TW201842258A - Method for transferring a colorant to a cellulosic substrate - Google Patents

Abstract

A method for transferring a colorant to a substrate comprising agitating a composition comprising the substrate, solid particles, the colorant and a liquid medium, wherein: the colorant is dissolved and/or dispersed in the liquid medium; the substrate is or comprises a cellulosic material; the solid particles have a size of from 1 to 50 mm.

Description

   Method for transferring colorant to cellulose substrate   

The present invention relates to a method for transferring colorants to a cellulose substrate using solid particles. This method is particularly useful for dyeing cotton, which is generally in the form of textiles.

PCT Patent Publication No. WO2006 / 040539 discloses a method for applying at least one substance to a substrate using polymer particles coated with the at least one substance. The substrate may be a textile and the substance may include a dye. This disclosure requires (mandatory or necessary features) to coat the polymeric particles with the substance. A coating of polymer particles is said to be necessary for the method of the invention.

Although the above methods provide good color leveling and color intensity on the substrate, the inventors sought: i. To further improve the color intensity of the coloring substrate in a specific amount of coloring agent; ii. To further improve the transfer of colorant to the base Material efficiency to reduce the amount of waste of colorants; iii. Reduce the amount of unfixed colorants at the end of the coloring method, thereby reducing the amount of waste of colorants; iv. Provide a method that particles can be used multiple times; v. Provide a particle that can be easily A method of cleaning to remove any small amount of toner residue on the particles.

The inventors have unexpectedly found that relative to the teachings of WO2006 / 040539, excellent results can be obtained when a colorant (such as a dye) is dissolved and / or dispersed in a liquid medium rather than, for example, coated on particles.

A first aspect of the present invention provides a method for transferring a colorant to a substrate, comprising agitating a composition including the substrate, solid particles, the colorant, and a liquid medium, wherein the colorant is dissolved and / Or dispersed in the liquid medium; the substrate is or contains a cellulose material; and the size of the solid particles is 1 to 50 mm.

Figure 1a shows the visual appearance of undyed cotton, and Figures 1b and 1c show the visual appearance of the cotton substrate after dyeing Comparative Examples 1 and 2, respectively.

Figure 2a shows the visual appearance of the dyed cotton prepared from Example 1, and Figure 2b shows the visual appearance of the dyed cotton prepared from Comparative Example 3 in which no solid particles are used.

Dissolve and / or disperse

The colorant can be dissolved in a liquid medium. The colorant can be dispersed in a liquid medium. Some colorants can also be dissolved, and the rest are dispersed in a liquid medium.

Preferably, the solid particles are not coated with any colorant. Solid particles may have small or trace amounts of colorants adsorbed to the particle surface, but they are not sufficient to form a coating. That is, any trace amount of colorant that may tend to be adsorbed on the particle surface does not form a continuous layer that surrounds or encapsulates the particle.

It should therefore be understood that the method of the present invention is suitably a step that does not include the effect of the colorant coating the solid particles. In particular, it should be understood that the solid particles were not coated with a colorant before the solid particles contacted the substrate. For example, the method of the present invention preferably does not include the absence of a liquid medium, especially in the absence of a liquid medium suitable for transferring color to a substrate, and in particular the absence of a liquid medium for transferring color to a substrate. Next, a step of mixing the colorant with the particles.

Preferably, the colorant is dissolved and / or dispersed in a liquid medium in the absence of any solid particles. In this way, a colorant solution and / or dispersion is prepared. The solid particles are preferably added after the colorant solution and / or dispersion have been prepared.

Preferably, the colorant and the solid particles are not heated together in the absence of a substrate.

Preferably, the colorant is dissolved and / or dispersed in a liquid medium in the absence of a substrate.

The colorant is preferably dissolved and / or dispersed in a liquid medium in the absence of a substrate and in the absence of solid particles.

Therefore, the first aspect of the present invention is preferably a method for transferring a colorant to a substrate. As defined above, the steps include: dissolving and / or dispersing the colorant in a liquid state in the absence of the solid particles A medium; and agitating the dissolving and / or dispersing agent in the liquid medium, the substrate and the solid particles.

Preferably, if the solid particles are separated from the liquid medium and the coloring agent before the substrate is processed, the solid particles contain less than 5 weight percent of the total amount of the coloring agent present in the composition, more preferably less than 2.5 weight percent, especially Is a coloring agent that is less than 1 weight percent, more particularly less than 0.5 weight percent, and most particularly less than 0.1 weight percent. If this colorant is present in the solid particles, it is not a coating. Instead, it is absorbed into the particles internally, or in a small area (without a coating) located on the surface of a solid particle.

Solid particles

The solid particles may include a polymeric material, a non-polymeric material, or a mixture thereof.

Preferably, the solid particles are or include a polymeric material.

Preferably, the polymeric material is thermoplastic.

The polymer particles may be polyamide, polyester, polyolefin, or polyurethane.

Preferred polymeric materials include polyolefins, especially polyethylene, polypropylene, and copolymers or physical blends thereof. Polypropylene is a particularly good polymeric material. These preferred polymers show particularly good results and the colorants tend not to diffuse into their structure, making them quite inert and reusable.

The solid particles are preferably hydrophobic.

