WO2016113436A1

WO2016113436A1 - Colour transfer-inhibiting material

Info

Publication number: WO2016113436A1
Application number: PCT/ES2015/070018
Authority: WO
Inventors: Guadalupe BORJA RODRÍGUEZ; Esther DELGADO RODRÍGUEZ; Janina SERRA COMELLAS; Mirko FACCINI; David Amantia; Rosa Escudero Moreno; Miguel OSSET HERNÁNDEZ; Laurent Aubouy
Original assignee: Acondicionamiento Tarrasense
Priority date: 2015-01-15
Filing date: 2015-01-15
Publication date: 2016-07-21
Also published as: EP3246462A1; ES2713241T3; EP3246462B1

Abstract

The invention relates to a colour transfer-inhibiting material consisting of a cellulose substrate functionalised with a quaternary ammonium compound, characterised in that the cellulose substrate consists of cellulose particles or of cellulose nanofibres obtained by electrospinning. This material has a high colour transfer-inhibiting capacity and, as such, is suitable for use as an additive in the washing of clothes. The invention also relates to a method for producing said material and to a clothes washing composition including same as a colour protector.

Description

COLOR TRANSFER-INHIBITING MATERIAL

Technical field

The present invention relates to laundry additives, in particular to a material that is suitable for inhibiting color transfer during washing.

Prior art

It is known that colored garments can lose a part of the coloring substances they contain during washing, which pass into the wash water and, from here, can be transferred to other garments present, of paler or white colors, resulting in to an unwanted coloration of the latter.

This is a major drawback for washing clothes both domestically and industrially.

A traditional method to avoid this color transfer between the washed clothes is simply to wash the clothes separately in the washing machine, depending on their color. However, making this separation is annoying, it is a certain obstacle to optimize the number of washes, and unwanted staining cannot always be avoided in this way. This separation also means an increase in washing time, and a greater consumption of water and electricity.

To respond to this problem, products have been developed as additives, typically in the form of wipes or in liquid form, which are added to the washing machine and easily absorb the possible colors detached during washing, and thus prevent other clothes from being dyed present. Special detergents for colored clothing have also been developed.

Different technical solutions that respond to this pattern have been described in the literature. Thus, for example, in the US patent US4380453, the use of a substrate to which it is applied or impregnated with a dye-capturing substance is described, for example a quaternary ammonium compound, of the glycidyl ammonium type, such as glycidyltrimethylammonium chloride , or a trisubstituted 2-hydroxy-3- halopropyl ammonium derivative. The substrate thus treated serves to adsorb the dyes that dissociate from the dyed materials, and thus avoid coloring other materials present in the wash bath. Among the substrates, there is mentioned a cellulose textile material that can be in the form of fabric, non-woven, rope, ball, knitting, or any other. French patent application FR-A-2761702 also refers to the same problem of color transfer in the washing process. In it, the use of finely divided lignocellulosic substances is proposed to fix the dyes that are released from the tissues during washing. Among these substances, the use of micronized and steam treated wood powder and micronized straw is described. It is also described that said substances are not incorporated into the detergent formulation, but are added to the wash bath separately, for example, inside a mesh bag adjusted to the particle size of the lignocellulosic substances, so that allow them to leave the bathroom, as it would be difficult to avoid redeposition of them on clothes.

European patent application EP-A-1621604 also raises the problem of color transfer during washing and proposes a dye-picking material comprising a substrate selected from a synthetic or natural fabric or nonwoven, or paper, and a additive comprising one of the following polymers: proteins, chitin, chitosan, cationic heterocyclic polymers, polyvinylamine, polyethylene amine, acrylic polymers, vinyl polymers, polyamine A / -oxide, and mixtures thereof. The additive is fixed or incorporated into the substrate by impregnation or spraying.

In the international patent application WO-A-2009/071296, an alternative solution is proposed to prevent coloration and cracking during textile washing, which comprises using a cationized cellulosic substrate prepared from remnants of low quality textile materials , such as pieces of thread and / or cut fibers. The substrate may also comprise cationized cellulose fibers. The substrate is preferably used in a container so that it does not come into contact with clothing.

International patent application WO-A-02/12424 describes the use of a cationically modified polyester substrate with a polyepoxyamine to reduce color transfer during washing.

The different solutions proposed in the state of the art have contributed to reducing the problem of color transfer in the washing of textiles, although they are not completely satisfactory, since in the face of certain dyes and / or types of textiles, they fail to avoid completely accidental dyeing of garments.

Therefore, despite the solutions described in the state of the art, there is still a need to provide new materials that are more effective in preventing the transfer of color during textile washing. Object of the invention

The object of the present invention is a color transfer inhibitor material.

A process for preparing said material is also part of the object of the invention.

The use of said material to inhibit color transfer during the washing process is also part of the object of the invention.

A washing process comprising the use of said material is also part of the object of the invention.

A composition comprising said material also forms part of the object of the invention.

Brief description of the drawings Figure 1

The results of the test of Example 9 where the adsorption capacity of Direct Red 83 dye at different times, by different materials according to the present invention (Examples 3 to 7), are compared in graphical form are shown in graphical form. to three commercial reference products (Reference Examples A, B and C). A solution of the dye was used at a concentration of 10 ppm, which was contacted with 10 mg of each material to be tested.

In ordinates the adsorption capacity expressed as mg of dye adsorbed for each gram of material tested is represented, and in abscissa the contact time between the material tested and the dye solution is represented.

