Silicone/Fluorinated Organic Compound Mixed Composition For Conferring Oleophobicity And/Or Hydrophobicity On A Textile Material

Abstract

Crosslinkable liquid composition which can crosslink to give a hydrophobic and/or oleophobic silicone elastomer coating, comprising a polyorganosiloxane (POS) resin A exhibiting, per molecule, on the one hand, at least two different siloxyl units chosen from those of M, D, T and Q types, one of the units being a T unit or a Q unit, and, on the other hand, at least three hydrolysable/condensable groups of OH and/or OR1 types, where R1 is a linear or branched C1 to C6, preferably C1 to C3, alkyl radical, a system for promoting attachment B and a polyfluoroacrylate F. Use of this composition to form a silicone elastomer sheath around the constituent yarns, fibres and/or filaments of a textile material and to confer long-lasting oleophobicity and/or hydrophobicity properties.

Description

EXAMPLES

1) Fluorinated compound (Pf):

Polyfluoroacrylate sold by DuPont de Nemours under the commercial reference FORAPERLE® F225. This polyfluoroacrylate is presented in the form of a solution in a solvent (n-butyl acetate) comprising approximately 30% on a dry basis of polyacrylate.

2) Crosslinkable liquid silicone formulation according to the invention (F1):

It has the following composition (the parts are given by weight):

A: mixture of:

• • hydroxylated MDT resin having 0.5% of OH by weight and composed of 62% by weight of CH₃SiO₃/2 units, 24% by weight of (CH₃)₂SiO_2/2 units and 14% by weight of (CH₃)₃SiO_1/2 units: 57 parts; and of
  • hydroxylated MQ resin having 2% of OH by weight and composed of 45% by weight of SiO_4/2 units and 55% by weight of (CH₃)₃SiO_1/2 units: 7 parts;

B: mixture of:

• • n-butyl (Bu) titanate of formula Ti(OBu)₄: 2 parts; and of
  • ethyl (Et) silicate of formula Si(OEt)₄: 4 parts;

D: white spirit: 30 parts.

It is rediluted in the white spirit before application, at the rate of a concentration of 15% by weight of A+B.

3) Crosslinkable liquid silicone formulation according to the invention (F2):

Mixture of 80 parts of F1 and of 20 parts of a hydroxylated gum C having of the order of 0.01% of OH by weight and composed to 100% by weight of (CH₃)₂SiO_2/2 units, having a viscosity of 4 000 000 mPa·s.

The mixture is rediluted in the white spirit before application, at the rate of a concentration of 15% by weight of A+B+C.

3) Test of the oleophobicity

The treated textile used is a woven textile made of polyamide-6,6 and elasthane (80/20). It is composed of elastic yarns in warp and weft based on an elasthane, 44 dtex, covered with some PA-6,6, 44 dtex/34 strands. These textile surfaces exhibit a high bidirectional elasticity (100% elongation in both directions) and a unit weight of 130 g/m².

The textile is treated by padding with the solutions. It is subjected to drying at ambient temperature for a few minutes and is then heat treated at 180° C. for 2 minutes.

The beading effect is measured by the Spray Test AATCC Test Method 22-1996. The test consists in spraying the sample of the textile article with a given volume of water. The appearance of the sample is subsequently evaluated visually and compared with the standards. A grade from 0 to 5 is assigned according to the amount of water retained. For 0, the sample is completely wet, for 5, the sample is completely dry.

The oleophobic nature is measured by the standardized test (AATCC Test Method 118-1997) known under the name of “Oil repellency: Hydrocarbon Resistance Test”. The “oil resistance test” consists in depositing drops of liquids with decreasing interfacial tensions on the textile and in determining the liquid LH starting from which spreading of the drops is observed. A grade of 0 to 8 is assigned depending on the LH obtained, 0 when liquid petrolatum spreads out (liquid paraffin, slight oleophobic nature), 3 when n-tetradecane spreads out (marked oleophobicity) and 8 when n-heptane no longer spreads out (very marked oleophobicity).

To test the longevity of the treatment, the samples are washed for 30 minutes in a continuous washing cycle at 50° C. in a commercial washing machine (Miele trade mark, Novotronic 824 model) in the presence of a standardized detergent (ECE Non-Phosphate Reference Detergent A—the formulation of which is given in BS1006: 1900: UK-T0) which corresponds to strong washing conditions. The amount of detergent used is 96 g (as the volume of water used by the machine is 12 l, this amount corresponds to a conventional concentration of 8 g/l). At the end of the cycle, 3 successive rinsing operations are carried out, followed by spin drying at 500 rev/min for 2 minutes. The textiles are subsequently dried in an oven at 150° C. for 1 min.