Preferably, the polymeric material is hydrophobic. The preferred polymeric material (hydrophobic) contains very little in its structure, or more preferably has no hydrophilic groups. Examples of the hydrophilic group (preferably without) include ionic groups such as carboxylic acid, sulfonic acid, phosphonic acid, boric acid, and hydrophilic nonionic groups such as -OH, -SH, -NH ₂ , -NH- ,-(OCH ₂ CH ₂ )-and the like. Preferably, the polymeric material contains only carbon and hydrogen atoms.

"Hydrophobic" preferably means that the contact angle between solid particles and water is large.

To increase preference, the contact angle of solid particles with pure water is preferably at least 70, 75, 80, 85, 90, 95, and 100 degrees. The contact angle between solid particles and pure water is preferably not more than 120 degrees, and more preferably not more than 115 degrees. Preferably, the measurement is recorded at a temperature of 20 or 25 ° C. The relative humidity for measuring the contact angle is preferably 65% RH. The contact angle can be measured according to the international standard ISO 15989: 2004. The contact angle may also and preferably be measured using a contact angle telescoping goniometer (eg using a device from Ramé-Hart), where the method comprises directly measuring the tangent angles of the three-phase contact points in the shape of a fixed drop. The static contact angle method is preferred. The drops are preferably background light.

Alternatively or in addition, "hydrophobicity" preferably means that the solid particle absorption relative to the weight of the solid particles is less than 5.0 weight percent, more preferably less than 2.5 weight percent, even more preferably less than 1 weight percent, and especially less than 0.5 weight percent. water. A preferred method for confirming water absorption is to contact the solid particles with water for a period of 24 hours, preferably at a temperature of 25 ° C. After this contact time, remove any water that is only outside the solid particles, suitably tapping the solid particles on a filter paper. The wet weight (Ww) of the solid particles was recorded after tapping. It is preferable to confirm the dry weight (Wd) of the solid particles by vacuum drying the particles, preferably at a temperature of 30 ° C, and preferably after drying for at least 8 hours. The water absorption weight percentage was then generated at 100 × (Ww-Wd) / Wd.

Optionally, the non-polymeric material may be or include ceramics, metals and alloys (such as steel), and glass.

Although the solid particles may be hollow, foamed, or porous, they are preferably substantially non-porous. The porosity is preferably measured by a gas adsorption / desorption method, and is preferably measured in a manner consistent with Brunauer-Emmett-Teller (BET) theory. The gas is preferably nitrogen, and the adsorption / desorption method is preferably performed at a temperature of about -195 ° C. The preferred device for measuring porosity is Micromeritics TriStar II.

The solid particles are preferably inert. "Inert" preferably means that the solid particles have little or no reactive functional groups. More preferably, the solid particles have little or no functional group that can react with the reactive group of the reactive dye. Examples of the reactive group in the reactive dye include: halide , Halopyrimidine, haloquine Pyrene, vinylamidine, and vinylamidine. Preferred that the solid particles do not contain an ionic group, do not contain a nucleophilic group, such as -OH, -SH, -NH-, and -NH _2.

In order to increase the preference, the size of the solid particles is preferably no greater than 40 mm, no greater than 30 mm, no greater than 25 mm, no greater than 20 mm, no greater than 15 mm, or no greater than 10 mm.

To increase preference, the size of the solid particles is preferably at least 2 mm, at least 3 mm, or at least 4 mm.

The surface area of the solid particles is preferably 10 mm 2 to 400 mm 2, more preferably 40 to 200 mm 2, and especially 50 to 190 mm 2.

The size is preferably an average size, and more preferably a number average size. The average is preferably taken from at least 100, at least 1,000, or at least 10,000 solid particles.

This size is preferably the longest linear dimension of the particles. The method of measuring particle size is preferably carried out by using a caliper, or using a particle size measurement method of image analysis, especially dynamic image analysis. The preferred device for dynamic image analysis is the Camsizer provided by Retsch.

To increase preference, the density of solid particles is preferably at least 0.5 g / cm3, at least 0.75 g / cm3, at least 0.9 g / cm3, at least 1.0 g / cm3, at least 1.1 g / cm3, and at least 1.2 g / cm3. Cubic cm, at least 1.25 g / cm3, at least 1.30 g / cm3, at least 1.35 g / cm3, at least 1.40 g / cm3, at least 1.45 g / cm3, at least 1.50 g / cm3, at least 1.55 g / cm3 Cm, at least 1.60 g / cm3, at least 1.65 g / cm3, at least 1.70 g / cm3, at least 1.75 g / cm3, at least 1.80 g / cm3, at least 1.85 g / cm3, or at least 1.90 g / cm3 Cm.

In order to improve the preference, the density of solid particles is preferably not more than 10 g / cm3, not more than 8 g / cm3, not more than 6 g / cm3, not more than 4 g / cm3, and not more than 3 g / cm3. No more than 2.5 g / cm3, no more than 2.2 g / cm3, and especially no more than 2.0 g / cm3.

The density of the solid particles may be 0.5 to 2.5 g / cm3, 1 to 2.2 g / cm3, or 1.1 to 2.0 g / cm3.

In particular, if it is desired that the cleaning power of the solid particles is particularly effective, the lower the density, the better. Therefore, densities of not more than 1.8, 1.6, 1.5, and 1.4 g / cm3 are also beneficial to the present invention. The cleaning power used herein preferably indicates the ability to appropriately remove the residual colorant from the solid particles after the method of the present invention. It is particularly desirable to reuse solid particles in the subsequent method of the first aspect of the present invention.

Preferably, the solid particles are denser than the liquid medium, more preferably denser than water, and especially denser than water containing a relevant amount of salt and an optional additive.