Figure 2

The results of the test of Example 10 where the maximum adsorption capacity of Direct Red 83 dye after a contact time of 60 minutes, by different materials according to the present invention (Examples 3 , 5 and 7), with respect to three commercial reference products (Reference Examples A, B and C). A solution of the dye was used at a concentration of 500 ppm, which was contacted with 10 mg of each material to be tested. In ordinates the adsorption capacity expressed as mg of dye adsorbed for each gram of material tested is represented, and in abscissa each material is represented. Figure 3

The results of an Lini-test test to measure the inhibition of color transfer during washing between a color donor fabric (Direct Orange dye 39) and a white cotton fabric are plotted in Figure 3. using various products according to the present invention (Examples 3-7) comparatively with a detergent without anti-transfer additives and three commercial products that inhibit color transfer (Reference Examples A, B and C), according to the results obtained in Example eleven .

In ordinates the anti-color transfer efficiency is represented, according to a numerical scale from 0 to 5, where 5 indicates maximum efficiency. In abscissa each of the materials tested is represented.

Figure 4

The results of an Lini-test test to measure the inhibition of color transfer during washing between a color donor fabric (Direct Red 83 dye) and a white cotton fabric are plotted in Figure 4. using various products according to the present invention (Examples 3-7) comparatively with a detergent without anti-transfer additives and three commercial products that inhibit color transfer (Reference Examples A, B and C), according to the results obtained in Example eleven .

Figure 5

The results of an Lini-test test to measure the inhibition of color transfer during washing between a color donor fabric (Direct Black 22 dye) and a white cotton fabric are plotted in Figure 5. using two products according to the present invention (Examples 3 and 4) comparatively with a detergent without anti-transfer additives and two commercial color transfer inhibitor products (Reference Examples A and C), according to the results obtained in Example 1 1 . In ordinates the anti-color transfer efficiency is represented, according to a numerical scale from 0 to 5, where 5 indicates maximum efficiency. In abscissa each of the materials tested is represented. Figure 6

Figure 6 shows the results of a test carried out in Lini.-test to measure the inhibition of color transfer during washing between a color donor tissue (Acid blue dye 13) and a white fabric. polyamide, using two products according to the present invention (Examples 3 and 4) comparatively with a detergent without anti-transfer additives and two commercial color transfer inhibitor products (Reference Examples A and C), according to the results obtained in the Example eleven .

Detailed description of the invention

The object of the present invention is a color transfer inhibitor material consisting of a cellulose substrate functionalized with a quaternary ammonium compound of formula (I):

where:

n is between 1 and 20;

Ri is selected from oxyranyl and 2-chloro-1-idroxyethyl;

R ₂ and R ₃ are independently selected from C _1-6 alkyl and benzyl groups;

R ₄ is selected from C _1-20 alkyl groups; Y

X is selected from the group consisting of Cl, Br, I, tetrafluoroborate, trifluoromethanesulfonate and nitrate; Y

wherein the cellulose substrate is selected from the group consisting of:

a) cellulose particles and

b) cellulose nanofibers obtained by electrospinning. The authors of the present invention have developed a new material prepared from a substrate formed by cellulose particles, or by cellulose nanofibers prepared by electrospinning, which, surprisingly, exhibits superior properties as a color transfer inhibitor with respect to products described in the state of the art, in particular with respect to commercial products where the cellulose support is not nanostructured, but in the form of a common textile material, of the wipes type. The developed material is suitable as an additive to be used in washing clothes to avoid unwanted staining of garments. The cellulose substrate

The color transfer inhibitor material, according to the present invention, is characterized in that it contains a particulate cellulose substrate, or in the form of nanofibers obtained by electrospinning, which has specific physical-chemical characteristics, well differentiated from textile cellulosic materials commonly used as support in anti-color transfer products, and which give said material remarkably superior properties for the inhibition of color transfer.

The cellulose substrate used in the present invention is in the form of cellulose particles, or in the form of cellulose nanofibers obtained by electrospinning.

In a preferred embodiment of the invention, the cellulose substrate consists of cellulose particles.

The cellulose particles used within the scope of the present invention are cellulose microparticles or nanoparticles, that is to say they have an average size of the order of micrometers (or microns), usually between 1 μηι and 1000 μηι, or of the order of nanometers, usually between 1 nm and 1000 nm.

The distinction between microparticles and cellulose nanoparticles is not always well defined, since usually the particles are not granular, that is, they do not have an approximately spherical shape, but are fibrillar, typically defined as a function of their average thickness (E) and their average length (L), so that, usually, cellulose particles are classified as nanoparticles if at least one of said dimensions, in particular the thickness, is less than 1 μηι. In the case of particles of fibrillar form, they are also usually characterized by the parameter called "aspect ratio", which is the relationship between the length and thickness of said fibers. Within the scope of the present invention, the cellulose particles used are characterized in that they have an average size between 0.01 μηι and 400 μηι, more preferably between 0.05 μηι and 200 μηι. Said average size of the cellulose particles, whose shape is irregular, as indicated above, usually refers to its equivalent mean diameter, that is, the diameter of a sphere of volume equivalent to that of the particle. In the context of the present invention the term average size is used interchangeably to refer to the average diameter, or equivalent average diameter.

The average size of the cellulose particles, defined according to their equivalent average diameter, can be determined according to the usual analytical procedures for measuring the average particle size, which are well known to the person skilled in the art, for example, by screening methods, by the method of the area sensitive to electric current (Coulter counter), by scattering of laser light, or by the use of electron microscopy, in particular the scanning electron microscope (SEM), or the electron microscope of transmission (TEM, transmission electron microscope). In the chapter Analysis of particle size, from the book M. E. Aulton, Pharmacy. The science of the design of pharmaceutical forms, second edition, Elsevier, Madrid, 2004, Chapter 10, pp154-167 describes the most common parameters and methods for defining and measuring particle size.

According to a preferred embodiment of the invention, the cellulose particles that act as a substrate for the color transfer inhibitor material are chosen from the group consisting of microcrystalline cellulose, powder cellulose, microfibrillated cellulose, nanocrystalline cellulose, and cellulose nanofibers obtained by electrospinning and crushed Preferably, cellulose particles chosen from microcrystalline cellulose, microfibrillated cellulose and cellulose nanofibers obtained by electrospinning and crushed are used. Even more preferably, cellulose particles chosen from microcrystalline cellulose and microfibrillated cellulose are used.

