaction is evaporated.

[0045] The preferred compounds of the invention have structure (D) wherein L is —CO—NR′—, with R′═H; W is a C8-C25 alkyl group; Rf has structure 1).

[0046] Mixtures of the above mentioned compounds (C) and (D) can also be used.

[0047] The Applicant has surprisingly found that by using the above defined (per) fluoropolyether derivatives as additives of formulations for the wood treatment, the combination of the above mentioned properties is obtained. This result is unexpected since the same compounds of structure (C) and (D) not used as additives in formulations for wood, but used alone as treating agents are not able to confer high oil- and hydro-repellence properties, the concentrations being the same. The Applicant has found that in order to obtain comparable hydro- and oil repellence values on wood, when the components of the invention are used alone dispersed in solvents, it is necessary to carry out repeated treatments (at least 3). From the industrial point of view this represents a remarkable application drawback besides higher costs.

[0048] The formulations for wood to which the additives of the invention are added are those known for the wood treatment: impregnating, antivegetative, insecticidal, anti-mould formulations, paints, etc. can be mentioned. Preferably said formulations for wood are based on solvents, such as for example ketones, alcohols, glycols, hydrocarbons.

[0049] The impregnating formulations prevailingly comprise as main components natural oils, acrylic and polyurethane polymers. The anti-vegetative formulations prevailingly comprise as main components limonene, alkyd resins and fluorinated acrylic polymers. The insecticidal formulations prevailingly comprise as main components dichlofluoranid, permethrin, linseed oil and dibutylphthalace.

[0050] The additives of the invention are added to the formulations in concentrations in the range 0.01-10% by weight, preferably 0.1-5% by weight with respect to the formulation weight. The application of the formulation can be carried out by brushing, spraying, etc. Optionally, if required by the industrial application process, after the treatment a thermal treatment can be carried out for a quicker removal of the solvent.

[0051] The present invention will be better illustrated by the following Examples, which have a merely indicative but not limitative purpose of the scope of the invention itself.

EXAMPLES

[0052] Evaluation of the oil-repellence properties

[0053] The oil-repellence properties conferred to a wood substratum by the perfluoropolyether (PFPE) products of the invention have been evaluated, after treatment of the wood specimen with a solution at different concentrations by weight of product, following the procedure reported below:

[0054] 10 μl of vaseline oil are deposited on the treated surface by a syringe;

[0055] the area increase of the deposited drop at subsequent times (5,10,15,20 minutes) is determined.

[0056] A greater diffusion of the drops deposited on the treated wood surface and therefore a higher area of the drop show a lower repellent power of the treatment and therefore lower oil-repellence conferred.

[0057] Evaluation of the hydro-repellence properties

[0058] The hydro-repellence properties conferred to a wood substratum by the perf luoropolyether products of the invention have been evaluated as follows: after treatment of the wood specimen with a solution at different concentrations by weight of product, the hydro-repellence of the treated wood is evaluated by depositing 5 μl of a mixture of water/isopropanol on the treated surface. The area of the deposited drops water/isopropanol (at two ratios by weight water/isopropanol equal to 60:40 and 30:70) is measured after one minute from the deposition. A higher drop area on the treated surface shows a lower repellent power of the treatment and therefore lower hydro-repellence conferred.

EXAMPLE 1

[0059] A monofunctional perfluoropolyether compound (PFPE) having formula:

Cl(C3F6O)nCF2—C(O)—NH—C18H37  (I)

[0060] is used, wherein n═2-5

[0061] To a commercial anti-vegetative formulation LINFO® (GEAL) containing limonene, alkyd resins and fluorinated acrylic polymers, the compound of formula (I) is additived at a concentration equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Hemlock wood specimen. At the end of the treatment, before carrying out the oil-repellence test, the wood specimen has been placed in a stove at T═60° C. for 2 hours in order to facilitate the solvent evaporation present in the anti-vegetative formulation.

[0062] The anti-vegetative formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already starting from only one coat application. The oil-repellence test values evaluated on Hemlock wood treated with different concentrations of the perf luoropolyether additive are reported in Table 1. Such data are compared with those of the not additived anti-vegetative formulation (first column) always applied in one single coat.