Where it is or comprises solid particles of a polymeric material, a filler may be incorporated into the solid particles. Therefore, the solid particles may be or include a polymeric material and a filler (preferably an inorganic filler).

Preferably, the solid particles include or consist essentially of or consist of a polymeric material and an inorganic filler in a weight ratio of 90:10 to 20:80, and more preferably 70:30 to 30:70 (polymer: filler). If good cleaning power is required, the solid particles suitably include a polymer material to inorganic filler of not less than 50:50, more preferably not less than 70:30, and especially not less than 90:10 by weight ratio.

The solid particles may include at least 5, at least 10, at least 20, at least 30, at least 35, at least 40, at least 45, or at least 50 weight percent fillers, which are preferably inorganic fillers. In a preferred embodiment, the solid particles contain at least 20 weight percent filler, especially if it is desired to separate solid particles from the substrate faster and / or more efficiently. The remaining solid particles required to make up 100 weight percent are preferably polymeric materials.

The solid particles may include fillers of no more than 90, no more than 80, and no more than 70 weight percent, which are preferably inorganic fillers. The remaining solid particles required to make up 100 weight percent are preferably polymeric materials.

Optionally, the solid particles may include a polymeric material and up to 30 weight percent of a filler. Optionally, the solid particles contain a polymeric material and no fillers (especially no inorganic fillers). The solid particles may be (completely) composed of a polymeric material.

The shape of the solid particles may be a cube, an ellipsoid, a sphere, and any shape therebetween.

It is preferred that the shape of the solid particles is an ellipsoid or a sphere, as these shapes are easy to adhere to the substrate, they tend to provide good colorant leveling and they tend to separate from the substrate faster.

The aspect ratio of the solid particles is preferably not more than 1.5, more preferably not more than 1.4, particularly not more than 1.3, and most particularly not more than 1.2. The aspect ratio is the ratio of the longest linear dimension to the shortest linear dimension of each particle. It is preferred that the aspect ratio is an average value, especially a number average. Preferably, the average is at least 100, more preferably at least 1,000, and especially at least 10,000 solid particles.

Preferably, the solid particles never become permanently attached, fixed, integrated, or bonded to the substrate. In other words, the solid particles can be easily separated from the substrate at the end of the method of the first aspect of the present invention.

Colorant

The colorant is preferably or contains a dye. Preferably, the colorant is soluble in a liquid medium, more preferably the colorant is soluble in pure water at 25 ° C, and even more preferably the colorant is soluble in pure water at 25 ° C to achieve a solubility of at least 1 g / liter.

The dye may be non-reactive, but is preferably reactive, and more preferably the dye has one or more reactive substrates (which are or contain a cellulosic material, such as cotton). It is preferable that the reactive dye has 1 to 3, and more preferably 1 to 2 reactive groups. The reactive dyes can be the same or different.

Other dyes suitable for use in the present invention include cationic dyes, direct dyes, vat dyes, and disperse dyes.

Preferably, the colorant is present in an amount of at least 0.1 weight percent, more preferably 0.5 weight percent, relative to the weight of the dye of the substrate. Preferably, the colorant is present in an amount of not more than 20% by weight, and more preferably not more than 10% by weight relative to the weight of the substrate.

Preferred reactive dyes contain one or more , Halopyrimidine, haloquine Morpholine, vinylamidine, amino nicotine three Quaternary group, a reactive group with vinylamidine.

The halogen group in the reactive group is preferably chlorine, fluorine, or a mixture thereof.

Examples of preferred reactive groups include monochlorotris Monofluorochlorotris Dichlorotri , Difluorochloropyrimidine, dichlorohaloquine Phenyl, trichloropyrimidine, vinylamidine, and vinylamidine.

Reactive dyes can also be homobifunctional or heterobifunctional reactive dyes, such as sold under the tradename Sumifix ^(TM) Supra from Sumika Chemtex Co Ltd. The reactive dye may be a Kaycelon React ^™ dye supplied by Standard Dyes.

It can use a single colorant, or two or more colorants.

Preferably, when the colorant is a dye, the dye is dissolved in a liquid medium before being added to the solid particles. Preferably, when the colorant is insoluble in the liquid medium, the colorant is dispersed in the liquid medium before adding the solid particles.

Liquid medium

The liquid medium is preferably aqueous. In other words, the liquid medium is preferably or contains water.

If water is used in combination with other liquids, these liquids can be organic liquids, such as alcohols, esters, ethers, amidines, and the like.

To increase preference, the liquid medium contains at least 50 weight percent, at least 60 weight percent, at least 70 weight percent, at least 80 weight percent, at least 90 weight percent, at least 95 weight percent, or at least 99 weight percent water. Most preferably, the liquid medium is composed of water and has no other liquid components.

Preferably, the pH of the liquid medium is at least 7, more preferably at least 10, and especially at least 11.

Cellulose material

The cellulosic material may be or include any natural cellulosic material, including wood pulp, flax, hemp, jute, ramie, and especially cotton.

The cellulosic material may be or include regenerated fibers. The regenerated fiber material may be or contain rhenium, such as slime fibers, high wet modulus and high breaking strength cellulose fibers (modal), and cellulose fibers (also known as tiancel fibers).

Cellulosic materials can be modified, such as nitrocellulose, cellulose esters, or cellulose ethers.

In addition to the cellulosic material, the substrate may include other materials. The substrate may optionally include polyamide (such as nylon), polyester, polyacrylic, wool, silk, Lycra (sometimes referred to as elastic fibers), or a mixture of one or more of these materials.

