CN112011657A - Composition for impregnating substrates, in particular watch straps - Google Patents

Abstract

The invention discloses a composition for impregnating a watch band or a part thereof, said composition comprising: a) an organic solvent or sol-gel, b) at least one reactive organic compound comprising groups preferably consisting of phosphonate groups and hydrophobic or superhydrophobic groups, and c) optionally one or more functional groups selected from i. In addition, two methods of functionalizing a watch strap or part thereof are disclosed, the first method comprising impregnating the watch strap or part thereof with a composition comprising an organic solvent, and the second method comprising impregnating the watch strap or part thereof with a silica sol-gel solution, optionally comprising at least one active organic molecule as described above.

Description

Composition for impregnating substrates, in particular watch straps

Brief description of the drawings

There is a need to improve the life of watchbands without affecting the natural look and feel of leather. Compositions have been developed that can improve water resistance and microbial resistance. Finished leather watchbands can be treated with the composition to improve customer satisfaction.

Advantageously, the leather bracelet can be handled completely assembled together, so that bracelets from different suppliers can be handled. This will distinguish the original belts provided by the applicant from other belts on the market.

Technical Field

The invention relates in particular to a composition and to a method for treating leather, vegetable leather or textiles used as watchbands.

The composition comprises a reactive organic compound (sometimes referred to in this specification as a "reactive molecule") comprising a phosphonic acid group and one or more hydrophobic or superhydrophobic functional groups (in particular alkyl groups, preferably fluoroalkyl groups), and optionally an antifouling functional group (preferably a polyalkylene glycol group) and/or a biologically active functional group (in particular an ammonium, imidazolium or triazolium group).

General description of the invention

Technical problem to be solved

Leather watchbands and leather jewelry are natural products that evolve over time. Under current wearing conditions, especially water and contact with the wearer's skin, they degrade rapidly in both aesthetics and olfaction. The rapid degradation of leather watchbands or leather jewelry is due, among other things, to the exposure of the watchbands to moisture, water and various organic materials (sweat, soap, dust, etc.) resulting from the activities performed during wear. In addition, the leather wristband may be a complex assembly made of different kinds of leather and/or other materials. It may include liners, topcoats, padding, and the like. The filler may be leather or other material. However, the user wishes to maintain the natural look and feel of the leather for as long as possible.

Brief description of the embodiments

The solution to this problem proposed by the invention consists in applying the composition to the watch band or to the elements used to manufacture the watch band, such as the external surface of the watch band, the lining, the stitches, and/or the internal elements, such as the filling or crack-arresting elements. The treatment provides hydrophobic and/or bactericidal and/or antifouling properties, thereby improving the durability of the wristband without negatively affecting the appearance and feel of the wristband.

State of the art

Porous substrates, such as watch bands, bracelets or necklaces, are items that are commonly used to contact the skin of a user. These substrates allow the passage of water vapor and maintain the comfort of the article. However, they have various waterproof properties. It is well known that the development of unpleasant odours on those products is due to bacterial growth on or within the substrate. However, watchbands, bracelets or necklaces are not easily cleaned.

The complex structure of porous substrates such as leather presents challenges in understanding the exact decay pattern of a particular substrate. Decay is dependent on a variety of factors, including environmental conditions. For leather, its treatment should also be considered. Exposure to environmental factors, including ultraviolet light, ozone, acids produced by sulfurous and nitrous contaminants in the air, perspiration, etc., can lead to chemical damage. It is also known that, in the case of leather, prolonged exposure to low relative humidity (less than 40%) leads to dehydration or irreversible change in the fibrous structure thereof (Pr e servers by jets de son patrimoine: Pr6cis de condensation prevalent; International Institute for condensation of Historic and aromatic works section)

Editions Mardaga，2001；ISBN 2870097662，9782870097663)。

Finishing treatments of substrates such as leather include a group of surface treatments aimed at improving the natural quality of the substrate and/or covering imperfections that may be present on the surface. Mechanical protection, color uniformity and tactile properties are the main requirements for finishing. Many acrylic, polyurethane and other film-forming synthetic polymers are common ingredients of finishing formulations; they are mixed with natural substances, including native and/or modified substances, such as oils, waxes, caseins, proteins, cellulose esters and other substances. A number of patents and articles describe these various approaches to improve antimicrobial, water and/or oil repellency and/or stain repellency.

In general, substrates that are water-repellent or stain-repellent, such as leather or textiles, are prepared by using chemicals that are capable of forming functional coatings with low surface free energy on the substrate surface. These coatings may be polymeric films containing silicone, fluoro or long chain hydrocarbons. However, the permeability of the treated substrate to air and water vapor may be compromised, and it remains a challenge to develop new methods for producing such substrates that retain their natural characteristics.

Examples of easy-to-clean coatings of fluoroalkylsilanes or alkylsilyl groups, i.e. coatings with oil-, water-and soil-repellent properties, are described in many documents (e.g. DE 834002, US 3,012,006, GB 935,380, US 3,354,022, DE 1518551, DE 3836815, DE 4218657, DE 19544763, WO 95/23830, EP 0799873, EP 0846716, JP 2001/115151, EP 1033395, EP 1101787). These coatings will provide protection to the leather but will be visible and/or perceptible and will give the leather a feel that has been treated and artificial.

Hydrolyzable fluorocarbon silanes can impart oil and water repellency to surfaces. Chemical bonding occurs between the silane and active hydrogen functional groups on the substrate. This is accomplished by initially hydrolyzing the hydrolyzable groups on the silane to silanol groups, which then condense with functional groups on the substrate. The more hydrolyzable groups in the fluorocarbon silane that are bound to the substrate, the more durable the coating (see WO 95/23830).

Leather watch bands containing antimicrobial agents are known and described, for example, in document DE 20315119U 1. According to this document, a wristband made of leather comprises an inner band (i.e. a lining) in contact with the skin of the wearer, made of antibacterial treated leather. The advantage of such a tape is that it does not produce an odour, especially in the case of perspiration. However, the addition of certain active ingredients to the tape, such as antimicrobial agents, may cause irritation or sensitization to the skin, especially in the case of long-term contact of the tape with the skin, and more especially in hot and humid conditions.

Description of the invention

In the present invention, the terms "a" or "an" mean "at least one" or "means" and/or "unless specifically stated otherwise.

One purpose of the treatment of the invention (referred to as "functionalization" in the present description) is to reduce or limit the presence of microorganisms in the bracelet that cause unpleasant odours, without impairing its appearance and sensory characteristics. The treated substrate will have improved moisture absorption, cleaning, stain resistance and/or odor adsorption properties. This functionalization process does not substantially degrade the substrate and will retain its original feel and appearance.

More particularly, the present invention relates to a functionalized composition, to a process for functionalizing a porous substrate, such as natural leather, vegetable leather (e.g., natural leather), and the like

Eucalyptus, bamboo, rubber tree, etc.), cork or fiber fabric (e.g., cotton, flax, silk, nylon, polyamide, aramid fabric, etc.), and to functionalized products made from the substrate.

Drawings

Fig. 1 is a graph showing water absorption rates or samples associated with the plasma pressures shown in table 2.

Fig. 2 shows the water absorption (%) of the samples obtained in tests 0, 23, 33 and 35 shown in table 9 as a function of the passage of time after surface preparation.