	TABLE 1
	PFPE concentrations of formula (I)
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	60.8 mm2	55	37.9	35.6
after 5 min.
Drop area	82.2 mm2	67.3	44.5	39.8
after 10 min.
Drop area	97.6 mm2	73.8	48.8	44.5
after 15 min.
Drop area	99.4 mm2	75.2	50.4	48
after 20 min.

[0063] The same wood specimen have furthermore been subjected to hydro-repellence tests by depositing drops of water/isopropanol mixtures having a ratio by weight 60/40 and 30/70 and evaluating the drop area after one minute. The obtained results, compared with those resulting from the application of the anti-vegetative not additived formulation (first column) always applied in one single coat, are reported in Table 2.

	TABLE 2
	PFPE concentrations of formula (I)
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	20 mm2	9.7	8.0	7.5
Drop area
H2O/IPA 30/70	56.3 mm2	43.2	15.4	15.0
Drop area

EXAMPLE 2

[0064] A bifunctional perfluoropolyether (PFPE) compound having formula:

H37C18NH—C(O)—CF2O(CF2CF2O)n(CF2O)mCF2—C(O)—NH—C18H37  (II)

[0065] is used.

[0066] The compound of formula (II) is dissolved in methylethylketone forming a solution at 50% by weight. Said solution is additived to the commercial anti-vegetative formulation LINFO® (GEAL) obtaining a final concentration of compound (II) equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Hemlock wood specimen.

[0067] The anti-vegetative formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 3, the hydro-repellence test values in Table 4, compared with those obtained with the not additived anti-vegetative formulation (first column) always applied in one single coat.

	TABLE 3
	Bifunctional PFPE concentrations of
	formula (II)
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	60.8 mm2	17.8	13.6	13.6
after 5 min.
Drop area	82.2 mm2	17.5	14	13.6
after 10 min.
Drop area	97.6 mm2	18.9	14.4	13.6
after 15 min.
Drop area	99.4 mm2	19.4	14.8	13.6
after 20 min.

[0068]

	TABLE 4
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	20 mm2	7.4	6.7	6.7
Drop area
H2O/IPA 30/70	56.3 mm2	10.0	8.1	7.7
Drop area

EXAMPLE 3

[0069] To a commercial impregnating formulation XYLOVALCERA® (VELECA) containing natural oils, acrylic and polyurethane polymers, the perfluoropolyether compound of formula (I) is additived at a concentration equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Hemlock wood specimen.

[0070] The impregnating formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 5, the hydro-repellence test values in Table 6, compared with those obtained with the not additived impregnating formulation (first column) always applied in one single coat.

	TABLE 5
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	200 mm2	91.2	36.2	32.2
after 5 min.
Drop area	200 mm2	134.6	34.1	35.2
after 10 min.
Drop area	200 mm2	150	60	38.6
after 15 min.
Drop area	200 mm2	180	64	47.2
after 20 min.

[0071]

	TABLE 6
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	100 mm2	9.8	8.9	10.4
Drop area
H2O/IPA 30/70	100 mm2	16	13.6	13.8
Drop area

EXAMPLE 4

[0072] The perfluoropolyether compound of formula (II) is dissolved in methylethylketone forming a solution at 50% by weight. Said solution is additived to the commercial impregnating formulation XYLOVALCERA°0 (VELECA) obtaining a final concentration of compound (II) equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Hemlock wood specimen.

[0073] The impregnating formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 7, the hydro-repellence test values in Table 8, compared with those obtained with the not additived impregnating formulation (first column) always applied in one single coat.

	TABLE 7
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	200 mm2	19.1	15.8	13.1
after 5 min.
Drop area	200 mm2	19.1	16	13.8
after 10 min.
Drop area	200 mm2	20.6	16	13.9
after 15 min.
Drop area	200 mm2	21.6	16.5	14
after 20 min.