Preferably, the cellulose material has one or more nucleophilic groups in its chemical structure. Preferred examples of the nucleophilic group are -NH ₂ , -NH-, -SH, and especially -OH.

Substrate

Preferably, the substrate is in the form of a filament, fiber, yarn, cloth, textile, or clothing.

The substrate may comprise at least 10 weight percent, more preferably at least 50 weight percent of a cellulosic material.

The substrate may be cotton, which may be denim.

Preferably, the substrate is not designed to assist in the collection of colorants and / or pre-fixation of colorants.

Transfer efficiency

To increase preference, at least 10% by weight, at least 20% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% Weight percent, at least 95 weight percent, at least 97 weight percent, at least 98 weight percent, or at least 99 weight percent are transferred to the substrate. The transfer efficiency is preferably confirmed by using a coloring amount that exists in the liquid medium after the method is implemented and is not successfully transferred to the substrate. The percentage amount of toner in the liquid medium after carrying out this method is therefore suitably equal to 100 minus the above-mentioned preferred transfer percentage.

Method conditions

In order to increase the preference, the method of the first aspect of the present invention is not higher than 100 ° C, not higher than 95 ° C, not higher than 90 ° C, not higher than 80 ° C, not higher than 70 ° C, or not higher than 60 ° C. Temperature implementation.

In order to increase the preference, the method of the first aspect of the present invention is performed at a temperature of not lower than 0 ° C, not lower than 5 ° C, not lower than 10 ° C, or not lower than 15 ° C.

A particularly preferred temperature range is 5 ° C to 95 ° C.

Agitation may be performed for a period of at least 1 second, at least 15 seconds, at least 30 seconds, or at least 1 minute.

Agitation can be performed for a period of no more than 48 hours, no more than 24 hours, no more than 16 hours, no more than 8 hours, no more than 5 hours, no more than 4 hours, no more than 3 hours, or no more than 2 hours.

The agitation is preferably performed for a period of 1 minute to 2 hours.

To increase preference, the weight ratio of dry solid particles to dry substrate is at least 0.01: 1, at least 0.1: 1, at least 0.3: 1, at least 0.5: 1, at least 1: 1, and at least 2: 1.

In order to increase the preference, the weight ratio of the dry solid particles to the dry substrate is not more than 100: 1, not more than 50: 1, not more than 30: 1, not more than 20: 1, not more than 10: 1, and not more than 5: 1 .

To increase preference, the weight ratio of dry solid particles to dry substrate is 0.01: 1 to 100: 1, 0.1: 1 to 50: 1, 0.1: 1 to 20: 1, 0.1: 1 to 10: 1, 1: 1 To 20: 1, 1: 1 to 10: 1, and 2: 1 to 10: 1.

agitation

Stirring can be performed by shaking, shaking, stirring, fluidizing, pulsating, or more preferably by turning (composition).

Device

Preferably, the agitation is performed in an apparatus including a processing chamber. The processing chamber may be shaken, oscillated, pulsed, or more preferably rotated. The rotation may be any suitable G-force, however, it is preferred that the G-force is 0.05G to 2G, preferably 0.05G to 1.5G, and particularly 0.05G to 0.95G. The G force is preferably calculated at the inner surface of the processing chamber. The processing chamber is preferably in the form of a cylinder. The G force can be calculated from G = 1.118 × R × (RPM / 1000) ² , where R is the radius in millimeters and RPM is the rotation speed in revolutions per minute.

The device may or may additionally include one or more agitators, fluidized beds, or ejectors designed to agitate the composition.

Selected composition ingredients

The composition may additionally include one or more of the following ingredients, as appropriate: chelating agent, lubricant, anti-wrinkle agent, pre-treatment agent, leveling agent, dispersant, defoaming agent, desizing agent, mercerizing agent, optical brightener , Salts, buffers, biocides, acids, bases, surfactants, organic solvents, fixing catalysts, enzymes, or anti-redeposition agents.

Salt

The liquid medium may contain salts dissolved therein. Preferably, the liquid medium contains no more than 150 g / L, more preferably no more than 100 g / L of salts. Optionally, the liquid medium contains no more than 90 g / L, no more than 80 g / L, no more than 70 g / L, no more than 60 g / L, no more than 50 g / L, no more than 40 g / L, Not more than 30 g / l, not more than 20 g / l, not more than 10 g / l, not more than 5 g / l, not more than 2.5 g / l, not more than 1 g / l, not more than 0.5 g / l, or Not more than 0.1 g / L of salt. Optionally, the liquid medium is completely salt-free.

When the amount of salt in the liquid medium is less than 20 g / L, the pH of the liquid medium is preferably neutral to acidic, more preferably pH 4 to 7, even more preferably pH 5 to 7. These preferred pH values can be obtained using citric acid / citrate buffer.

Examples of such salts include sodium salts, especially sodium chloride and / or sodium sulfate.

The weight ratio of the liquid medium to the dry substrate is preferably greater than 2: 1, and more preferably greater than 3: 1.

The weight ratio of the liquid medium to the dry substrate is preferably not more than 100: 1, more preferably not more than 50: 1, especially not more than 20: 1, more particularly not more than 15: 1, and most particularly not more than 10: 1.