Fig. 3 shows the water absorption (%) obtained in tests 0 and 22 to 25 summarized in table 10 as a function of the treatment time.

Fig. 4 shows the water absorption (%) versus the treatment solution concentration for tests 0, 23, and 26 to 29 given in table 11.

FIG. 5 shows the ratio of water absorption (%) to TEOS-AM _ 7.

Fig. 6 schematically shows two embodiments of the invention described below.

The present invention provides the following aspects:

1. a composition for impregnating a watch band or a part thereof, said composition comprising

a) An organic solvent or a sol-gel,

b) at least one active organic compound comprising-PO, preferably with phosphonate groups₃H₂And a hydrophobic or superhydrophobic group, and

c) optionally one or more functional groups selected from i.

2. Composition according to item 1, wherein the hydrophobic or superhydrophobic group of the reactive organic compound is a linear or branched alkyl group having 2 to 18 carbon atoms, which may be partially or totally substituted with halogen, preferably with chlorine or fluorine, most preferably with fluorine.

3. The composition according to item 1 or 2, wherein the active organic compound is

i.CH₃(CH₂)_nPO₃H₂N is between 2 and 18, or

ii.CF₃(CF₂)_n(CH₂)_mPO₃H₂N and m are between 2 and 18, and m and n are the same or different.

4. The composition of claim 1, wherein the anti-fouling functional group of the active organic compound is of the formula-O ((CH)₂)_mO)_nA polyalkylene glycol group of (a); wherein m is 2, 3 or 4, preferably 2; n is 2 to 18; and having hydrogen or C_1-6Alkyl as end group.

5. The composition of item 1 or 4, wherein the active organic compound is RO (CH)₂CH₂O)_n(CH₂)_mPO₃H₂Wherein n and m are 2-18, n and m are the same or different, and R is H or CH₃。

6. The compound according to item 1, wherein the bioactive functional group of the active organic compound is an imidazolium group, a triazolium group or optionally substituted with 1 to 3C₁-C₆Or by 0, 1 or 2C₁-C₆Alkyl and C₁₀-C₁₈Alkyl-substituted ammonium group of (1).

7. The compound of claim 1 or 6, wherein the active organic compound is CH₃(CH₂)_n(N(CH₃)₂)⁽⁺⁾(CH₂)_mPO₃H₂ Cl^(-)Wherein n and m are 2 to 18, and m and n are the same or different, 1-methyl-3- (dodecylphosphonic acid) imidazolium bromide or 1-methyl-3- (dodecylphosphonic acid) imidazolium bis (trifluoromethylsulfonyl) imide.

8. The compound according to any one of the preceding claims, further comprising bioactive metal nanoparticles, preferably silver nanoparticles.

9. The compound according to any one of the preceding claims, wherein the organic solvent is ethanol or isopropanol, preferably ethanol.

10. A method for functionalizing a substrate by impregnation comprising the steps of

i. Selecting a substrate;

degassing the substrate;

treating the substrate with an oxygen plasma or an air plasma;

at least partially impregnating or coating the substrate with a composition according to any one of items 1 to 8, wherein the composition is a composition comprising an organic solvent;

v. drying the treated substrate.

11. A method for functionalizing a substrate by impregnation comprising the following steps

i. Selecting a substrate;

preparing a sol-gel solution from a hydrolysable silane precursor under acidic or basic conditions;

aging the sol-gel solution;

at least partially impregnating or coating the substrate with the sol-gel solution;

v. drying the treated substrate;

fixing the sol-gel on the substrate by tempering.

12. The method according to claim 11, wherein the sol-gel contains at least one reactive organic compound according to any one of items 1 to 9.

13. The method of any one of claims 10-12, wherein the substrate is selected from the group consisting of natural leather, natural leather substitutes made from plant fibers, cork and textile fabrics, and combinations thereof.

14. The method of any of claims 10-13, wherein the substrate is a watch band or a portion thereof.

15. Use of a composition according to any one of items 1 to 9 for reducing the water absorption of a substrate, preferably a watch band or one or more parts thereof.

16. A watch band obtainable by the method of any one of items 10 to 14.

17. Watch band comprising at least one reactive organic molecule according to any one of items 1 to 9 and/or a silica sol-gel network.

Detailed description of the invention

Means for solving the problems

It is well known that microorganisms require water to be active. By functionalizing the substrate either hydrophobically or superhydrophobic, the presence of water within and/or on the surface of the substrate can be limited. This will affect the activity of the microorganism. Therefore, the substrate does not generate an unpleasant odor or requires more time to generate such an unpleasant odor.

Another way to prevent bad smells is to avoid microbial contamination. This can be done by a simple mechanical action, such as rubbing or wiping the wrist against the substrate, to remove the microorganisms. Furthermore, the compounds may also exhibit a biological activity that is detrimental to the microorganisms causing the bad smell.

To limit the development of odours, the limitation of the microbial growth on or inside the lining of leather watchbands can be achieved in two different ways: the surface of the substrate is subjected to an antifouling treatment to limit the adhesion of organisms causing undesirable odor, or a treatment with a bactericide. A combination of anti-fouling and anti-bacterial treatments is also possible. Avoiding biofilm due to dead or non-dead microorganisms will prevent the generation of bad odors. The anti-fouling treatment by limiting the presence of microorganisms will avoid or at least limit the occurrence of bad odours. The degradation of the leather can also be slowed down.

In all embodiments of the invention, the inventors used three methods:

A. hydrophobic or superhydrophobic treatments can be employed to control the water concentration of the substrate and avoid water ingress into the substrate. The accumulation and concentration of malodorous causing substances may be limited by the inactivation of microorganisms by adverse hydrogen containing conditions.

B. Treatments based on "antifouling" polyalkylene glycols (e.g., polyethylene glycol) will prevent microorganisms and cells deposited on the surface from adhering thereto. Thus, a simple mechanical action, wrist rubbing or wiping, will allow it to be eliminated.

C. The treatment to obtain a cationic bioactive surface will have the same "anti-fouling" effect as the polyalkylene glycol treatment.

In one and the same reactive molecule (reactive organic compound), method A can be combined with other methods according to the invention. In general, one reactive molecule or a mixture of two or more different reactive molecules may be used in the present invention.

Functional group

The active organic compound in the functionalized composition of the invention has a phosphonic acid group and a hydrophobic or superhydrophobic group. The compounds comprising hydrophobic and/or superhydrophobic groups used in the compositions of the invention are alkyl phosphonates or haloalkylphosphonates, preferably fluoroalkylphosphonates. The alkyl group may be linear or branched, and may have 2 to 18 carbon atoms. The haloalkylphosphonate compound may be fully or partially halogenated. Typical compounds having hydrophobic or superhydrophobic functionality for use in the present invention are e.g. CH₃(CH₂)_nPO₃H₂Wherein n is between 2 and 18; or CF₃(CF₂)_n(CH₂)_mPO₃H₂Wherein n and m are from 2 to18, m and n are the same or different. Preferably a haloalkylphosphonate salt, most preferably a fluoroalkylphosphonate salt.

The term "phosphonate" is used herein to designate phosphonic acids and salts thereof. The counter ion of the salt may be any suitable cation, such as a metal cation (e.g., sodium, potassium, calcium, magnesium, and any other metal cation that does not impair the properties of the compound) or an organic cation (e.g., ammonium). Phosphonic acid groups are preferred.