[0074]

	TABLE 8
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	100 mm2	8.6	8.4	7.4
Drop area
H2O/IPA 30/70	100 mm2	11.4	11.3	10.9
Drop area

EXAMPLE 5

[0075] To a commercial insecticidal formulation XYLAMON® (SOLVAY) containing dichlofluoanide, pernetrine, linseed oil and dibutylphtalate, the perfluoropolyether compound of formula (I) is additived at a concentration equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Hemlock wood specimen.

[0076] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 9, the hydro-repellence test values in Table 10, compared with those obtained with the not additived insecticidal formulation (first column) always applied in one single coat.

	TABLE 9
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	51 mm2	48.8	37	36
after 5 min.
Drop area	61 mm2	55.8	42.5	39
after 10 min.
Drop area	73.7 mm2	56.0	52.7	41
after 15 min.
Drop area	84.8 mm2	58.9	59	58.5
after 20 min.

[0077]

	TABLE 10
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	22.2 mm2	9.2	7.9	7.3
Drop area
H2O/IPA 30/70	43.8 mm2	18.7	16.3	13.3
Drop area

EXAMPLE 6

[0078] The perfluoropolyether compound of formula (II) is dissolved in methylethylketone forming a solution at 50% by weight. Said solution is additived to the commercial insecticidal formulation XYLAMON® (SOLVAY) obtaining a final concentration of compound (II) equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Hemlock wood specimen.

[0079] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 11, the hydro-repellence test values in Table 12, compared with those obtained with the not additived insecticidal formulation (first column) always applied in one single coat.

	TABLE 11
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	51	mm2	30.8	13.8	12.3
after 5 min.
Drop area	61	mm2	32.6	14.1	12.3
after 10 min.
Drop area	73.7	mm2	33.8	14.5	12.9
after 15 min.
Drop area	84.8	mm2	35.1	15.3	13.5
after 20 min.

[0080]

	TABLE 12
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	22.2	mm2	7.9	7.8	7.6
Drop area
H2O/IPA 30/70	43.8	mm2	9.8	8.4	8.3
Drop area

EXAMPLE 7

[0081] To the commercial insecticidal formulation XYLAMON® (SOLVAY) the perfluoropolyether compound of formula (I) is additived at a concentration equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Parquet wood specimen.

[0082] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 13, the hydro-repellence test values in Table 14, compared with those obtained with the not additived insecticidal formulation (first column) always applied in one single coat.

	TABLE 13
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	200	mm2	65	38	34
after 5 min.
Drop area	200	mm2	87	40	40
after 10 min.
Drop area	200	mm2	90	49	43
after 15 min.
Drop area	200	mm2	106	49	44
after 20 min.

[0083]

	TABLE 14
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	100	mm2	8	8	8
Drop area
H2O/IPA 30/70	100	mm2	18	14	13
Drop area

EXAMPLE 8

[0084] The perfluoropolyether compound of formula (II) is dissolved in methylethylketone forming a solution at 50% by weight. Said solution is additived to the commercial insecticidal formulation XYLAMON® (SOLVAY) obtaining a final concentration of compound (II) equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a Parquet wood specimen.

[0085] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 15, the hydro-repellence test values in Table 16, compared with those obtained with the not additived insecticidal formulation (first column) always applied in a single coat.

	TABLE 15
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	200	mm2	14	11	12
after 5 min.
Drop area	200	mm2	14	12	13
after 10 min.
Drop area	200	mm2	15	13	13
after 15 min.
Drop area	200	mm2	15	13	13
after 20 min.

[0086]

	TABLE 16
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	100	mm2	8	7	7
Drop area
H2O/IPA 30/70	100	mm2	10	9	9
Drop area

EXAMPLE 9

[0087] To the commercial insecticidal formulation XYLAMON® (SOLVAY) the perfluoropolyether compound of formula (I) is additived at a concentration equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a pine wood specimen.

[0088] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 17, the hydro-repellence test values in Table 18, compared with those obtained with the not additived insecticidal formulation (first column) always applied in one single coat.