Fixation

It is often advantageous to raise the composition temperature to a temperature of at least 40 ° C, more preferably at least 50 ° C, and especially at least 60 ° C, more particularly at least 70 ° C, and most particularly at least 80 ° C. This helps to fix the colorant to the substrate. This fixation is particularly useful as a coloring agent for dyes, especially reactive dyes.

reuse

The solid particles are preferably reused, and are preferably used for the method of the first aspect of the present invention once or more.

Therefore, the method of the first aspect of the present invention preferably further comprises: i. Separating the substrate from the solid particles; ii. Reusing the solid particles in the toner transfer method of the first aspect of the present invention.

Preferably in a method comprising agitating a composition comprising a substrate, separated solid particles, a colorant, and a liquid medium, the above step ii. Includes transferring the colorant to the substrate

Wherein: the colorant is dissolved and / or dispersed in the liquid medium; the substrate is or contains a cellulose material; and the size of the separated solid particles is 1 to 50 mm.

Generally, the toner in step ii. Is fresh or unused and / or the liquid medium is fresh or unused and / or the substrate is fresh or unused.

Cleaning of solid particles may be required between steps i. And ii. It can be performed by washing solid particles with a liquid medium, especially water. Water optionally contains one or more surfactants and / or organic liquids. It has surprisingly been found that hydrophobic and especially polyolefin solid particles are cleaned particularly well. As mentioned above, solid particles with lower density and / or less filler content are also preferred as they tend to be better cleaned between steps i. And ii.

Steps i. And ii. Can be repeated any number of times, preferably steps i. And ii. Are repeated at least 5 times, at least 10 times, at least 20 times, at least 50 times, and at least 100 times.

It is preferred that after the method of the present invention, the solid particles contain no more than 5 weight percent, more preferably no more than 1 weight percent, even more preferably no more than 0.5 weight percent, and more preferably after the colorant is transferred to the substrate. It is not more than 0.1% by weight of the initial coloring amount. In the method of the first aspect of the present invention, these preferences are preferably obtained even after the solid particles have been reused at least 5 times, at least 10 times, at least 25 times, at least 50 times, or at least 100 times.

Selected method steps

The method of the first aspect of the present invention may further include one or more of the following steps: a) bleaching the substrate; b) washing the substrate; c) cleaning the substrate (for example, to remove unfixed colorant); d) Colorant fixes to the substrate; e) extracts the liquid medium; f) separates the substrate from solid particles; g) dries the substrate; h) irons or flattens the substrate; i) sew and glue the substrate , Forming and / or cutting, especially if the substrate is a textile; j) surface treating the substrate.

Preferably, steps (a) and (b) are performed before agitating a composition containing solid particles, colorants, and a liquid medium.

Steps (c) to (j) are preferably performed after agitating a composition containing solid particles, a colorant, and a liquid medium.

Substrate

A second aspect of the present invention provides a cellulose substrate obtained or obtainable by the method of the first aspect of the present invention.

Overview

In the full description of this specification and the scope of patent application, the words "including" and "containing" and their variants mean "including but not limited to", and they are not intended (and) not to exclude other parts, additives, ingredients, integers, Or steps. In the entire description of this specification and the scope of patent applications, the singular includes the plural unless the context requires otherwise. In particular, it should be understood that if an indefinite article is used, this specification considers plural and singular, unless the text clearly requires it. Thus, for example, one coloring agent means one or more coloring agents, and one substrate means one or more substrates.

It should be understood that the features, integers, characteristics, compounds, chemical moieties, or radicals described in connection with the specific aspects, specific embodiments, or embodiments of the present invention are applicable to any other aspects, specific embodiments described herein , Or Examples, unless incompatible with it. All features disclosed in this specification (including any accompanying patent application scope, abstract, and drawings) and / or all steps of any method or procedure disclosed, except for at least some of these features and / or steps are mutually exclusive In addition to the combination, it can be combined in any combination. The invention is not limited to the details of any of the above specific embodiments. This invention extends any novelty, or any novel combination, of the features disclosed in this specification (including any accompanying patent application scope, abstract, and drawings), or any novelty of the steps of any method or procedure disclosed, Or any novel combination.

The invention is now exemplified with reference to the following examples, but in no way limits its scope.

    [Example]     [Comparative Example 1-Using solid particles prepared according to WO2006 / 040539 patent] Step 1-preparing solid particles

It is made of polypropylene by hot melt extrusion and has a density of 0.9 g / cm3, a size (longest linear dimension) of 3 to 4 mm, and is oval-shaped solid particles.

Step 2-preparing a colorant solution

4 grams of Reactive Red 120 (Procion Red HE-3B supplied by Dystar) was dissolved in 96 grams of deionized water to prepare a colorant solution. Reactive Red 120 has 2 monochlorotris Reactive dyes

Step 3-try coating the solid particles

In order to attempt to coat the solid particles prepared in step 1 with a colorant, the toner solution prepared in step 2 was added to 50 grams of polypropylene solid particles, and the resulting mixture was heated at pH 7 to 50 ° C. for a period of 30 minutes. This coating method is essentially disclosed on page 8 of WO 2006/040539, lines 16 to 26.

Step 4-Isolate `` coated '' solid particles

The polypropylene solid particles prepared in step 3 were then removed from the colorant solution by filtration, the polypropylene particles were washed with 50 grams of deionized water to remove any uncoated colorant, and air-dried at ambient temperature.

Step 5-preparing a cotton substrate

Preparation of a white cotton textile substrate that has been double-washed, bleached, and does not contain an optical brightener.