In one embodiment of the invention, the cellulose particles used as support are microcrystalline cellulose.

Microcrystalline cellulose is a crystalline powdery substance, obtained by controlled hydrolysis of α-cellulose, the characteristics of which are well known and described, for example, in the manual of pharmaceutical excipients, R. C. Rowe, P. J. Sheskey and P.J. Weller, Handbook of Pharmaceutical Excipients, fourth edition, Pharmaceutical Press, 2003.

Microcrystalline cellulose has an average particle size that usually varies between 20 μηι and 300 μηι, depending on the different suppliers and procurement procedures Preferably, a microcrystalline cellulose with an average particle size between 40 μηι and 150 μηι is used, more preferably between 50 μηι and 120 μηι, and even more preferably between 70 μηι and 100 μηι.

The microcrystalline cellulose particles are granular, with an approximately spherical shape, with an "aspect ratio" usually between about 1 and 3.

Microcrystalline cellulose can be obtained commercially from various suppliers, for example through the company FMC Biopolymer, under the general trade name AVICEL ^® ; or through the Acros Organics company that distributes microcrystalline cellulose with an average particle size of 50 μηι or 90 μηι; Sigma-Aldrich also distributes microcrystalline cellulose under the name Cellulose microcrystalline 310697, with an average particle size of 20 μηι; and also JRS (J. Rettenmaier & Sóhne) sells microcrystalline cellulose under the names VIVAPUR ^® or HEWETEN ^® , in different particle sizes, for example the so-called HEWETEN ^® 102, with an average particle size of 90 μηι.

In another embodiment of the invention, the cellulose particles used as support are pulverulent cellulose.

Powdered cellulose is a powder obtained by reducing the size of α-cellulose by mechanical means, the characteristics of which are specified, for example, in the RC Rowe book, cited above, and having a particle size usually between 20 μηι and 250 μηι. Powdered cellulose can be obtained commercially, for example through the company J. Rettenmaier & Sóhne, under the general trade name ARBOCEL ^® , according to the varieties ARBOCEL ^® M80 or ARBOCEL ^® A300, for example.

In another embodiment of the invention, the cellulose particles used as support are microfibrillated cellulose.

Microfibrillated cellulose (MFC) has dimensions that usually vary between 0.01 μηι and 4 μηι of average thickness, preferably between 0.01 μηι and 0.1 μηι, and between 1 μηι and 100 μηι of average length. Usually, they have an "aspect ratio" of up to 100, maximum. Alternatively, microfibrillated cellulose can be characterized by the average diameter, or equivalent average diameter of the particles, which is usually between 0.05 μηι and 15 μηι. Microfibrillated cellulose is obtained from cellulose, or from microcrystalline cellulose, by a mechanical treatment of high pressure homogenization, optionally accompanied by a chemical or enzymatic treatment. Microfibrillated cellulose has a thickness usually less than 1 μηι, so it is usually described as nanocellulose, or cellulose nanoparticles.

Microfibrillated cellulose is well known by the person skilled in the art, and can be obtained commercially, in different sizes, from various suppliers, in particular from the company J. Rettenmaier & Sóhne, for example, the one known by the trade name ARBOCEL ^® UFC 100, whose fibers have a length of approximately 8 μηι.

In another embodiment of the invention, the cellulose particles used as support are nanocrystalline cellulose.

Nanocrystalline cellulose is a highly crystalline form of cellulose, which is presented in the form of needles and is obtained by hydrolysis of cellulose with a strong acid under controlled conditions, for example, as described in the Habibi eí al article. Cellulose nanocrystals: chemistry, self-assembly, and applications, Chem. Rev., 2010, 1 10, p3479-3500. The nanocrystalline cellulose has dimensions usually between 3 nm and 5 nm thick and up to 200 nm in length.

In the chapter Aspler eí al. fiéview oí nanocellulosic producís and íheir applicaíions, from the book: Biopolymer nanocomposiíes. Processing, properíies and applicaíions, Edited by A. Dufresne, S Thomas and L.A. Pothan, 2013, John Wiley & Sons (ISBN 978-1 -1 18-21835-8), chapter 20, pp461-508, describes the properties of the cellulose microparticles and nanoparticles mentioned above.

In another embodiment of the invention, the cellulose particles used as support are prepared by crushing cellulose nanofibers obtained by elecrospinning. The particles thus obtained, in the form of fibers or filaments, generally have an average diameter between 0.1 μηι and 1 μηι, more preferably between 0.3 μηι and 0.8 μηι, and an average length usually between 2 μηι and 100 μηι, more preferably comprised between 3 μηι and 80 μηι, and even more preferably comprised between 4 μηι and 50 μηι.

The technique known as elecrospinning is well known to the person skilled in the art, and allows the preparation of nanofibers from a solution of a certain material, usually polymers, by applying electric current with a sufficiently high voltage, which causes the expulsion of fine wires from a capillary, while the solvent evaporates, thereby forming nanofibers of said material. To prepare cellulose nanofibers, it can be used, for example, a solution of cellulose acetate in a solvent or a mixture of solvents, for example, a mixture of acetone / dimethylacetamide. Cellulose acetate can be obtained commercially. For example, the Sigma-Aldrich company distributes cellulose acetate with an average molecular weight (Mn) of 30,000.

Suitable conditions for electrospinning cellulose acetate are, for example, a voltage of 30 kV, a flow of between 3 and 4 mL / h, a distance to the collector of 12 cm, and a rotation speed of 500 rpm.