	TABLE 17
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	250	mm2	100	44	47
after 5 min.
Drop area	250	mm2	121	56	64
after 10 min.
Drop area	250	mm2	165	74	75
after 15 min.
Drop area	250	mm2	181	79	84
after 20 min.

[0089]

	TABLE 18
	Monofunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	100	mm2	10	10	9
Drop area
H2O/IPA 30/70	100	mm2	16	12	13
Drop area

EXAMPLE 10

[0090] The perf luoropolyether compound of formula (II) is dissolved in methylethylketone forming a solution at 50% by weight. Said solution is additived to the commercial insecticidal formulation XYLAMON® (SOLVAY) obtaining a final concentration of compound (II) equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a pine wood specimen.

[0091] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 19, the hydro-repellence test values in Table 20, compared with those obtained with the not additived insecticidal formulation (first column) always applied in one single coat.

	TABLE 19
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	250	mm2	14	14	13
after 5 min.
Drop area	250	mm2	15	14	13
after 10 min.
Drop area	250	mm2	15	14	14
after 15 min.
Drop area	250	mm2	15	14	15
after 20 min.

[0092]

	TABLE 20
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	100	mm2	9	8	7
Drop area
H2O/IPA 30/70	100	mm2	10	10	10
Drop area

EXAMPLE 11

[0093] The perfluoropolyether compound of formula (II) is dissolved in methylethylketone forming a solution at 50% by weight. Said solution is additived to the commercial insecticidal formulation XYLOVALCERA® (VELECA) obtaining a final concentration of compound (II) equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a pine wood specimen.

[0094] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 21, the hydro-repellence test values in Table 22, compared with those obtained with the not additived insecticidal formulation (first column) always applied in one single coat.

	TABLE 21
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	55 mm2	12	11	11
after 5 min.
Drop area	56 mm2	13	12	11
after 10 min.
Drop area	58 mm2	14	12	12
after 15 min.
Drop area	58 mm2	14	13	13
after 20 min.

[0095]

	TABLE 22
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	17 mm2	8	8	7
Drop area
H2O/IPA 30/70	34 mm2	9	9	8
Drop area

EXAMPLE 12

[0096] The perfluoropolyether compound of formula (II) is dissolved in methylethylketone forming a solution at 50% by weight. Said solution is additived to the commercial insecticidal formulation XYLOVALCERA® (VELECA) obtaining a final concentration of compound (II) equal to 1%, 5% and 10% by weight. The resulting product is applied by brushing to a parquet wood specimen.

[0097] The insecticidal formulation additived with the compound of the invention results effective in conferring hydro-/oil-repellence properties already with only one coat application. The oil-repellence test values are reported in Table 23, the hydro-repellence test values in Table 24, compared with those obtained with the not additived insecticidal formulation (first column) always applied in one single coat.

	TABLE 23
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
Drop area	51 mm2	16	14	12
after 5 min.
Drop area	51 mm2	16	14	14
after 10 min.
Drop area	54 mm2	17	15	14
after 15 min.
Drop area	54 mm2	17	15	14
after 20 min.

[0098]

	TABLE 24
	Bifunctional PFPE concentrations
	—	1% by wt.	5% by wt.	10% by wt.
H2O/IPA 60/40	17 mm2	8	8	8
Drop area
H2O/IPA 30/70	34 mm2	11	10	10
Drop area

EXAMPLE 13 (comparative)

[0099] The perfluopropolyether compound of structure (I) is not used as additive of a formulation for the wood treatment as in Examples 1-12, but used dispersed in a n-hexane solution containing the compound (I) at a concentration equal to 5% by weight.

[0100] 3 coats of product have been necessary to obtain a good coating of the surface of the hemlock wood specimen and to observe a conferring of hydro- and oil-repellence properties comparable to the case of Examples 1-12, in which only one coat application has been sufficient.

[0101] The oil-repellence test values are reported in Table 25, the hydro-repellence test values in Table 26, compared with the results of Examples 1, 3, 5 wherein the compound (I) is combined with various formulations for the wood treatment and applied in a single coat at the same concentrations.