Step 6-Dyeing the cotton substrate

The cotton substrate prepared in step 5 was dyed in a Roaches Pyrotec 3 dyeing machine.

The dyeing step 6 is as follows: the amount of the cotton substrate used is 10 g, and the amount of the polypropylene particles prepared in step 4 is 50 g.

The cotton substrate was loaded into a dyeing machine, the substrate was wetted with water (20 g), and the polypropylene particles prepared in step 4 were added. The cloth was squeezed to remove excess water from the cotton substrate, and approximately 10 grams of water remained on the substrate.

The temperature inside the dyeing machine was increased from the ambient temperature at a rate of 1.5 ° C per minute, and then maintained at 95 ° C for 45 minutes, after which the temperature was cooled to 65 ° C.

The pH of the water used is 7; in all the dyeing steps, the drum of the dyeing machine is rotated at 25 rpm, which is equal to a G force of 0.14G on the inner wall of the drum; the dyed cotton substrate is removed from the dyeing machine and washed with water That is, twice with 200 grams of cold water and once with 200 grams of water at 70 ° C. The cotton substrate was air-dried after cleaning.

Measurement methods

Using a Konica Minolta CM-3600A spectrophotometer equipped with a D65 light source, and using SpectraMagic NX Colour Data Software CM-S100w, Professional / Lite Ver2.2, the amount of dye successfully transferred to the cotton substrate was quantified spectrophotometrically. Record the L *, a *, and b * CIE color space values at 4 different points on the dyed cotton substrate, and record the values as the average of 4 measurements. Calculate the △ E * value using Equation 1: △ E * = [(L * ₂ -L * ₁ ) ² + (a * ₂ -a * ₁ ) ² + (b * ₂ -b * ₁ ) ² ] ^1/2 Equation 1

Where L * ₁ , a * ₁ , and b * ₁ values are taken from the average color space measurement of an undyed cotton textile substrate, and L * ₂ , a * ₂ , and b * ₂ values are taken from the one prepared in Comparative Example 1. Average color space measurement of the dyed substrate.

[Comparative Example 2—The conventional dyeing without solid particles] Step 1-preparing a colorant solution

4 grams of Reactive Red 120 (Procion Red HE-3B supplied by Dystar) was dissolved in 96 grams of deionized water to prepare a colorant solution.

Step 2-preparing a cotton substrate

Preparation of a white cotton textile substrate that has been double-washed, bleached, and does not contain an optical brightener.

Step 3-dye the cotton substrate

The cotton substrate prepared in step 2 was dyed in a Roaches Pyrotec 3 dyeing machine.

The dyeing step 3 is as follows: the amount of the cotton substrate used is 10 g, and the amount of the toner solution prepared in step 1 is 3.3 g.

The cotton substrate was loaded into a dyeing machine, and the substrate was wetted with a colorant solution.

The internal temperature of the dyeing machine was increased from the ambient temperature at a rate of 1.5 ° C per minute, and then maintained at 95 ° C for 45 minutes, after which the temperature was cooled to 65 ° C before the cotton substrate was removed.

The pH of the water used is 7; in all the dyeing steps, the drum of the dyeing machine is rotated at 25 rpm, which is equal to a G force of 0.14G on the inner wall of the drum; the dyed cotton substrate is removed from the dyeing machine and washed with water That is, twice with 200 grams of cold water and once with 200 grams of water at 70 ° C. The cotton substrate was air-dried after cleaning.

Using the same method as disclosed in Comparative Example 1, the amount of dye successfully transferred to the cotton substrate was quantified spectrophotometrically.

result

The results of dyeing Comparative Examples 1 and 2 are shown in Table 1 below.

The larger the value of △ E * is, the darker and thicker the hue is, the more dyes are successfully transferred.

The quantitative spectrophotometric results and visual appearance of Figures 1a, 1b, and 1c confirm that the coating method of the WO2006 / 040539 patent does not provide superior results compared to the conventional dyeing method (without solid particles). This is an observation that the particles used in the coating method of Comparative Example 1 were exposed to a colorant whose total amount was much larger than that of the coloring agent present in Comparative Example 2. Although not wishing to be bound by any particular theory, it assumes that the coating method used in the patent WO2006 / 040539 is particularly ineffective, especially when the solid particles are hydrophobic (as is the case with polypropylene). Therefore, the solid particles are essentially uncoated and very little if any colorant is transferred to the substrate.

[Example 1-Uncoated solid particles] Step 1-preparing solid particles

Solid particles containing polypropylene and inorganic fillers with a density of 1.76 g / cm3, a surface area of about 60 square millimeters, a size (longest linear dimension) of about 4 millimeters, and oval / spherical solids were prepared by hot melt extrusion.

Step 2-preparing a colorant solution

4 grams of Reactive Red 120 (Procion Red HE-3B supplied by Dystar) was dissolved in 96 grams of deionized water to prepare a colorant solution.

Step 3-preparation of cotton substrate

Preparation of a white cotton textile substrate that has been double-washed, bleached, and does not contain an optical brightener.

Step 4-Dyeing the cotton substrate

The cotton substrate prepared in step 3 was dyed in a Roaches Pyrotec 3 dyeing machine.

The dyeing step 4 is as follows: the amount of the cotton substrate used is 10 g, the amount of polypropylene particles prepared in step 1 is 100 g, and the amount of the toner solution prepared in step 2 is 70 g.

The cotton substrate was loaded into a dyeing machine, and the substrate was wetted with water (20 g). The cloth was squeezed to remove excess water from the cotton substrate, and approximately 10 grams of water remained on the substrate.