Preferred active organic compounds containing hydrophobic or superhydrophobic groups for use in the present invention are octylphosphonic acid, dodecylphosphonic acid, n-octadecylphosphonic acid, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexadecylphosphonic acid, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecylphosphonic acid, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecylphosphonic acid.

Optionally, the reactive organic compound may additionally comprise at least one of the following functional groups:

i. an antifouling functional group; and

a bioactive functional group.

The functional groups according to the present invention are selected to achieve at least one of the above effects. Advantageously, the compound combines at least two of these effects.

Compounds which provide an "antifouling" effect to the substrate surface are, for example, polyalkylene glycols, such as polyethylene glycol, compounds containing propylene glycol or butylene glycol.

Furthermore, compounds containing polyalkylene glycols usually have alkoxy end groups, obtained by alkylating hydroxyl end groups, such as methyl, ethyl, propyl or butyl end groups. If the end is not alkylated, the end group is a hydroxyl group.

Compounds in which a phosphonate group, a hydrophobic group or a superhydrophobic group and a polyalkylene glycol group are combined are particularly suitable for the composition according to the invention.

Compounds in which a hydrophobic or superhydrophobic group is bound to an antifouling group are, for example, RO (CH)₂CH₂O)_n(CH₂)_mPO₃H₂(wherein n and m are 2-18, n andm is the same or different, and R is H or CH₃). A specific and preferred example of such compounds which can be used according to the invention is 6- [2- [2- (2-methoxyethoxy) ethoxy ] ethoxy]Ethoxy radical]Hexylphosphonic acid, 2- [2- (2-methoxyethoxy) -ethoxy]Ethylphosphonic acid, 2- [2- (2-methoxyethoxy) ethoxy group]Hexylphosphonic acid, 2- [2- (2-hydroxyethoxy) ethoxy]Ethylphosphonic acid, 2- [2- (2-hydroxyethoxy) ethoxy]-hexylphosphonic acid and {2- [2- [2- [2- [2- [2- [2- [2- [2- [2- [2- [2- [2- [2- (2-hydroxyethoxy) -ethoxy ] -ethoxy-)]Ethoxy radical]Ethoxy radical]Ethoxy radical]Ethoxy radical]Ethoxy radical]Ethoxy radical]Ethoxy radical]Ethoxy radical]Ethoxy radical]Ethoxy radical]-ethyl radical]Phosphonic acid.

The compound having a bioactive functional group for imparting a cationic property to the surface of the substrate is, for example, an ammonium-containing compound, a triazolium-containing compound and/or an imidazolium-containing compound. In the case of an ammonium group, the compound may have an ammonium group-NH₃ ⁺Or an alkyl-substituted ammonium group, forming an ammonium group through a covalent bond with the remainder of the molecule. It preferably has C on nitrogen₁₀-C₁₈Alkyl chains and hydrogen or lower alkyl radicals, e.g. C_1-6Alkyl, preferably ethyl. The biologically active functional group is linked to the phosphonate group through a hydrophobic or superhydrophobic group, i.e., it is located "on the other end" of the hydrophobic or superhydrophobic group relative to the phosphonate group.

The counter ion may be any anion, such as halide, sulfate, nitrate, phosphate, trifluoromethylsulfonyl or other anion of an inorganic or organic acid. Preferred are halides and trifluoromethylsulphonyl, especially preferred are chloride, bromide and trifluoromethylsulphonyl.

The compound combined with the super-hydrophobic, antifouling and bioactive groups is CH₃(CH₂)_n(N(CH₃)₂ ⁽⁺⁾(CH₂)_nPO₃H₂C1(-) (wherein n and m are 2-18 and m and n are the same or different).

Preferred examples of such molecules are 12-aminododecylphosphonic acid hydrochloride, (12-dodecylphosphonic acid) triethylammonium chloride and (12-dodecylphosphonic acid) -N, N-dimethyl-N-octadecylammonium chloride.

Examples of compositions comprising phosphonate, hydrophobe and imidazolium groups suitable for use in the compounds of the present invention are 1-methyl-3- (dodecylphosphonic acid) imidazolium bromide and 1-methyl-3- (dodecylphosphonic acid) imidazolium bis (trifluoromethylsulfonyl) imide. An example of a compound having a hydrophobic group and a triazolium group is 1-methyl-1, 2, 4- (dodecylphosphonic acid) triazolium bromide.

In addition, bioactive nanoparticles, such as silver nanoparticles, may be included in the functionalized composition.

The active organic compound may be a mixture of different molecules having a specific effect.

In particular, compounds containing phosphonic acids and hydrophobic or superhydrophobic groups are compatible and soluble in ethanol and have very low reactivity with natural leather, and are therefore preferred according to the present invention.

The compounds used in the present invention are commercially available or can be synthesized from commercially available precursor compounds according to methods known in the art.

Active molecule tested (AM)

Alkyl chains, fluoroalkyl chains and/or linear polyether chains, e.g. with phosphonate (-PO)₃H₂) Polyalkylene glycols of radicals (e.g. PAG, PEG), or phosphonate cationic molecules, e.g. C₁₆H₃₀N₂PO₃H₂ ⁽⁺⁾Br^(-)(1-methyl-3- (dodecylphosphonic acid) imidazolium bromide) and C₁₆H₃₀N₂PO₃H₂ ⁽⁺⁾C₂F₆NO₄S₂ ^(-)、H₃N⁽⁺⁾C₁₂H₂₄PO₃H₂C1^(-)(1-methyl-3- (dodecylphosphonic acid) imidazolium bis (trifluoromethylsulfonyl) imide).

Examples of molecules tested are shown in the table below.

The examples described in this specification are those using a concentration of 1.21 · 10 in ethanol^-2mol·L^-1AM _7 solution (12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecyl phosphonic acid) (referred to as "solution 1").

The sol-gel treated watch band elements have been subjected to external allergy substance testing: no such substances were found, and the partially treated bracelet had been worn within 6 months and without any irritation.

TABLE 1

Method of producing a composite material

According to the invention, the substrate can be functionalized using different methods, for example impregnation with organic solvents, sol-gel methods or any other suitable means.

The organic solvent is selected according to the nature of the substrate to be treated, the treatment temperature and the solubility of the compound.

Combinations of methods are also possible.

In addition, the substrate may be pretreated, e.g. O₂Or air plasma treatment, degassing and/or cleaning.

For impregnation, it has been tested that the structure comprising natural leather is not damaged by ethanol at the selected temperature and duration range.

To evaluate the samples and the method steps, water absorption measurements were performed on the treated samples.

First embodiment

The impregnation method with active molecules and organic solvents comprises the following steps:

1) selecting a substrate, such as natural leather, vegetable leather or fabric;

2) degassing the substrate to remove additional excess water or control the amount of water therein;

3) with O₂Carrying out surface activation treatment on the base material by using plasma or air plasma;

4) impregnating or coating at least a portion of said substrate with at least one selected active organic compound dissolved in a selected organic solvent;

5) drying the treated substrate to remove remaining liquid.

Base material

According to the invention, the wristband may be a complex combination of various leathers and/or other materials (e.g., textiles). In this case, the band has a multilayer structure. The wristband may comprise a lining, i.e. a layer in direct contact with the skin and arranged inside the wristband.