4) Experimental results:

	Before washing	After washing
		Debeading	Oil	Debeading	Oil
Com-		(Spray	resistance	(Spray	resistance
position	Concentration	test)	test	test)	test
Pf	2%	3	6	1	2
Pf	6%	4	7	1	2
Pf	10%	5	8	1	2
F1	6%	4	0	2	0
F1 + Pf	2% + 2%	5	7	3	2
F1 + Pf	6% + 2%	5	8	3	6
F1 + Pf	10% + 2%	5	8	3	6
F2	8%	3	0	2	0
F2 + Pf	8% + 2%	4	8	3	7

The results show:

the poor longevity of the treatments carried out using the polyfluoroacrylate (Pf) alone;

the improvement in the oleophobic properties of the mixtures of silicone composition F1 or F2 and polyfluoroacrylate Pf;

the addition of the silicone composition makes it possible to reduce by a factor of 5 the amount of polyfluoroacrylate necessary in order to obtain the maximum grade in the oil resistance test, which constitutes a saving in cost insofar as polyfluoroacrylates are expensive;

the improvement in the longevity of the oil-repellent and water-repellent treatment with the mixtures combining silicone composition F1 or F2 and polyfluoroacrylate Pf.

It should be clearly understood that the invention defined by the appended claims is not limited to the specific embodiments indicated in the above description but encompasses the alternative forms thereof which depart neither from the scope nor from the spirit of the present invention.

Claims

1.-26. (canceled)

27. Crosslinkable liquid composition which can crosslink to give a hydrophobic and/or oleophobic silicone elastomer coating, comprising a polyorganosiloxane (POS) resin A exhibiting, per molecule, on the one hand, at least two different siloxyl units selected from those of M, D, T and Q types, one of the units being a T unit or a Q unit, and, on the other hand, at least three hydrolysable/condensable groups of OH and/or OR1 types, where R1 is a linear or branched C1 to C6, preferably C1 to C3, alkyl radical, a system for promoting attachment B and a polyfluoroacrylate F.

28. Composition according to claim 27, comprising a system for promoting attachment comprising: either B-1 at least one metal alkoxide of general formula: M[(OCH2CH2)aOR2]n   (I)in which: M is a metal selected from the group formed by: Ti, Zr, Ge, Si, Mn and Al;n=valency of M;the R2 substituents, which are identical or different, each represent a linear branched C1 to C12 alkyl radical;a represents zero, 1 or 2;with the conditions according to which, when symbol a represents zero, the alkyl radical R2 has from 2 to 12 carbon atoms and, when the symbol a represents 1 or 2, the alkyl radical R2 has from 1 to 4 carbon atoms;optionally the metal M is connected to a ligand;or B-2 at least one metal polyalkoxide resulting from the partial hydrolysis of the monomeric alkoxides of formula (I) mentioned above in which the symbol R2 has the abovementioned meaning with the symbol a representing zero;or a combination of B-1 and B-2;or B-3 at least one optionally alkoxylated organosilane comprising, per molecule, at least one C2-C6 alkenyl group (B 3/1), and/or at least one organosilicon compound comprising at least one epoxy, amino, ureido, isocyanato and/or isocyanurate radical (B 3/2);or B-4 a combination of B-1 with B 3/1 and/or B 3/2, a combination of B-2 with B 3/1 and/or B 3/2, or a combination of B-1 and B-2 with B 3/1 and/or B 3/2.

29. Composition according to claim 27, furthermore comprising a functional additive C comprising: either C-1 at least one silane and/or at least one POS which is essentially linear and/or at least one POS resin, each of these organosilicon compounds being equipped, per molecule, on the one hand, with attaching functional group(s) (AF) capable of reacting with A and/or B or capable of generating, in situ, functional groups capable of reacting with A and/or B and, on the other hand, with applicational functional group(s) (UF);or C-2 at least one hydrocarbonaceous compound comprising at least one saturated or unsaturated, linear or branched hydrocarbonaceous group and optionally one or more heteroatom(s) other than Si (such as, for example, an oxygen, fluorine or nitrogen atom) and existing in the form of a monomeric, oligomeric (linear, cyclic or branched) or polymeric (linear, cyclic or branched) structure, the said hydrocarbonaceous compound being equipped, per molecule, on the one hand, with attaching functional group(s) (AF) capable of reacting with A and/or B or capable of generating, in situ, functional groups capable of reacting with A and/or B and, on the other hand, with applicational functional group(s) (UF);or a mixture of C-1 and C-2.