Polypropylene particles are added, followed by a colorant solution.

Increase the internal temperature of the dyeing machine from the ambient temperature at a rate of 1.5 ° C per minute, and then maintain it at 95 ° C for 15 minutes. After this temperature is cooled, once it reaches 65 ° C, add 0.3 grams of sodium alkali ash solution in water (15 grams / Liter) solution, and then the temperature was raised to 95 ° C and held at this temperature for a period of 30 minutes, after which the temperature was cooled to 65 ° C.

The pH of the water used was 7 before the addition of sodium base and 11.5 after the addition of sodium base; during all dyeing steps, the drum of the dyeing machine was rotated at 25 rpm, which is equal to a G force of 0.14G on the inner wall of the drum.

The dyed cotton substrate was removed from the dyeing machine and washed with water, that is, twice with 200 grams of cold water and once with 200 grams of water having a temperature of 70 ° C. The cotton substrate was air-dried after cleaning. In this way, the base material 1 is manufactured.

[Comparative Example 3—A conventional method without solid particles]

Example 1 was repeated except that no solid particles were present in the dyeing step 4. Therefore, this comparative example represents a conventional method without any solid particles. In this way, the comparative base material 3 was produced.

Measurement methods

Using a Konica Minolta CM-3600A spectrophotometer equipped with a D65 light source, and using SpectraMagic NX Colour Data Software CM-S100w, Professional / Lite Ver2.2, the amount of dye successfully transferred to the cotton substrate was quantified spectrophotometrically. Record the L *, a *, and b * CIE color space values at 4 different points on the dyed cotton substrate prepared in step 4, and record the values as the average of 4 measurements. Calculate the △ E * value using Equation 1: △ E * = [(L * ₂ -L * ₁ ) ² + (a * ₂ -a * ₁ ) ² + (b * ₂ -b * ₁ ) ² ] ^1/2 Equation 1

Where L * ₁ , a * ₁ , and b * ₁ values are taken from the average color space measurement of an undyed cotton textile substrate, and L * ₂ , a * ₂ , and b * ₂ values are obtained from Example 1 or Average color space measurement of the dyed substrate of Comparative Example 3.

result

The results of Dyeing Example 1 and Comparative Example 3 are shown in Table 2 below.

A larger ΔE * value corresponds to a stronger hue, so the more successful the transfer of the colorant to the substrate.

It clearly proves that, contrary to the teaching of WO2006 / 040539 patent, an excellent colorant to substrate transfer is obtained when the colorant is not applied to the solid particles. The results are superior to conventional methods in which no solid particles are used.

Although not wishing to be bound by any particular theory, it is assumed that, especially when the solid particles are hydrophobic (as is the case with polypropylene), the solid particles are not substantially coated with a colorant. Surprisingly, however, this coating is not important for colorant transfer, and superior results are obtained compared to conventional methods that do not use solid particles. It is assumed that the mechanical action exerted by the solid particles on the cellulose substrate assists in colorant transfer.

[Washing Example]

The dyeing substrates prepared in Example 1 and Comparative Example 3 were each cleaned by the following method. The dyed cotton substrate was washed 5 times, each time using (fresh) deionized water. In each cleaning, the ratio of the washing water to the substrate is 20: 1 by weight. The temperature of the washing water was 75 ° C. Each cleaning is carried out for a period of 10 minutes to allow any unfixed or hydrolyzed dye to be washed off the substrate. Washing was performed on a hot plate using a stirrer in a 500 ml beaker. The final cleaned substrate was air-dried at ambient temperature.

The ΔE * value of the dyed substrate and the ΔE * value after washing were recorded using the aforementioned method.

ΔE * changes (stained-washed) are calculated and the table is shown in Table 3 below.

The smaller the ΔE * change is equivalent to the more dye being fixed to the substrate during the dyeing process.

The results in Table 3 show that the substrate prepared by the method of the present invention also exhibits an increased degree of color fixation (due to the stronger coloration) compared to the conventional method without using solid particles.

Therefore, it has been unexpectedly found that the method of the present invention provides a colored substrate having a relatively strong hue and a large number of colorants successfully fixing to the substrate.

It has also been found that the method of the present invention, in which the colorant is dissolved or dispersed in a liquid medium, causes the solid particles to be less contaminated by trace amounts of colorant and / or easier to be removed by cleaning than the coated particles of WO2006 / 040539 Any trace colorant. Cleaner solid particles can be used when changing the hue of the colorant so that there is no color to color contamination. Cleaner solid particles also mean that solid particles can be reused more times.

Reactive black 5

Example 1 and Comparative Example 3 were repeated, except that the coloring agent used was Reactive Black 5. Reactive black 5 is a reactive dye having two vinylamidine reactive groups. The results of this comparison again show a stronger and more effective coloration of the substrate and at the same time better coloration of the substrate (as opposed to the conventional method in which there are no solid particles).