The liner typically has two edges of different textures. The outer side is the side in contact with the skin and the inner side is the side in contact with the crack stop layer or filler. The inner side is typically more "rough", i.e. more porous.

The outermost surface layer is usually a leather layer which gives the watch band its appearance when the watch is worn. Tear resistant intermediate reinforcing layers (crack stop layers) and/or fillers and the like may also be present. The filler may be leather or other material. The various parts of the bracelet may be assembled by any known technique suitable for the combination of materials, i.e. sewing, gluing, etc.

According to the invention, all the different parts of the bracelet may be functionalized separately, i.e. lining, thread, padding, etc., and may be a substrate.

Furthermore, only some or all of the components can be functionalized prior to assembly of the wristband.

As an alternative, according to the invention, the assembled watch band or the preassembled watch band elements can be functionalized.

All of these alternatives are suitable substrates according to the present invention.

Advantageously, the substrate is porous, such as natural leather, vegetable leather, i.e. natural leather substitutes made of fibres, such as cellulose fibres extracted from vegetable leaves (for example

Pineapple, eucalyptus, bamboo, rubber tree, etc.), cork, textile fabrics (e.g., cotton, flax, silk, nylon, polyamide, aramid fabrics, etc.).

In the manufacture of vegetable leather, vegetable materials such as long vegetable fibers, i.e., pineapple or eucalyptus fibers, mushroom mycelia, etc., are used to manufacture a nonwoven fabric substrate, the appearance of which is very similar to that of natural leather.

Preferably, most of the watchband and its individual parts, such as the lining, padding and outer surface layer, are made of a porous material. However, some components, such as tear protection layers (crack stop layers), are generally non-porous.

Porous substrates are to be understood in the broad sense, for example substrates containing void spaces or voids through which air or solvent may pass. Porosity can take many forms, from interconnected microscopic pores, folds and inclusions to macroscopic pores visible at the outer surface. The spaces between the threads or fibers of the fabric may be assimilated into pores.

Porous means permeable to water vapor in particular.

According to the invention, natural leather is preferably used as the substrate.

Surface preparation

The surface of the substrate is prepared (pretreated) according to the method of the invention before the application of the functionalization treatment. The main stages of the preparation treatment are degassing and treatment with air or O₂And (4) carrying out plasma treatment.

In the present invention, degassing a substrate such as leather is important to obtain good functional quality. It primarily ensures the removal of water in the liner. Typically, degassing is accomplished by heating to moderate temperatures under vacuum. An example of degassing is treating the substrate at 40 ℃ for 16 hours at a pressure of 0.1 hpa.

It is also possible to degas the substrate prior to applying the functionalization process of the present invention and then "rewet" to a specific preselected humidity to stabilize the substrate and avoid further drying. For example, rewetting can be accomplished by storing the substrate in an environmental chamber at a particular preselected humidity and appropriate temperature until the system is in equilibrium.

Treatment of a substrate (e.g., natural leather) by irradiating oxygen or air plasma onto the surface of the substrate for a predetermined duration and at a selected power has been demonstrated to increase workCan be used for energy conversion. Air plasma display ratio O₂Plasma results somewhat better and is therefore preferred. The plasma is generated by the skilled person using conventional methods known to the skilled person. By the plasma treatment, the surface of the substrate is activated.

The high power plasma does not improve the surface activity. The results show that satisfactory results are obtained at powers of 25-60W; advantageously, a power of 30W is used according to the invention. For example, air or O may be used₂Plasma was applied at 0.3-3hpa, 25-60W for 30s to 6 minutes.

The surface activity cannot be improved by a longer treatment time. Treatment times between 30 seconds and 6 minutes gave satisfactory results; advantageously, a duration of between 30 seconds and 4 minutes is used, more advantageously a duration of 30 seconds is used.

The concentration of ethanol is 1.21-10^-2mol·L^-1No significant effect of plasma pressure changes was observed after treatment with AM _7 solution (a). The results are shown in Table 2.

TABLE 2

The test results are shown in fig. 1.

The best functionalization was obtained with a preparation treatment consisting of degassing at 40 ℃ for 16 hours at a pressure of 0.1hpa, then treating with air plasma for 30s, 30W and 0.5 hpa.

Time after surface activation

Functionalization also needs to be performed directly after air plasma or oxygen plasma pretreatment. It was observed that the effect of the pretreatment disappeared only after 30 minutes. Therefore, according to the method of the present invention, the functionalization process is performed within 30 minutes after the completion of the plasma process.

Functionalization process

Several parameters have been found to be important for the functionalization process according to the invention.

Solvent(s)

The solvent is an organic solvent. Ethanol and isopropanol are suitable solvents for preparing the functionalized compositions of the invention.

Other aliphatic alcohols such as methanol, n-propanol are also suitable.

Furthermore, other organic solvents or combinations of organic solvents are possible, such as linear or cyclic alcohols; linear and cyclic ethers such as diethyl ether, diethyl tert-butyl ether, tetrahydrofuran, dioxane; esters, such as ethyl acetate; ketones such as acetone, diethyl ketone, ethyl methyl ketone; dipolar aprotic solvents as long as they protect the substrate and are compatible with the reactive molecule. The solvent should not have a strong odor and should not be highly toxic when contacted with the skin or inhaled. In addition, it should be compatible with the substrate. The solvent is a polar solvent.

Surprisingly, ethanol showed the best results.

The most preferred organic solvent for use in the first embodiment of the present invention is ethanol.

Treatment of

Typically, the functionalization process is performed by immersing the pretreated substrate in a solution of reactive molecules. However, other methods are also suitable, such as coating or spraying. However, care must be taken that the solution is in intimate contact with the substrate so that the reactive molecules are able to penetrate sufficiently into the substrate.

The depth of penetration may be controlled by the viscosity of the composition or any other suitable means. The penetration depth can reach 100 percent.

Time of treatment

After a certain immersion time, the water-repellent properties of the treated surface are not further improved. For example, after 6 hours of immersion, increasing the immersion time does not significantly affect the properties of the substrate. Therefore, preferably, the immersion time is between 6 hours and 10 hours.

The impregnation treatment may be carried out at room temperature (i.e., 22-25 ℃) and atmospheric pressure. Other conditions may be used as long as the leather does not deteriorate.

Concentration of active molecule

The concentration of active molecules should be as high as possible without any precipitate formation; therefore, it should be set as close as possible to the solubility limit of the active molecules in the respective solvents.

Optimal functionalization can be achieved by preparing the surface with air plasma (e.g., 30s, 30W, 0.5hpa), then immersing the substrate in the composition containing the reactive molecule within 1 minute or less after surface plasma treatment, and immersing the substrate in the solution for 6 hours for immersion.

Drying

The substrate is dried after impregnation. Suggested drying temperatures are 20 ℃ to 85 ℃, preferably 25 ℃ to 65 ℃ to maintain the leather structure, more preferably 30 ℃. Until the solvent was sufficiently evaporated, and drying was complete. The duration of 15 hours at 85 ℃ allowed the solvent to evaporate well. The duration of 72 hours at 30 ℃ allowed the solvent to evaporate well.

Advantageously, the air is ventilated during the drying process.

For example, the substrate may be placed in a Greiner Tube (Greiner Tube) for drying.