Then, the cellulose acetate nanofibers obtained are hydrolyzed, usually with a solution of sodium hydroxide to deacetylate the product and obtain cellulose nanofibers. The solid obtained is filtered and dried, preferably at a temperature between 40 ^e C and 80 ^e C, more preferably between 55 ^e C and 65 ^e C for a period usually between 0.5 and 3 hours, preferably for approximately one hour.

The nanofibers obtained according to this electrospinning process are crushed, for example with an IKA A 1 1 basic mill, to obtain cellulose particles. The crushing step can be done on the cellulose acetate nanofibers obtained directly from the electrospinning process and / or after the hydrolysis stage, once the cellulose is deacetylated.

In another embodiment of the invention, the cellulose support used in the color transfer inhibitor material is cellulose nanofibers, prepared by electrospinning, without crushing.

Quaternary Ammonium Compound

The color transfer inhibitor material consists of a cellulose support functionalized with a quaternary ammonium compound, characterized in that it has a high affinity for dyes or dyes.

In particular, the quaternary ammonium compound used in the material object of the present invention is a product of formula (I):

(|)

where:

n is between 1 and 20;

Ri is selected from oxyranyl and 2-chloro-1-idroxyethyl;

R ₂ and R ₃ are independently selected from Ci alkyl groups _R4 is selected from Ci- ₂₀ alkyl groups; Y

X is selected from the group consisting of Cl, Br, I, tetrafluoroborate, trifluoromethanesulfonate and nitrate.

Definitions

In the context of the present invention, a Ci- ₆ alkyl group refers to a saturated hydrocarbon group having between 1 and 6 carbon atoms, which can be linear or branched, and includes, among others, the methyl, ethyl groups, n-propyl, isopropyl, sec-butyl, ferf-butyl, n-pentyl, 1-methylbutyl or n-hexyl.

Similarly, a C _1-20 alkyl group refers to a saturated hydrocarbon group having between 1 and 20 carbon atoms, which can be linear or branched, and includes, among others, the methyl, ethyl, n-propyl, isopropyl groups , sec-butyl, ferf-butyl, n-pentyl, 1-methylbutyl, n-hexyl, n-octyl, n-decyl, n-dodecyl n-tetradecyl, n-hexadecyl or n-octadecyl.

An n-C ₈ -C ₁₈ alkyl group refers to a saturated linear hydrocarbon group having between 8 and 18 carbon atoms, and is formed by the n-octyl, n-nonyl, n-decyl, n-undecyl groups, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl.

The oxyranyl group refers to the radical:

The 2-chloro-1-hydroxyethyl group refers to

to the radical:

In turn, the tetrafluoroborate anion refers to the BF ₄ ^{~ group} , the trifluorometosulfonate (or triflate) is the anion S0 ₃ (CF ₃ ) ^~ , and the nitrate group corresponds to the anion N0 ₃ ^~ .

In a preferred embodiment of the invention, the compound of formula (I) is characterized in that n is 1, R ₂ , R ₃ and R ₄ are selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and X is select from the group consisting of Cl, Br, and I. In an even more preferred embodiment, R ₂ , R ₃ and R ₄ are methyl and X is Cl.

In a preferred embodiment of the invention Ri is oxyranyl.

According to various particular embodiments of the invention, the quaternary ammonium compound of formula (I) is characterized in that:

- n is between 1 and 20, preferably between 1 and 10, more preferably between 1 and 5, and even more preferably n is 1; Ri is selected from: oxyranyl and 2-chloro-1-hydroxyethyl; more preferably R ^ is oxyranyl;

R ₂ and R ₃ are independently selected from Ci- ₆ alkyl groups, more preferably independently selected from the group consisting of methyl, ethyl, n-propyl and isopropyl; and even more preferably R ₂ and R ₃ are both methyl;

R ₄ is an alkyl group Ci- _20, more preferably is selected from methyl, ethyl, n- propyl, isopropyl, or n-alkyl C ₈ Ci _8, most preferably R ₄ is methyl; - X is selected from the group consisting of Cl, Br, I, tetrafluoroborate, trifluoromethanesulfonate and nitrate, preferably X is selected from Cl, Br and I, and even more preferably X is Cl.

In a particularly preferred embodiment of the invention, the compound of formula (I) is characterized in that n is 1, Ri is oxyranyl; R ₂ , R ₃ and R ₄ are methyl and X is selected from Cl, Br, I, more preferably X is Cl. According to this embodiment, the product of formula (I) is glycidyltrimethylammonium chloride (CAS number 3033-77- 0), which is commercially available from various suppliers, for example, Sigma-Aldrich (Switzerland), or from SKW Quab Chemicals (product Quab ^® 151).

In another particularly preferred embodiment of the invention, the compound of formula (I) is characterized in that n is 1, R is 2-chloro-1-hydroxyethyl, R ₂ , R ₃ and R ₄ are methyl and X is selected from Cl, Br, I; more preferably X is Cl. According to this embodiment, the product of formula (I) is (3-chloro-2-hydroxypropyl) trimethylammonium chloride (CAS number 3327-22-8), which can be obtained through the Sigma company -Aldrich, or through the company SKW Quab Chemicals (product Quab ^® 188).