30. Composition according to claim 27, comprising a polyfluoroacrylate comprising at least one polymer chain unit derived from a fluoroalkyl (meth)acrylate monomer.

31. Composition according to claim 30, comprising a polyfluoroacrylate comprising at least one polymer chain unit derived from a perfluoroalkyl (meth)acrylate monomer.

32. Composition according to claim 30, in which the polymer comprises at least one unit —C═0—O—(CH2)n—(CF2)m—CF3, with n between 0 and 15, preferably from 1 to 10, better still from 1 to 4, more preferably 2, and m between 0 and 20, preferably between 1 and 20, better still between 2 and 20, more preferably between 3 and 12.

33. Composition according to claim 30, in which the polyacrylate additionally comprises a polymer chain unit derived from an alkyl (meth)acrylate monomer.

34. Composition according to claim 33, in which the polyacrylate comprises at least one unit —C(═O)—O-(alkyl), with alkyl representing a linear, branched or cyclic alkyl having from 1 to 25 C, preferably from 1 to 9 C; preferably, at least one unit Y′: —C(═O)—O—(CH2)p—CH3, with p between 0 and 24, preferably between 1 and 15, better still between 1 and 8.

35. Composition according to claim 30, in which the polyacrylate additionally comprises one or more polymer chain units derived from a (meth)acrylate monomer carrying one or more polar groups.

36. Composition according to claim 35, in which the polymer comprises one or more polar groups selected from amine, quaternary amine, alkyl or carboxylate groups or an anionic group having a counter-ion of ammonium, alkylammonium or alkali metal type.

37. Composition according to claim 27, in which the proportion by weight of polyfluoroacrylate F to the sum of the dry components A, B and optionally C is between 1% and 99% by weight, in particular between 5% and 80% by weight, preferably between 10% and 60% by weight.

38. Composition according to claim 27, additionally comprising at least one constituent D which is an organic solvent or diluent and/or water.

39. Composition according to claim 27, comprising A—at least one polyorganosiloxane (POS) resin exhibiting, per molecule, on the one hand, at least two different siloxyl units selected from those of M, D, T and Q types, one of the units being a T unit or a Q unit, and, on the other hand, at least three hydrolysable/condensable groups of OH and/or OR1 types, where R1 is a linear or branched C1 to C6, preferably C1 to C3, alkyl radical;B—at least one system for promoting the attachment of the said network to the surface of the textile material preferably comprising:either B-1 at least one metal alkoxide of general formula: M[(OCH2CH2)aOR2]n   (I)in which: M is a metal selected from the group formed by: Ti, Zr, Ge, Si, Mn and Al;n=valency of M;the R2 substituents, which are identical or different, each represent a linear branched C1 to C12 alkyl radical;a represents zero, 1 or 2;with the conditions according to which, when the symbol a represents zero, the alkyl radical R2 has from 2 to 12 carbon atoms and, when the symbol a represents 1 or 2, the alkyl radical R2 has from 1 to 4 carbon atoms;optionally the metal M is connected to one or more ligands, for example those obtained using a particular β-diketone, β-ketoesters and malonic esters (for example, acetylacetone) or triethanolamine;or B-2 at least one metal polyalkoxide resulting from the partial hydrolysis of the monomeric alkoxides of formula (I) mentioned above in which the symbol R2 has the abovementioned meaning with the symbol a representing zero;or a combination of B-1 and B-2;or B-3 at least one optionally alkoxylated organosilane comprising, per molecule, at least one C2-C6 alkenyl group (B 3/1), and/or at least one organosilicon compound comprising at least one epoxy, amino, ureido, isocyanato and/or isocyanurate radical (B 3/2);or B4 a combination of B-1 with B 3/1 and/or B 3/2, a combination of B-2 with B 3/1 and/or B 3/2, or a combination of B-1 and B-2 with B 3/1 and/or B 3/2;C—optionally at least one functional additive comprising:either C-1 at least one silane and/or at least one POS which is essentially linear and/or at least one POS resin, each of these organosilicon compounds being equipped, per molecule, on the one hand, with attaching functional group(s) (AF) capable of reacting with A and/or B or capable of generating, in situ, functional groups capable of reacting with A and/or B and, on the other hand, with hydrophobicity functional group(s) (HF);or C-2 at least one hydrocarbonaceous compound comprising at least one saturated or unsaturated, linear or branched hydrocarbonaceous group and optionally one or more heteroatom(s) other than Si (such as, for example, an oxygen, fluorine or nitrogen atom) and existing in the form of a monomeric, oligomeric (linear, cyclic or branched) or polymeric (linear, cyclic or branched) structure, the said hydrocarbonaceous compound being equipped, per molecule, on the one hand, with attaching functional group(s) (AF) capable of reacting with A and/or B or capable of generating, in situ, functional groups capable of reacting with A and/or B and, on the other hand, with hydrophobic functional group(s) (HF);or a mixture of C-1 and C-2;D—at least one non-reactive additive system comprising:.(i) at least one organic solvent or diluent and/or one non-reactive organosilicon compound; (2i) and/or water; andwith, per 100 parts by weight of constituent A: from 0.5 to 200, preferably from 0.5 to 100 and more particularly from 1 to 70 parts of constituent B,from 0 to 1,000, preferably from 1 to 1,000 and more preferentially from 1 to 300 parts of constituent C,per 100 parts of constituent A, from 1 to 10,000, preferably from 1 to 5,000 parts of constituent D.