Advantageously, the functionalized substrate is dried for 72 hours at 30 ℃ under ventilated air.

Optimum parameters for the impregnation method

Most preferably, the first embodiment comprises

Active molecules

Omicron 12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecyl phosphonic acid (AM _7)

Solution of

Concentration in o-ethanol is 1.21 · 10^-2mol·L^-1(12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecyl phosphonic acid) (AM _7)

Optimization of the Process

O degassing the substrate at 40 ℃ for 16 hours at a pressure of 0.1 hPa;

treatment with air plasma (30W, 30s, 0.5 hPa);

o dipping within 1 minute after air plasma treatment;

o immersing the substrate at room temperature for 6 hours, i.e. 22-25 ℃ and atmospheric pressure;

the substrate was dried (under ventilated air, 30 ℃, 72 hours).

Second embodiment

In a second embodiment of the invention, the leather substrate is impregnated with silica particles using a sol-gel process. Optionally and preferably, the sol-gel further comprises at least one active molecule. The reactive molecule may be selected from those described in the first embodiment of the present invention.

The method of the second embodiment of the present invention preferably comprises the following steps

1) Selecting a substrate;

2) preparing a sol-gel solution under acidic or basic conditions;

3) aging the sol-gel;

4) at least partially impregnating or coating the substrate with the sol-gel;

5) drying the treated substrate to remove remaining liquid;

6) fixing the sol-gel on the substrate by tempering.

Base material

The same base material as that of the first embodiment can be suitably used in the present embodiment.

Surface preparation

No specific surface preparation is required for this embodiment. However, in the alternative, the degassing and/or plasma pretreatment may be carried out on the substrate to be treated, as described in the example of the first embodiment.

Sol-gel preparation

The sol-gel solution can be prepared under acidic or basic conditions.

Usually, by the alkaline sol-gel method (so-called Startbot method)

Method), silica (i.e., silica) particles, preferably nanoparticles, are formed. A hydrolysable precursor, usually Tetraethoxysilane (TEOS), first reacts with water in an alcoholic solution, and the resulting molecules then react further to form larger structures. According to the conditionsThe reaction produces silica particles having a diameter of 50 to 2000 nm.

By the acidic sol-gel silica method, an extended network can be obtained, which can be directly attached to the substrate surface and/or the internal structure of the substrate. The depth of penetration may be controlled by the viscosity of the sol-gel solution or any other suitable means. The penetration depth can reach 100 percent.

As precursors, hydrolyzable silanes are suitable, such as tetraalkoxysilanes, alkyltrialkoxysilanes, dialkyldialkoxysilanes, etc., where alkyl refers to a straight or branched or cyclic C_1-8Alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, alkoxy means alkoxy having 1 to 8 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, which may all be straight-chain or branched.

Preferably Tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMOS), methoxypropoxysilane or butoxysilane is used according to the invention.

The pH in the acidic process is generally from 0.5 to 4, preferably from 1 to 2.5, most preferably from 1.5 to 2. In the alkaline process, the pH is generally from 7 to 10, preferably from 8 to 9.

Typically, sol-gels are prepared from precursors and a suitable solvent such as ethanol by stirring and heating for a suitable period of time, e.g. 1 to 4 hours, preferably 2 hours at an elevated temperature of 30 to 85 ℃, preferably 40 to 70 ℃, typically 62 ℃, and then cooling to room temperature, i.e. 22-25 ℃. The leather substrate is then coated by a suitable method, such as dipping (immersion), and the coated substrate is then tempered.

Under acidic conditions, the sol-gel solution preferably comprises at least 3g teos in 15-1g EtOH and 1.5-0.5g 0.5M HCl (pH 1.5-2), and optionally at least one active molecule at a concentration less than or about its solubility limit in the sol-gel solution;

under alkaline conditions, using a Startbot catalyst based on ammonia

Conditions specified in the procedure (see W.

A. fink et e.j.bohn, j.coll.interface Sci, 1968, 26, 62). Optionally, the sol-gel comprises at least the reactive molecule at a concentration less than or about its solubility limit in the sol-gel solution.

Furthermore, bioactive metal nanoparticles, preferably silver nanoparticles, may be added to the sol-gel.

Sol-gel solutions with or without reactive molecules

The sol-gel is preferably prepared with the selected solution (appropriate TEOS/EtOH ratio) under stirring and refluxing for a suitable period of time, e.g., at elevated temperatures of 30-85 deg.C, 40-70 deg.C, typically 62 deg.C, for 1-4 hours, preferably 2 hours. The sol-gel is cooled for a suitable time, typically at least 20 minutes.

For example, a sol-gel without reactive molecules is prepared by mixing a solution containing 3.0g TEOS (3.2mL, 1.44. 10)^-2mol) of 15.0g of ethanol and 1.1g of 0.5 mol. L^-1HCl in the presence of hydrogen peroxide. The molar ratio of TEOS to EtOH to H₂O is selected as required. Preferably 1: 23: 4.

For example, leather substrates are treated by soaking in a sol-gel for about 5 minutes.

The substrate is then tempered in an oven at elevated temperature for a period of time, typically at 85 ℃ for 15 hours.

Leather substrate treatment efficiency varied from batch to batch.

Concentration of reactive molecules in sol-gel solution

Preferably, reactive molecules (i.e., reactive organic compounds) may be added to the sol-gel prepared as previously described. The reactive molecule is the same as described for the first embodiment of the present invention. Preferred examples of the reactive molecule are the same as those in embodiment 1. In particular, in the present embodiment, AM _7 and AM _5 were tested in a sol-gel solution, and are particularly preferred. One active molecule or a mixture of two or more different active molecules may be used. Typically, the reactive molecule is added to the sol-gel in the form of a solution in a suitable solvent, preferably in ethanol.

The concentration ratio of the precursor (e.g., TEOS) to the reactive molecule of the sol-gel solution may be selected in the range of 10: 1 to 100: 1. Preferably, the ratio of TEOS: AM is 15: 1 to 65: 1, and 17: 1, 43: 1 and 62: 1 can be specifically used. However, the variation in the concentration of active molecules has no significant effect on the final properties of the treated leather.

Aging of the sol-gel solution with AM

The term aging as used in this specification does not necessarily match what is known in sol-gel chemistry. Here, it is used to basically represent the laboratory procedure.

Herein, the term aging means stirring at a certain temperature for a certain time, usually under reflux. Although the reflow parameters for the aged sol-gel were changed, the water absorption did not change significantly from sample to sample.

By increasing the ageing temperature, the desired sol-gel properties can be maintained, resulting in the advantage of a shorter treatment time. However, the higher the reflux temperature, the longer the cooling time.

The aging temperature of the sol-gel solution may range between 20 ℃ and 70 ℃ for 24 to l hours.

Advantageously, a temperature from 56 ℃ to 62 ℃ for 3 hours 50 minutes to 1 hour 45 minutes can limit the cooling time while maintaining a reasonable duration of the aging step.

Functionalization process

The sol-gel treatment of the substrate is carried out by dip coating or any other suitable technique known to those skilled in the art. The shortest treatment time (5-10min) was chosen to allow the sol-gel solution to fully impregnate the leather substrate.