In another preferred embodiment of the invention, the compound of formula (I) is characterized in that n is 1, Ri is 2-chloro-1-hydroxyethyl; R ₂ and R ₃ are methyl, R ₄ is chosen from an n-C ₈ -Ci ₈ alkyl, more preferably it is chosen from n-octyl, n-dodecyl, n-hexadecyl, and n-octadecyl; and X is chosen from Cl, Br, I, more preferably X is Cl. According to this embodiment, usually the compound of formula (I) is a mixture of at least two compounds, with different R ₄ , in different proportions. Some of these products are commercially available, through the company SKW Quab Chemicals, for example the commercial product Quab ^® 342 where R ₄ is n-dodecyl, the commercial product Quab ^® 360, a mixture of R ₄ = n- octyl and R ₄ = n-octadecyl; or the commercial product Quab ^® 426, a mixture of R ₄ = n-dodecyl, R ₄ = n-hexadecyl and R ₄ = n-octadecyl; in all of them R is 2-chloro-1-hydroxyethyl, R ₂ and R ₃ are methyl, and X is Cl. Preparation Procedure

In the material of the invention, the cellulose support is functionalized with the quaternary ammonium product of formula (I). This means that said product binds to cellulose by reaction with the hydroxyl groups present therein, to form cellulose particles or functionalized cellulose nanofibers, according to the following structure, where the circle represents the cellulose support:

Also part of the object of the invention is a process for preparing the material of the invention. In order to prepare said material, that is, to functionalize the cellulose particles, or the cellulose nanofibers obtained by electrospinning, for example, a process comprising the following steps can be used:

a) preparing an aqueous suspension of the cellulose substrate together with the quaternary ammonium compound of formula (I) at alkaline pH between 12 and 14, and keeping the assembly under stirring;

b) filter and subject the resulting soaked cellulosic material at a temperature between 60 ^e C and 1 10 ^e C;

c) wash the resulting material with water until neutral pH and dry at a temperature between 60 ^e C and 80 ^e C.

To obtain the aqueous suspension at alkaline pH, any alkalizing agent can be used, such as, for example, alkali hydroxides, or alkali carbonates. Preferably, sodium hydroxide is used as alkalizing agent.

In the suspension initially prepared, in step a), the concentration of sodium hydroxide is preferably between 2% and 10%, more preferably between 3% and 5%. and even more preferably between 4% and 4.5%; the concentration of the quaternary ammonium compound of formula (I) is preferably between 2% and 15%, more preferably between 5% and 10%, and even more preferably between 8% and 9%; and the cellulose concentration is preferably between 1% and 10%, more preferably between 3% and 5%, and even more preferably between 4% and 4.5%; where all percentages are expressed in weight. Thus, the molar ratio between the cellulosic material / sodium hydroxide / compound of formula (I) is preferably between the following values: 1 / (3-10) / (1, 5-5), more preferably between 1 / (4.0-4.5) / (2.0-2.5) and even more preferably said molar ratio is 1 / 4.1 / 2.1.

In step a) the assembly is kept under stirring at room temperature, for example between 10 minutes and 3 hours, preferably between 15 minutes and 1.5 hours, by mechanical agitation at, for example, between 600 and 1500 rpm, or under magnetic stirring.

Then, according to step b) of the process, most of the solution is removed by filtration and the soaked cellulosic material is introduced into an oven, at a temperature between 60 ^e C and 1 10 ^e C, preferably at 100 ^e C, for a period preferably between 15 minutes and 24 hours.

In step c), the functionalized cellulose obtained is washed with water repeatedly until the wash water has approximately neutral pH. The resulting material is dried at a temperature between 60 ^e C and 80 ^e C, for a period of time preferably between 12 and 24 hours.

In step a) two alternative procedures can be followed. According to a first alternative, an aqueous solution of the alkalizing agent, preferably sodium hydroxide, is initially prepared with the quaternary ammonium compound of formula (I) and on said solution the cellulose particles or cellulose nanofibers obtained by electrospinning are added, stirring then the assembly for a period of time preferably between 10 minutes and 3 hours, more preferably between 15 minutes and 1.5 hours.

Alternatively, a mixture can be prepared first by adding the cellulosic material onto an aqueous solution of the alkalizing agent, preferably sodium hydroxide, stirring for a period preferably between 5 minutes and 1.5 hours, and then the quaternary ammonium compound of formula (I), stirring again, preferably for between 5 minutes and 1.5 hours.

According to this procedure, cellulose particles and cellulose nanofibers were functionalized. The effectiveness of the functionalization was assessed by conducting an elementary analysis of the prepared materials and calculating the percentage of N incorporated, that is, the grams of N per 100 g of functionalized cellulose. Values ranging from 0.3 to 0.9 (see Examples 3 to 8) were obtained for the cellulose particles or cellulose nanofibers of the material of the invention. The same elementary analysis test performed with commercial wipes allowed verify that these products had comparable functionalization values, between 0.4-0.6 (see Examples 3 to 8).

Use of the material of the invention

Various application tests were performed to compare the color anti-transfer material according to the present invention, and other commercial products based on cellulosic textile materials, of the wipe type.

Thus, in Examples 9 and 10 the capacity of the material of the invention was evaluated, comparatively with three commercial products of the type anti-color transfer wipes, to adsorb the dyes, observing that the product of the invention has greater absorption capacity, and also allows discoloration more quickly than commercial products compared.

The results of the tests described in Examples 9 and 10 have been plotted in Figure 1, where the dye adsorption capacity is compared against time, and in Figure 2, where the maximum adsorption capacity of dye at 60 minutes.

On the other hand, in Example 1 1 the efficacy of the material of the invention was evaluated in order to avoid the transfer of color between fabrics, according to an assay carried out in a Lini-test device that simulated washing conditions in a washing machine, and in the that white colored fabrics and fabrics were introduced, together with a detergent without anti-color transfer additives and the material of the invention, or three commercial products, in addition to said detergent as a reference. Colored fabrics with various dyes, and white cotton and polyamide fabrics were tested.

It was observed that the products according to the present invention were surprisingly more effective than the reference products to prevent color transfer to white tissues, especially under the conditions of greatest danger of color transfer, ie between direct dyes and cotton fabrics , and between acid and polyamide type dyes. The test results for these especially relevant cases have been represented graphically in Figures 3, 4, 5 and 6, where it can be seen that the material according to the present invention (dark bars) was more effective in preventing color transfer than the reference products (clear bars), obtaining values close to total inhibition (5).