	TABLE 25
	Formu-	Formu-		With	With
	lation	lation	With Anti-	impreg-	insecti-
	absence	absence	vegetative	nant	cidal
	1 coat	3 coats	1 coat	1 coat	1 coat
Drop area	72 mm2	20	37.9	36.2	37
after 5 min.
Drop area	75 mm2	21.1	44.5	34.1	42.5
after 10 min.
Drop area	78 mm2	21.2	48.8	60	52.7
after 15 min.
Drop area	82 mm2	22.0	50.4	64	59
after 20 min.

[0102]

	TABLE 26
	Formu-	Formu-		With	With
	lation	lation	With Anti-	impreg-	insecti-
	absence	absence	vegetative	nant	cidal
	1 coat	3 coats	1 coat	1 coat	1 coat
H2O/IPA 60/40	30 mm2	9.6	8	8.9	7.9
Drop area
H2O/IPA 30/70	33 mm2	12.2	15.4	13.6	16.3
Drop area

EXAMPLE 14 (comparative)

[0103] The perfluopropolyether compound of structure (II) is not used as additive of a formulation for the wood treatment as in Examples 1-12, but used dispersed in a n-hexane solution containing the compound (II) at a concentration equal to 5% by weight.

[0104] 3 coats of product have been necessary to obtain a good coating of the surface of the hemlock wood specimen and to observe a conferring of hydro- and oil-repellence properties comparable with the case of Examples 1-12, in which only one coat application has been sufficient.

[0105] The oil-repellence test values are reported in Table 27, the hydro-repellence test values in Table 28, compared with the results of Examples 2, 4, 6 wherein the compound (II) is combined with various formulations for the wood treatment and applied in one single coat at the same concentration.

	TABLE 27
	Formu-	Formu-		With	With
	lation	lation	With Anti-	impreg-	insecti-
	absence	absence	vegetative	nant	cidal
	1 coat	3 coats	1 coat	1 coat	1 coat
Drop area	41 mm2	11.4	13.6	15.8	13.8
after 5 min.
Drop area	44 mm2	11.4	14	16	14.1
after 10 min.
Drop area	46 mm2	12.4	14.4	16	14.5
after 15 min.
Drop area	47 mm2	12.5	14.8	16.5	15.3
after 20 min.

[0106]

	TABLE 28
	Formu-	Formu-		With	With
	lation	lation	With Anti-	impreg-	insecti-
	absence	absence	vegetative	nant	cidal
	1 coat	3 coats	1 coat	1 coat	1 coat
H2O/IPA 60/40	25 mm2	11	6.7	8.4	7.8
Drop area
H2O/IPA 30/70	30 mm2	8.4	8.1	11.3	8.4
Drop area

EXAMPLE 15 (comparative)

[0107] A monofunctional perfluoropolyether (PFPE) phosphate having the formula:

[Cl(CF3F6O)pCF2CH2O(CH2CH2O)n]mP(O)m-3

[0108] is used, with p═2−5, n═1−4, m═1−3 Said compound is used dispersed in a solution of isopropyl alcohol at a concentration equal to 5% by weight. Although up to 3 coats of product on a hemlock wood specimen have been applied, it has not been possible to obtain suitable hydro-repellence values as in the case of Examples 1-12, wherein only one coat application has been sufficient.

[0109] The hydro-repellence test values of the monofunctional phosphate are reported in Table 29 compared with the hydro-repellence values conferred by the compounds of structure (I) and (II) of the invention reported in Examples 1 and 2.