Tempering of samples functionalized with AM sol-gel solution

After the sol-gel is applied to the substrate, tempering, i.e. heating to a predetermined temperature for a period of time, is performed. By a tempering step, the sol-gel polymerization to silica and solvent evaporation are achieved. If the tempering time is too short, complete polymerization of the sol-gel and complete evaporation of the solvent cannot be achieved.

The increase in temperature shortens the reaction time. However, higher temperatures can lead to degradation of the leather. No visual modification of the samples treated at 105 ℃ and 120 ℃ was detected, but due to the nature of the substrate, shrinkage of the leather samples was observed at temperatures greater than 85 ℃.

The tempering time must allow for complete polymerization of the sol-gel and complete evaporation of the solvent. The results show that the polymerization is complete after 17 hours at 65 ℃.

The minimum tempering time is about 5 hours in the selected temperature range. Tempering is not required for more than 24 hours. Even a short period of time is sufficient, leaving the sample overnight (about 15 to 17 hours).

Preferably, a tempering temperature of 55 ℃ to 85 ℃, preferably 65 ℃, is recommended to maintain the leather structure.

Sol-gel composition/precursor/AM ratio

Changing the TEOS/AM ratio affects the water absorption (%) of the leather substrate. Generally, there is an optimum range for the precursor concentration for each AM concentration, and above or below this range, the water absorption increases. Through simple experimental tests, the optimal ratio of precursor (preferably TEOS)/active molecule can be selected.

An increase in AM concentration generally results in a decrease in the water absorption of the leather substrate.

For example, when the AM _7 concentration is increased by a factor of 7 (8.54. multidot.10)^-2mol·L^-1Substitute 1.21. 10^-2mol·L^-1) The water absorption increased only 4%, as shown in fig. 5.

For example, for a TEOS concentration of 0.09 mol% AM (based on the total sol-gel solution including AM), a water absorption of 17% is preferred, with a TEOS concentration of 2.9 mol%. For the same 0.09 mol% AM-7 and 1.8 mol% or 3.8 mol% TEOS concentration, the water absorption is higher.

"multilayer"

In order to improve the mechanical or physicochemical properties of the sol-gel treatment, a continuous treatment may be used. That is, the steps of embodiment 2 are repeated using the same or different compositions. The layers may be of the same nature or of alternating nature, i.e. a first layer without reactive molecules, then a functional layer (i.e. a layer with reactive molecules), etc. Alternatively, it may also be a layer with different reactive molecules, e.g. no AM/no AM, AM1/AM2/…, AM1/AM1 or any combination.

Mechanism of substrate functionalization

For leather, the sol-gel solution chosen has good chemical compatibility with the collagen structure. Thus, the three-dimensional network of sol-gel is also at least partially incorporated inside the leather. Analysis by SEM-EDX showed that the sol-gel prepared under acidic conditions penetrated deeply into the leather, preferably substantially throughout the entire thickness, and had no significant effect on the topology of the leather. SEM-EDX failed to identify any film or microstructure. However, silica is present in the observation region. According to the results, the sol-gel network appears to be a nano-scale network directly connected to the collagen network of the leather.

SEM-EDX analysis shows that the sol-gel prepared under alkaline conditions consists of silica particles with a diameter of 50-2000 nm. The particles penetrate into the leather interior, which is related to the porosity and the size of the silica particles.

For SEM-EDX measurements, MEB Zeiss Sigma 300 with EDX was used.

The same logic applies to other porous substrates, such as fabrics. One effect of the functionalization according to the second embodiment of the present invention is to reduce at least some of the interstitial spaces or fill at least some of the voids to reduce the void fraction in which microorganisms can find suitable growth conditions.

Optimum parameters for the sol-gel method

Finally, the most preferred embodiment of the sol-gel embodiment of the invention is

Active molecules

Omicron 12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecyl phosphonic acid (AM _7)

Sol-gel composition

3.0g TEOS and 15.0g 1.21.10 in ethanol^-2mixing the 12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecyl phosphonic acid (AM _7) solution in mol/l to prepare TEOS, EtOH and H₂Tetraethoxysilane (TEOS) sol-gel solution with a molar ratio of O of 1: 23: 4. The pH was adjusted to pH 2 by adding 1.5g of 0.5M HCl.

Optimization method

O stirring and refluxing for 2 hours at 62 ℃ to prepare the sol-gel.

Cooling the sol-gel for at least 20 minutes.

The substrate is treated by dipping and stirring for 5 minutes.

O temper the substrate in an oven at 65 ℃ for 17 hours.

Examples

All the examples described in this specification are made with a natural leather lining made of alzavel (calf leather).

The water absorption measurements in the examples were carried out using the thermogravimetric principle with a dewatering balance. The experimental device is an OHAUS^TMMB 35. The sample to be tested is usually dried before the measurement (the last operation is a channel in an oven or a previous water intake measurement).

The protocol for the samples was as follows:

placing a weighing pan in a thermal weigher;

completely immersing the sample in a container containing ultrapure water for one minute;

wipe the sample with a paper towel;

repeat the soaking and wiping operations 5 times;

placing the sample on a weighed pan;

starting a drying program; this procedure heats the sample to 60 ℃ and tracks the sample weight as water evaporates under the influence of heat.

Comparison between active molecules

Different reactive molecules on the substrate were treated with air plasma (30 or 60W, 30s, 0.5hpa) and then in ethanol solution (active molecule concentration 10)^-2M) comparison after immersion for 6h at room temperature.

The results of the samples tested 40, 41, 43, 44 and 45 show that these active molecules are hydrophobic. These hydrophobic functionalized substrates show no water drop to diffuse through the surface of the substrate.

For the measurement, a drop of water is deposited on the leather; the water uptake time (visual inspection) was timed.

Furthermore, for substrates made from leather layer liners, either alone or in combination with a tear resistant layer and/or filler and/or top layer, water does not penetrate into most liners after immersion in the functionalizing solution for 48 hours.

Surprisingly, it was observed that the surfaces functionalized with polyethylene glycol containing active molecules (trials 46 to 49) were relatively hydrophobic in terms of drop angle (drop angle) and that no drop of water diffused through the treated surface. However, the entry of water into the whole sample immersed in water is almost instantaneous and consistent with the reactive molecule used. There is no difference between PEG containing active molecules with terminal hydroxyl functionality and PEG with methoxy functionality.

When the calf leather (Alzavel) was soaked in water, the maximum water increase was 56%. Different types of leather and different batches of the same leather type may have different water saturation levels, as is well known to the skilled person.

The drop angle was measured by goniometry. The results are shown in Table 3.

TABLE 3

Test of	Active molecules tested	Water absorption (%)	Water drop angle	Time (h) until water absorption reaches saturation
					0	Untreated leather substrate	56	116	＜0.25
38	AM_3	53	70.3	2-16
					39	AM_4		97.2	1
40	AM_5	15
					41	AM_5	22	106.2	＞48
42	AM_6		123.3	2-16
					43	AM_7	18	138.6	＞48
44	AM_8		131	＞48
					45	AM_9	8	123	＞48
46	AM_13	55	105.1	＜0.1
					47	AM_14		109.6	＜0.1
48	AM_15	50	108.5	＜0.1
					49	AM_16		103.7	1

Surface preparation

Degassing of gases

Degassing was accomplished by treating the substrate at 40 ℃ for 16 hours at a pressure of 0.1 hPa.