Therefore, the use of the material of the invention to inhibit color transfer during the laundry process is part of the object of the present invention. Thus, the material of the invention is suitable to be added as an additive during laundry, typically in automatic washing using any commercially available type of washing machine. Said material can be added, for example, at the beginning of the main washing program, together with the detergent, or immediately before or after adding the detergent.

The material of the invention is added to the washing machine in an amount usually between 1 g and 50 g per Kg of clothes, although said quantity can be conveniently adjusted according to the needs.

Also part of the object of the invention is a process for washing textiles comprising the use of said material.

Said procedure consists in following the usual washing process for each washing machine, according to any of the available programs, at any temperature, and of any duration, and is characterized by the addition of the color transfer inhibitor material of the present invention during washing, it is preferably added together with the detergent, or alternatively immediately before or after adding the detergent, so that it acts during the main washing stage, which is when there is a greater risk of color transfer.

The product of the invention, in the form of fine functionalized cellulose particles, acts in the wash bath, adsorbing the dye that can be released from the colored garments, and is simply removed during rinsing, leaving no residue and without damaging the clothes. Therefore, the elimination of the anti-transfer product is not required at the end of the wash, as is the case with other commercial products, such as wipes.

The material of the invention can be incorporated into any composition suitable for use in washing clothes, for example, a laundry additive or a detergent composition.

For example, the material of the invention can be added to a detergent composition, so that a detergent is obtained which already has a color transfer inhibitor product incorporated.

Detergent compositions suitable for incorporating the color transfer inhibitor product according to the present invention may be, without limitation, any type of detergent composition suitable for washing textile garments, and which are well known to those skilled in the art, by example, as described, in the book JJ García Domínguez, Surfactants and Detergency, Editorial Dossat, Madrid, 1986 (ISBN 84-237-0687-7); or in the book G. Jakobi and A. Lóhr, Detergents and Textile Washing. Principies and Practice. VCH Verlagsgesellschaft, Weinheim, 1987 (ISBN 3-527-2681 1 -1).

Thus, a laundry washing composition comprising the color transfer inhibitor material of the present invention is also part of the object of the invention.

Examples

Preparative Example 1: Preparation of cellulose nanofibers by electrospinning

A 22% by weight solution of cellulose acetate (Sigma Aldrich 180955, average molecular weight M _n , 30,000) was prepared in a mixture of the solvents acetone and dimethylacetamide in a 1: 1 weight ratio.

The resulting solution was subjected to an electrospinning process in the commercial equipment, model NF-103 of the company MECC Co. Ltd. The conditions used in this process were the following: voltage = 30 kV, flow = 3-4 mL / h , distance to the collector = 12 cm, speed of rotation of the collector = 500 rpm. Cellulose acetate nanofibers were obtained, forming a mesh.

These nanofibers were then deacetylated, for which they were immersed in 3.5 L of a 0.3 M NaOH solution for 1 hour, and the deacetylation was controlled by infrared spectroscopy (IR / ATR, Infraed / Attenuated Total féflection), for which a commercial equipment, model IRAffinity-1 with accessory Miracle ™ ATR of the company SHIMADZU was used.

Then the nanofibers were filtered, washed with water, and dried at a temperature of 60 ^and C, overnight.

The cellulose nanofibers thus obtained were characterized using a scanning electron microscope (SEM), specifically using a JSM-6010-LV model from JEOL. The diameter of said fibers was 452 nm ± 130 nm.

Preparative Example 2: Preparation of cellulose particles by crushing cellulose nanofibers obtained by electrospinning

Starting from the cellulose nanofibers prepared in the preparation Example 1, which were crushed using an IKA A 1 1 basic mill for 15 minutes until a fine powder was obtained. The size of said particles obtained was characterized using the scanning electron microscope, observing that the particles prepared from the nanofibers were approximately between 4 and 20 μηι in length. Examples 3 to 8: Functionalized cellulose particles

The following cellulose particles were functionalized: microcrystalline cellulose (ACROS ORGANICS, Product 38231, particle size 90 μηι), microfibrillated cellulose (Arbocel, Product UFC 100, average particle size between 6-12 μηι (d ₅₀ )), and the particles prepared in Preparative Example 2.

These substrates were functionalized with glycidyltrimethylammonium chloride (Allorachem, product 43831949).

As a starting product, 12 g of the particles obtained in Preparative Example 2, and 100 g of microcrystalline cellulose and microfibrillated cellulose were used.

To prepare the anti-color transfer material from said cellulose particles, two alternative procedures were followed, described below, which are totally analogous, and only differ in the order in which the reagents are added. In the case of the cellulose particles of Preparative Example 2, only the first one was followed (procedure 1), while microcrystalline cellulose and microfibrillated cellulose were functionalized by both methods.

Procedure 1: An aqueous solution was prepared in a container with

NaOH and glycidyltrimethylammonium chloride, and cellulose particles were added to said solution, so that the proportion by weight of the cellulose particles in all cases was 4.2%, the proportion by weight of NaOH was 4, 3% and the concentration of glycidyltrimethylammonium chloride was 8.3%, which represented a molar ratio cellulose / NaOH / glycidyltrimethylammonium chloride of 1 / 4.1 / 2.1. The whole was stirred for 1 hour at room temperature by mechanical stirring at 1000 rpm.

Then, the cellulose particles were filtered to remove most of the solution, leaving the soaked cellulosic material, and thereupon the material was placed in an oven at 100 C for 30 minutes ^and. Subsequently, the final product was washed with water repeatedly until the wash water had a neutral pH. The resulting material at 80 C ^and dried for 20 hours.