	TABLE 29
			Compound (I)	Compound (II)
	Phosphate	Phosphate	with Anti-	with Anti-
	PFPE	PFPE	vegetative	vegetative
	1 coat	3 coats	1 coat	1 coat
H2O/IPA 60/40	100 mm2	100	8.0	6.7
Drop area
H2O/IPA 30/70	100 mm2	100	15.4	8.1
Drop area

Claims

1. Use of mono- and bifunctional (per)fluoropolyether compounds as additives in formulations for the wood treatment, excluding the formulations based on paraffin waxes dissolved in hydrocarbon solvents, said perfluoropolyether compounds having the following structures: Rf—CFY—L—W(C) W—L—YFC—O—Rf—CFY—L—W(D) wherein: L is an organic group selected from —CH2—(OCH2CH2)n—, —CO—NR′—, with R′═H or C1-C4 alkyl group; n═0-8, preferably 1-3; Y═F, CF3; W is selected from C1-C50 alkyl groups, preferably C8-C25, optionally containing one or more ether O, C6-C50 aryl groups, C7-C50 alkyl-aryl or aryl-alkyl groups; Rf has a number average molecular weight in the range 350-8,000, preferably 500-3,000 and it comprises repeating units having at least one of the following structures, statistically placed along the chain: (CFXO), (CF2CF2O), (CF2CF2CF2O), (CF2CF2CF2CF2O), (CR4R5CF2CF2O), (CF(CF3)CF2O), (CF2CF(CF3)O), wherein X═F, CF3; R4 and R5, equal to or different from each other, are selected from H, Cl, or perfluoroalkyl from 1 to 4 carbon atoms.

2. Use according to claim 1, wherein Rf is selected from the following structures: 1) —(CF2O)a′—(CF2CF2O)b′—with a′/b′ in the range 0.5-2, extremes included, a′ and b′ being integers such as to give the above mentioned molecular weight; 2) (C3F6O)r—(C2F4O)b—(CFXO)t—with r/b═0.5-2.0; (r+b)/t is in the range 10-30, b, r and t being integers such as to give the above mentioned molecular weight, X has the above mentioned meaning; 3) —(C3F6O)r′—(CFXO)t′—when t′ is different from O then r′/t′═10-30, r′, and t′ being integers such as to give the above mentioned molecular weight; x has the above indicated meaning; 4) —(OCF2CF(CF3) )z—OCF2(R′f)y—CF2O—(CF(CF3)CF2O)z—wherein z is an integer such that the molecular weight is the above mentioned one; y is an integer between 0 and 1 and R′f is a fluoro-alkylene group having for example 1-4 carbon atoms; 5) —(OCF2CF2CR4R5)q—OCF2(R′f)y—CF2O—(CR4R5CF2CF2O)s—wherein: q and s are integers such that the molecular weight is the above mentioned one; R4, R5, R′f, y have the above mentioned meaning; 6) —(C3F6O)r′″(CFXO)t′″—OCF2(R′f)y—CF2O(CF(CF3)CF2O)r′″(C—FXO)t′″—wherein r′″/t′″═10-30, r′″ and t′″ being integers such as to give the above mentioned molecular weight;

3. Use according to claims 1-2, wherein in the structure (C) the other end group is of the T—O— type, wherein T is a (per) fluoroalkyl group selected from: —CF3, —C2F5, —C3F7, —CF2Cl, —C2F4Cl, —C3F6Cl; optionally one or two F atoms, preferably one, being replaced by H.

4. Use according to claims 1-3, wherein the perfluoropolyether compounds have structure (D) wherein L is —CO—NR′—, with R′═H; W is a C8-C25 alkyl group; Rf has structure 1).

5. Use according to claims 1-4, wherein the formulations for the wood treatment are selected from the impregnating, antivegetative, insecticidal, anti-mould formulations, paints, preferably based on solvents, such as ketones, alcohols, glycols, hydrocarbons.

6. Use according to claim 5, wherein the impregnating formulations comprise as main components natural oils, acrylic and polyurethane polymers.

7. Use according to claim 5, wherein the anti-vegetative formulations comprise as main components limonene, alkyd resins and fluorinated acrylic polymers.

8. Use according to claim 5, wherein the insecticidal formulations comprise as main components dichlofluoanid, pernethrin, linseed oil and dibutylphthalate.

9. Use according to claims 1-8, wherein the compounds are added to the formulations in concentrations in the range 0.01-10% by weight, preferably 0.1-5% by weight with respect to the formulation weight.

10. Use according to claims 1-9, wherein the formulation is applied by brushing, spraying.