Comparison of the water absorption without degassing and with degassing shows that for any pretreatment (air or O)₂) The improvement in degassing is shown in Table 4 below. The concentration of ethanol is 1.21-10^-2mol·L^-1Samples 1-6 were functionalized with AM _7 solution (a).

TABLE 4

Surface activation (see test results 4-21 in Table 5)

Using AM _7 solution (concentration 1.21.10) in ethanol^-2mol·L^-1) Samples 4-21 were functionalized.

The results in table 5 below show that:

plasma and plasma-free

Treating a substrate, such as natural leather, by irradiating oxygen or air plasma onto the substrate surface for a predetermined duration and at a selected power has been shown to improve functionalization.

·O₂With air plasma

Air plasma display ratio O₂Better results with plasma.

Plasma power

Plasma powers of 30W-300W have been tested. High power plasmas do not improve surface activation. The results show that a power of 25-60W provides satisfactory results; advantageously, a power of 30W is used.

Plasma treatment time

Treatment times have been tested between 30 seconds and 8 minutes. Longer treatment times do not improve surface activation. The results (see tests 17-21 in table 5) show that treatment times between 30 seconds and 6 minutes give satisfactory results; advantageously, the duration is between 30 seconds and 4 minutes, more advantageously, the duration is 30 seconds.

Pressure of the plasma

The pressure varies between 0.1hPa and 3 hPa. As shown in fig. 1, it is noted that no significant effect of plasma pressure variation was observed.

As shown in Table 5 below, AM _7 (concentration 1.21. multidot.10) in ethanol was used with 30s, 30W and 0.5hPa degassing and air plasma^-2mol·L^-1) An optimal functionalization can be obtained.

TABLE 5

Sol-gel preparation

Sol-gel

The sol-gel was prepared with the selected solution (appropriate TEOS/EtOH ratio) under stirring and refluxed at 62 ℃ for 2 hours. The sol-gel is cooled for at least 20 minutes. 15.0g of a suspension containing 3.0g of TEOS (3.2mL, 1.44.10)^-2mol) of ethanol with 1.1g of HCl 0.5 mol. L^-1Mixing to obtain sol-gel without active molecules. TEOS: EtOH: H₂The molar ratio of O is 1: 23: 4.

The leather substrate was treated by dipping in the sol-gel for 5 minutes. The substrate was then tempered in an oven at 85 ℃ for 15 h. The results summarized in table 6 show that the mass ratio reached 1.11, the higher the TEOS concentration in ethanol, the lower the water absorption. The results are shown in Table 6.

TABLE 6

0.20-1 g EtOH for 0.2g TEOS

It is noted that different batches of leather substrate have been used and that the change in treatment efficiency is directly related to this.

Concentration of reactive molecules in sol-gel solution

The sol-gel was prepared with the chosen solution (appropriate molar concentration) under stirring and refluxed at 62 ℃ for 2 hours. The sol-gel is cooled for at least 20 minutes.

Sol-gel a and sol-gel B have been used.

Example 1: sol-gel A

TEOS∶EtOH∶H₂Tetraethoxysilane (TEOS) sol-gel solution with a molar ratio of O of 1: 23: 4 was prepared by mixing 3.0g TEOS and 15.0g 1.21.10^-2And (3) mixing the ethanol solution of 12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecyl phosphonic acid (AM 7) in mol/l. The pH was adjusted by adding 1.5g of 0.5M HCl.

Example 2: sol-gel B

TEOS∶EtOH∶H₂Tetraethoxysilane (TEOS) sol-gel solution with a molar ratio of O of 1: 23: 4 was prepared by mixing 3.0g TEOS and 15.0g 1.21.10^-2And mixing the ethanol solution of n-octadecyl phosphonic acid (AM _5) by mol/l. The pH was adjusted by adding 1.5g of 0.5M HCl.

The leather substrate was treated by dipping in the sol-gel for 5 minutes. The substrate was then tempered in an oven at 85 ℃ for 15 h. The results are shown in Table 7.

TABLE 7

Test of	Solutions of	Molar ratio of TEOS to AM	Number of samples	Water absorption (%)
					71	Sol-gel B	62∶1	6	20.8
72	Sol-gel B	17∶1	2	20.7
					73	Sol-gel B	43∶1	2	19.7
74	Sol-gel A	62∶1	8	20.0
					75	Sol-gel A	62∶1	7	17.9

The treatment with n-octadecylphosphonic acid (AM _5) as the active molecule (sol-gel B) was less effective than with 12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecylphosphonic acid (AM _7) (sol-gel a), but the difference was small.

Within the scope of the study, variations in the concentration of active molecules did not significantly affect the final properties of the treated leather.

Example 3: sol-gel C

TEOS: EtOH: H was prepared by mixing 3.0g TEOS with 15.0g ethanol and 0.66 wt% silver nanoparticles (40nm or 60nm)₂Tetraethoxysilane (TEOS) sol-gel solution with O molar ratio of 1: 23: 4. The pH was adjusted by adding 1.5g of 0.5M HCl.

Example 4: sol-gel D

By mixing 3.0g of MTMOS with 15.0g of 1.21.10^-2Preparation of MTMOS: EtOH: H by mixing mol/l of 12, 12, 13, 13, 14, 14, 15, 15, 15-nonafluoropentadecyl phosphonic acid (AM _7) in ethanol₂Methyltrimethoxysilane (MTMOS) sol-gel solution with O molar ratio of 1: 23: 4. The pH was adjusted by adding 1.5g of 0.5M HCl.

Other examples of solutions

Preparation of an ethanol solution of n-octadecylphosphonic acid from a predetermined concentration of 1.21-10^-2mol·L^-1To the solubility limit. The solution was heated at about 60 ℃ and stirred to completely dissolve the solid. Treatment of the substrate with this second solution showed the same trend as solution 1.

Aging of sol-gel solution and AM

It has been found that the water absorption is greatly reduced between an untreated liner (54.6%) and a treated liner (between 27% and 22%). However, despite the change in reflow parameters used to age the sol-gel, the water absorption did not change significantly from sample to sample.

The results of the respective tests are shown in table 8 below. As can be seen from the results in table 8, functionalization has a greater effect on the inside of the liner, which is more porous than the outside.

TABLE 8

On untreated liner, moisture absorption was too fast to make any measurements on the inner surface of the liner

-not measuring

There was a significant improvement in the hydrophobicity (water drop angle) of the inner surface of the liner between the treated and untreated liners, but the variation between different liners was not significant.

Functionalization process

Mixing the selected reactive molecule (AM) with the selected solvent. Is composed of^-4M and the solubility-limited solution of the selected active molecule in the selected solvent (e.g. ethanol) are mixed for 6 hours. Other solvents or solvent mixtures are also possible, as long as they are compatible with the substrate and the sol-gel process. If desired, the mixture may be heated and/or stirred until the reactive molecule is completely dissolved.

Solvent(s)

Ethanol and isopropanol have been tested. Both are suitable.

Time after surface activation (tests 23, 33-35)

Functionalization also needs to be performed directly after pretreatment with oxygen plasma or air plasma. It has been observed that the effect of the plasma pre-treatment will substantially disappear only after 30 minutes. The results are shown in Table 9.

TABLE 9

The results of this test are shown in figure 2.