Procedure 2: An aqueous NaOH solution was prepared in a vessel, the cellulose particles were added, and the whole was stirred for 30 minutes at room temperature by mechanical stirring at 1000 rpm. Glycidyltrimethylammonium chloride was then added, and mechanically stirred at 1000 rpm for Another 15 minutes at room temperature. As in the previous procedure, the proportion by weight of the cellulose particles in all cases was 4.2%, the proportion by weight of NaOH was 4.3% and the concentration of glycidyltrimethylammonium chloride was 8 , 3%, which represented a molar ratio cellulose / NaOH / glycidyltrimethylammonium chloride of 1 / 4.1 / 2.1.

The cellulose particles were then filtered to remove most of the solution, and from this point it was continued as in procedure 1, after filtration.

According to said procedures, functionalized cellulose particles were obtained with the quaternary ammonium compound glycidyltrimethylammonium chloride. To verify the degree of functionalization, an elementary analysis of said products was carried out, and the% of N containing, that is, the grams of N per 100 grams of sample analyzed, was calculated. The results are shown in Table 1 .

TABLE 1

The degree of functionalization was also compared with that of three commercial products (Reference Examples A, B and C), all of them in the form of wipes, also analyzing in this case the% N contained in said products. The percentage of functionalization was verified, in the case of Reference Examples A and B they were comparable to those of the products of the invention. Reference Example C, presented a large dispersion of the results (between 0.194 and 2.802), obtained in 6 repetitions of the test for different samples of the same product, so it did not calculate the average value since the distribution of the ammonium compound Quaternary was not homogeneous in the sample.

Example 9: Test of the adsorption capacity of dyes by the material of the invention: kinetic study

A test was carried out to evaluate the adsorption capacity of Direct Red 83 dye (CAS 15418-16-3) by the material object of the present invention, comparatively with respect to commercial products, based on contact time (or kinetic study) .

For this purpose, the amount of dye adsorbed by the material, expressed as mg of dye per gram of material, was determined at different times (1, 5, 10, 15, 30, 45 and 60 minutes).

10 mg of the material to be tested in 10 ml of a 10 ppm solution of Direct Red 83 dye was contacted. To determine the amount of dye adsorbed on the material at different times the absorbance of the solution was measured by UV spectroscopy. visible, and these values were interpolated in a dye calibration line.

The results obtained are shown in Table 2, and are plotted in Figure 1. It can be seen that all the materials tested according to the present invention had a higher adsorption capacity compared to commercial products, and also showed a higher speed of action.

The theoretical maximum adsorption capacity for the tested solution of Direct red 83 dye. 1 is 10 mg dye / g material. When the observed adsorption capacity was equal to the theoretical one, the complete discoloration of the solution was observed.

TABLE 2

Adsorption capacity (mg dye / g material)

Material 1 min 5 min 10 min 15 min 30 min 45 min 60 min

Example 3 10.2958 10.5378 10.4124 10,5009 10.0428 10.4465 10.4278

Example 4 2.8210 6.2198 8.4512 9.33354 9.8157 10.4498 10.4430 Example 5 6,0074 8,8080 10.2615 9,9017 10,381 1 10,3166 10,0888

Example 6 4.5296 8.0827 9.9589 10.2894 10.3579 10.3731 10.3396

Example 7 8.9479 10.4402 10.3980 10.5415 10.5930 10.5525 10.4449

Ex. A 6.6590 4.1 1 13 3.4077 3.0607 2.4993 3.5731 2.2704

E.g. Ref B 0,7794 3,0809 3.9133 5.6563 6.7562 6.5282 7.6293

Ex. Ref. 2,7951 3,2671 3.6412 3.7493 4.2507 4.4080 4.5198

All the materials according to the present invention were able to adsorb all the dye, producing the total discoloration of the solution. Complete adsorption occurred after 1, 25, 10, 15 and 5 minutes for Examples 3, 4, 5, 6 and 7, respectively. In contrast, none of the Reference Examples reached this theoretical maximum value, but showed lower maximum adsorption values.

Example 10: Test of the adsorption capacity of dyes by the material of the invention: study at 60 minutes

In this test the adsorption capacity of the Direct dye was evaluated

Network 83 (CAS 15418-16-3) by the material object of the present invention, comparatively with respect to commercial products, setting a contact time of 60 minutes.

A procedure analogous to that described in Example 9 was followed, contacting 10 mg of the material to be tested with 10 mL of a solution of Direct Red 83 dye with a concentration of 500 ppm.

The materials tested were those corresponding to Example 3 (cellulose nanofiber support prepared by electrospinning and crushed), Example 5 (microcrystalline cellulose support) and Example 7 (microfiber cellulose support), comparatively with respect to three commercial products in the form of wipes (Reference Examples A, B and C).

The results obtained are shown in Table 3, and are plotted in Figure 2.

TABLE 3

Adsorption capacity at 60 minutes

Material

(mg color ante / g material) Example 3 169.85

Example 5 93.18

Example 7 131, 90

Reference Example A 80.30

Reference Example B 15.65

Reference Example C 7.01

It can be seen that all the materials according to the invention showed an adsorption capacity of the dye superior to that of the reference materials. Example 1 1: Test of the efficacy of the materials of the invention as anti-color transfer agents

A test was carried out to evaluate the efficacy as anti-transfer agents of the color of the materials according to the present invention in the washing of garments. Specifically, in this test the ability of several products to avoid transferring a donor tissue to an acceptor tissue was evaluated. This test is recommended by the A.I.S.E. (International Association for Soaps, Detergents and Maintenance Products) and the one defined by the EU in Ecolabel for color laundry detergents.

The color acceptor fabrics used in the test were: - 100% cotton with green lines in accordance with ISO 2267.

Dimensions of each test piece: (5.5 x 16) cm

Polyamide according to ISO 105 F03. Dimensions of each test piece: (6 x 16) cm.

Acceptors tissues were pre-washed 3 times at 60 C ^and in a cotton with detergent without brighteners.