40. Composition according to claim 27, comprising a mixture A-3: of at least one resin exhibiting, in its structure, at least two different siloxyl units selected from those of formula (R3)3SiO0.5 (M unit), (R3)2SiO (D unit) and R3SiO1.5 (T unit), at least one of these units being a T unit, it being possible for the H and/or OR1 groups to be carried by the M, D and/or T units and the content by weight of OH and/or OR1 groups being between 0.2% and 10% by weight, andof at least one other resin exhibiting, in its structure, at least two different siloxyl units selected from those of formula (R3)3SiO0.5 (M unit), (R3)2SiO (D unit) and R3SiO1.5 (T unit) and SiO2 (Q unit), at least one of these units being a Q unit, it being possible for the OH and/or OR1 groups to be carried by the M, D and/or T units and the content by weight of OH and/or OR1 groups being between 0.2% and 10% by weight, the R3 radicals present in these resins being identical or different and selected from C1-C6 alkyl radicals which are linear or branched, C2-C4 alkenyl radicals, the phenyl radical or the 3,3,3-trifluoropropyl radical.

41. Composition according to claim 27, in which the constituent B-1 comprises an alkyl titanate, an alkyl zirconate, an alkyl silicate or a mixture of at least two of them, and/or the constituent B-2 comprises a polytitanate B-2 originating from the partial hydrolysis of isopropyl, butyl or 2-ethylhexyl titanates, a polyzirconate B-2 originating from the partial hydrolysis of propyl and butyl zirconate, a polysilicate B-2 originating from the partial hydrolysis of ethyl and isopropyl silicate or a mixture of at least two of them.

42. Composition according to claim 41, in which the constituent B-1 comprises a compound selected from ethyl titanate, propyl titanate, isopropyl titanate, butyl titanate, 2-ethylhexyl titanate, octyl titanate, decyl titanate, dodecyl titanate, β-methoxyethyl titanate, β-ethoxyethyl titanate, β-propoxyethyl titanate or the titanate of formula Ti[(OCH2CH2)2OCH3]4, propyl zirconate, butyl zirconate, methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, and mixtures of at least two of them.

43. Composition according to claim 27, in which the constituent C-1 comprises: (i) an essentially linear diorganopolysiloxane comprising a hydroxyl group at each chain end, of formula:

44. Composition according to claim 43, comprising a hydroxylated MDT resin having a content by weight of OH group of from 0.2% to 10% by weight.

45. Composition according to claim 27, additionally comprising a polycondensation catalyst.

46. Composition according to claim 27, additionally comprising a filler.

47. A method of treating a textile material and conferring long-lasting oleophobicity and/or hydrophobicity properties thereon, the method comprising treating the textile material with the composition of claim 27 so that the composition is crosslinked around the constituent yarns, fibers and/or filaments of the textile material.

48. The method according to claim 47, in which the constituent yarns, fibers and/or filaments of the textile material are treated directly.

49. The method according to claim 47, in which the textile material is treated.

50. The method according to claim 47, in which the constituent yarns, fibers and/or filaments of the textile material are treated directly and then the textile material itself is treated directly.

51. The method according to claim 47, wherein the treatment results in the formation of a sheath of silicone elastomer around the constituent yarns, fibers and/or filaments of the textile material.

52. Textile article, textile material or yarns, fibers and/or filaments for a textile material coated with a silicone elastomer is obtained by crosslinking a composition according to claim 27.