Treatment time (trials 22-25)

It has been shown that after a certain immersion time, the water repellency of the treated surface is not improved. For the concentration of 1.21-10 in ethanol^-2mol·L^-1AM _7 (solution 1) of (a) after 6 hours of immersion, the absorption was 18% and the performance of the substrate was not significantly affected by the extended time. The results are shown in Table 10.

Watch 10

The results of this test are shown in figure 3.

Concentration of the solution (tests 23 and 26-29)

The concentration of active molecules should be as high as possible without the formation of precipitates. Therefore, it should be set as close as possible to the solubility limit of the active molecule in various solvents, as shown in table 11.

The concentration of ethanol is 1.21-10^-2mol·L^-1The most preferable functionalization of AM-7 (solution 1) of (1) was carried out by immersing the substrate in the solution for 6 hours or less for 1 minute after the surface plasma treatment with air plasma (30s, 30W, 0.5 hPa).

TABLE 11

The results of this test are shown in fig. 4.

Tempering of sol-gel solutions and AM functionalized samples

Sol-gel a containing AM _7 as described above was prepared by stirring and refluxing (aging of the sol-gel solution) at 56 ℃ for 3.5 hours. The sol-gel is cooled for at least 20 minutes. The leather substrate was treated by dipping in the sol-gel for 5 minutes under the above conditions.

The substrate was then tempered in an oven for various times and temperatures. The results are shown in Table 12.

TABLE 12

Tests 62 and 68 have a higher initial water absorption measurement and a lower second measurement. This phenomenon may be related to the tempering time, which seems to be too short to allow complete polymerization of the sol-gel and complete evaporation of the solvent.

The increase in temperature shortens the reaction time. However, higher temperatures can lead to degradation of the leather. No visual modification of the samples treated at 105 ℃ and 120 ℃ was detected, but due to the nature of the substrate, shrinkage of the leather samples was observed at temperatures greater than 85 ℃.

Drying

The substrate is dried after impregnation. Suggested drying temperatures are 20 ℃ to 85 ℃, preferably 25 ℃ to 65 ℃ to maintain the leather structure, more preferably 30 ℃. Drying is carried out until the solvent evaporates. The duration of 15 hours at 85 ℃ allowed the solvent to evaporate well. The duration of 72 hours at 30 ℃ allowed the solvent to evaporate well. Advantageously, the air is ventilated during the drying process.

For example, the substrate may be dried by placing it in a Greiner Tube (Greiner Tube).

Advantageously, the substrate is dried under ventilated air at 30 ℃ for 72 hours.

Sol-gel composition

FIG. 5 shows the water absorption obtained for different TEOS/AM _7 ratios.

Fig. 5 shows that by varying the TEOS/AM _7 ratio, the water absorption (%) of the leather substrate is affected. For each AM _7 concentration, there is an optimum range for the TEOS concentration, and above or below this range, the water absorption increases.

For example, for a TEOS concentration of 0.09 mol% AM (based on the total sol-gel solution including AM), a water absorption of 17% is preferred, with a TEOS concentration of 2.9 mol%. For the same TEOS concentration of 0.09 mol% AM-7 and 1.8 mol% or 3.8 mol%, the water absorption was higher.

An increase in the concentration of AM _7 generally results in a decrease in the water absorption of the leather substrate.

When the AM _7 concentration is increased by 7 times (8.54. multidot.10)^-2mol·L^-1Substitute 1.21. 10^-2mol·L^-1) Only a gain in water absorption of 4% was observed, as shown in fig. 5.

Claims (17)

1. A composition for impregnating a watch band or a part thereof, said composition comprising

a) An organic solvent or a sol-gel,

b) at least one active organic compound comprising-PO, preferably with phosphonate groups₃H₂And a hydrophobic or superhydrophobic group, and

c) optionally one or more functional groups selected from i.

2. Composition according to claim 1, characterized in that the hydrophobic or superhydrophobic group of the reactive organic compound is a linear or branched alkyl group having 2 to 18 carbon atoms, which may be partially or totally substituted by halogen, preferably by chlorine or fluorine, most preferably by fluorine.

3. The composition according to claim 1 or 2, wherein the active organic compound is

i.CH₃(CH₂)_nPO₃H₂N is between 2 and 18, or

ii.CF₃(CF₂)_n(CH₂)_mPO₃H₂N and m are between 2 and 18, and m and n are the same or different.

4. The composition of claim 1, wherein the anti-fouling functional group of the reactive organic compound is of the formula-O ((CH)₂)_mO)_nA polyalkylene glycol group of (a); wherein m is 2, 3 or 4, preferably 2; n is 2 to 18; and having hydrogen or C_1-6Alkyl as end group.

5. The composition of claim 1 or 4, wherein the active organic compound is RO (CH)₂CH₂O)_n(CH₂)_mPO₃H₂Wherein R is H or CH₃N and m are 2 to 18, and n and m are the same or different.

6. The compound of claim 1, wherein the biologically active functional group of the active organic compound is an imidazolium group, a triazolium group or optionally substituted with 1-3C₁-C₆Or by 1 or 2C₁-C₆Alkyl and C₁₀-C₁₈Alkyl-substituted ammonium group of (1).

7. The compound of claim 1 or 6, wherein the active organic compound is CH₃(CH₂)_n(N(CH₃)₂)⁽⁺⁾(CH₂)_mPO₃H₂Cl^(-)Wherein n and m are 2 to 18, and m and n are the same or different, 1-methyl-3- (dodecylphosphonic acid) imidazolium bromide or 1-methyl-3- (dodecylphosphonic acid) imidazolium bis (trifluoromethylsulfonyl) imide.

8. Compound according to any one of the preceding claims, characterized in that it further comprises bioactive metal nanoparticles, preferably silver nanoparticles.

9. Compound according to any one of the preceding claims, characterized in that the organic solvent is ethanol or isopropanol, preferably ethanol.

10. A method for functionalizing a substrate by impregnation comprising the steps of

i. Selecting a substrate;

degassing the substrate;

treating the substrate with an oxygen plasma or an air plasma;

at least partially impregnating or coating said substrate with a composition according to any one of claims 1 to 8, wherein said composition is a composition comprising an organic solvent;

v. drying the treated substrate.

11. A method for functionalizing a substrate by impregnation comprising the following steps

i. Selecting a substrate;

preparing a sol-gel solution from a hydrolysable silane precursor under acidic or basic conditions;

aging the sol-gel solution;

at least partially impregnating or coating the substrate with the sol-gel solution;

v. drying the treated substrate;

fixing the sol-gel on the substrate by tempering.

12. The method according to claim 11, characterized in that the sol-gel contains at least one reactive organic compound according to any one of claims 1 to 9.

13. The method according to any one of claims 10 to 12, wherein the substrate is selected from natural leather, natural leather substitutes made from vegetable fibres, cork and textile fabrics and combinations thereof.

14. The method of any one of claims 10-13, wherein the substrate is a watch band or a portion thereof.

15. Use of a composition according to any one of claims 1 to 9 for reducing the water absorption of a substrate, preferably a watch band or one or more parts thereof.

16. A watch band obtainable by the method according to any one of claims 10 to 14.

17. Watchband comprising at least one reactive organic molecule according to any of claims 1-9 and/or a silica sol-gel network.

Images