The color donor tissues used in the trial were: Direct Orange 39 (CAS 1325-54-8), Direct Red 83 (CAS 15418-16-3), Direct Black 22 (CAS 6473-13-8) and Acid Blue 1 13 (CAS 3351 -05-1), all of them commercially available, for example, through EMPA or WFK. 0.3 g of each donor tissue was used for the tests.

To carry out the test, a Lini-Test Atlas device was used. Said equipment consists of a water bath in which a device with 8 closed containers tightly rotated at a speed of (40 ± 2) rpm. A donor tissue and an acceptor of each type were included in each vessel along with 100 ml of a solution of the product to be tested.

When the water bath reached the temperature of 30 ^e C (± 0.5 ^e C) the prepared containers were introduced. At this time the bath continued to warm at a speed of 2 ^e C / min until reaching 60 ^e C and remained constant for 20 minutes. After the test time, the acceptor tissues were removed and rinsed under running water. The tissues were allowed to dry in the air avoiding direct light.

The tissues were evaluated spectrophotometrically at the beginning and at the end of the test in order to calculate the amount of color accepted (dyed) for each specimen.

For evaluation, a Datacolor Spectraflash SF 600 PLUS-CT spectrophotometer was used under the following reading conditions:

- Measurement geometry: d / 8 ^e

- Observed D65 / 10 ^e

420 nm cut off

The cotton and polyamide fabrics were evaluated independently, since their behavior is totally different, as were each of the dyes.

The materials of the invention prepared in Examples 3, 4, 5, 6 and 7 were tested, all at a dose of 0.5 g, comparatively with respect to three types of anti-color transfer wipes (Reference Examples A, B and C), dosed according to the manufacturer's recommendations according to a certain surface and not by weight.

The products of Examples 3-7 and Reference Examples A-C were tested together with a simple commercial detergent, without anti-color transfer additives, which was also tested on its own, as a reference (Product Det).

The evaluation of the anti-transfer efficiency was based on a numerical evaluation assigned based on a gray scale following the UNE EN ISO 105- A04 standard. Values range from 0 (black) to 5 (white). At higher value, better inhibition of color transfer.

Table 4 summarizes the results obtained in the test for the materials according to the present invention (Examples 3 to 7), comparatively with respect to commercial products (Reference Examples A, BC), and with respect to commercial detergent without any anti additive -transfer of color (Det). The color transfer for each donor tissue was independently tested for each type of acceptor tissue (cotton and polyamide). TABLE 4

It is observed that for the three direct dyes tested {Direct Orange, Direct Red and Direct Black), the anti-color transfer results with the products of the invention are remarkably superior to the comparative commercial products in the tests carried out with cotton as a fabric acceptor In the case of polyamide, the inhibition of color transfer is easier for all products, since direct dyes have more affinity for cotton than for polyamide, so the results obtained do not discriminate the effectiveness of The different products analyzed.

It is also observed that for the acid dye tested {Acid blue), the anti-color transfer results obtained with the material of the invention in polyamide are clearly superior to those obtained with the commercial reference products. Acid dyes have a higher affinity for polyamide, so in the cotton test the results of color transfer inhibition They were good for all products, and did not allow discriminating efficacy between them.

The results of Table 4 for the three direct dyes in cotton, and for the acid dye in polyamide have been plotted in Figures 3, 4, 5 and 6. In all of them the superiority of the material of the invention can be observed in comparison with the commercial products evaluated.

Claims

1 .- Color transfer inhibitor material consisting of a cellulose substrate functionalized with a quaternary ammonium compound of formula (I):

where:

n is between 1 and 20;

Ri is selected from oxyranyl and 2-chloro-1-idroxyethyl;

R ₂ and R ₃ are independently selected from C _1-6 alkyl and benzyl groups; R ₄ is selected from C _1-20 alkyl groups; Y

wherein the cellulose substrate is selected from the group consisting of:

a) cellulose particles and

b) cellulose nanofibers obtained by electrospinning.

2. Material according to claim 1, characterized in that the cellulose substrate is cellulose particles.

3. Material according to claim 2, characterized in that the cellulose particles have an average size between 0.01 μηι and 400 μηι.

4. - Material according to any of claims 2 or 3, characterized in that the cellulose particles are chosen from the group consisting of microcrystalline cellulose, powdery cellulose, microfibrillated cellulose, nanocrystalline cellulose, and cellulose nanofibers obtained by electrospinning and crushed.

5. - Material according to claim 4, characterized in that the cellulose particles are chosen from the group consisting of microcrystalline cellulose, microfibrillated cellulose and cellulose nanofibers obtained by electrospinning and crushed.

6. - Material according to claim 5, characterized in that microcrystalline cellulose with an average particle size between 40 μηι and 150 μηι is used.

7. Material according to claim 5, characterized in that microfibrillated cellulose with an average particle size between 0.05 μηι and 15 μηι is used.

8. Material according to any of claims 1 to 7, characterized in that in the compound of formula (I) n is 1; R ₂ , R ₃ and R ₄ are selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and X is selected from the group consisting of Cl, Br, and I.

9. Material according to claim 8, characterized in that R ₂ , R ₃ and R ₄ are methyl and X is Cl.

10. - Material according to claim 9 characterized in that the product of formula (I) is glycidyltrimethylammonium chloride.

eleven . - Method for preparing the color transfer inhibitor material according to any one of claims 1 to 10 comprising the following steps:

a) preparing an aqueous suspension of the cellulose substrate together with the quaternary ammonium compound of formula (I) at alkaline pH between 12 and 14 and keeping the assembly under stirring;

12. - Use of the material according to any of claims 1 to 10 to inhibit color transfer during the laundry process.

13. - Procedure for washing textiles comprising the use of the material according to any of claims 1 to 10.

14. - Composition for washing clothes comprising the material according to any of claims 1 to 10.