[Example 2-Standard reactive dyeing with solid particles but no salt]

Load 2.5 kg of clothing in a 14 kg drum-type washing machine with a liquid agent ratio (liquid medium to dry substrate) of 7: 1. For experiments with solid particles, the particles were polypropylene particles disclosed in Example 1, and these particles were added to the wet clothes in the drum. The amount of reactive blue 19 dye added to the clothes was 25 grams (1 weight percent of clothes). The laundry was then mixed with dye at 10 rpm for 20 minutes at a temperature of 60 ° C. Then, 169 grams of sodium carbonate was added to the dyed clothes over a period of 20 minutes, and then rolled at 60 ° C for 45 minutes. Then wash the dyed clothes at 30 ° C for 5 minutes and check the pH to ensure that the pH is between 6 and 7 before dehydrating and refilling the drum with 30 ° C water. Then 203 grams of 40% formic acid (for neutralization) was added to the dyed laundry and run for 10 minutes. Adjust the pH of the solution to 5.5-6.5. Then, at 95 ° C, 40 ° C, 60 ° C, and 35 ° C, a series of washings are performed at a liquid ratio of 7: 1, and each washing step is run for 10 minutes to ensure that no color is removed from the clothes except. An additional washing step is continued at 40 ° C until the washing liquid is clear to ensure that all the hydrolyzed dye is removed from the laundry. The above dyeing method was repeated using 3: 1 and 5: 1 solid particle ratios. The results are shown in Table 4 below. A high △ E value indicates that the dye has a high fixing effect on the cotton substrate.

The results in Table 4 show that compared to the absence of solid particles, the dye fixation is better in the presence of solid particles.

[Example 3-Standard reactive dyeing with or without salt and solid particles]

Example 2 was repeated in a drum with a lower liquid agent ratio of 4: 1 as recommended by the dye industry in the presence of salt (50 g / l). The results are shown in Table 5.

[Example 4- Peripheral temperature / low temperature reactive dyeing with or without solid particles and salt]

The above experiment was repeated as follows. The cotton substrate (10 g) was dyed in a roller. The cotton substrate was loaded into a drum, and the substrate was wet with water with a liquid-to-agent ratio of 5: 1. Adjust the pH of the water to 7. An excess of liquid solution remaining in the drum was used to dissolve 0.2 grams of Procion Red PX-8B dye (printing dye; DyStar, Singapore). The reactive dye and cotton pieces were thoroughly mixed in a roller at room temperature for 20 minutes. Sodium carbonate (0.75 g; Sigma Aldrich, UK) was then added to raise the pH to 12, and the dye was fixed to the cotton substrate for 45 minutes. The dyed cotton substrate was then washed with 200 grams of 30 ° C soft water (pH 7), followed by 200 grams of water at a temperature of 60 ° C. The dyed cotton cloth block was washed at 40 ° C with solid particles for 3 times to remove any unfixed dyes, and washed 6 times without solid particles to obtain the same degree of colored drainage. The cotton substrate was then air-dried, and the amount of dye successfully transferred to the cotton substrate was quantified spectrophotometrically using the same method shown above. Then, the average ΔL * value of each experiment was calculated, and the results are shown in Table 6 below.

The above steps were repeated using Remazol Navy RGB dye (DyStar, Singapore). The results are shown in Table 7 below.

Particle analysis using a spectrophotometer (as described above) before and after 20 dyeing cycles showed that the color change (ΔE *) on the particle surface was extremely small. No blue dye adsorption was observed visually on the particle surface. These results are shown in Table 8 below.

The polypropylene particles and the nylon particles were compared before and after the above 20 dye treatment cycles. In contrast to polypropylene particles, nylon particles exhibit significant color pick-up. Table 8 below shows the color change (ΔL *) measured using the above spectrophotometer.

Claims (30)

    A method for transferring a colorant to a substrate, comprising agitating a composition including the substrate, solid particles, the colorant, and a liquid medium, wherein: the colorant is dissolved and / or dispersed in the liquid medium; the The substrate is or contains a cellulosic material; the size of the solid particles is 1 to 50 mm.         The method of claim 1, wherein the solid particles are not substantially coated with any colorant.         The method of any of the above claims, wherein the solid particles are hydrophobic.         A method as in any above, wherein the solid particles are or comprise a polymeric material.         The method of claim 4, wherein the polymeric material is or comprises a polyolefin.         The method of any one of the above claims, wherein the weight ratio of the liquid medium to the dried substrate is greater than 2: 1.         The method of claim 6, wherein the weight ratio of the liquid medium to the dried substrate is from 3: 1 to 20: 1.         The method according to any one of the preceding claims, wherein the liquid medium contains no more than 100 g / L of salts.         The method of any one of the above claims, wherein the size of the solid particles is 1 to 10 mm.         The method of any one of the above claims, wherein the solid particles have a density of 0.5 to 2.5 g / cm3.         The method according to any one of the above claims, wherein the solid particles comprise a polymer material and an inorganic filler in a weight ratio of 90:10 to 20:80.         The method of any of the above claims, wherein the colorant is or comprises a dye.         The method of claim 12, wherein the dye is a reactive dye.     The method of claim 13, wherein the reactive dye contains more than one reactive group selected from halide , Halopyrimidine, haloquine Morpholine, vinylamidine, amino nicotine three Quaternary, and vinylamidamine.     A method as in any above, wherein the cellulosic material is or comprises cotton.         A method as claimed in any one of the preceding claims, wherein the agitation is carried out in a device comprising a rotating processing chamber.         The method of claim 16, wherein the turning is performed to provide a G force of 0.05 to 0.95 on the inner surface of the processing chamber.         The method of any one of the above claims, wherein the agitation is performed for a period of 1 minute to 2 hours.         The method according to any one of the above claims, which is carried out at a temperature of 5 to 95 ° C.         The method of any of the above claims, wherein the substrate is in the form of a filament, fiber, yarn, cloth, textile, or clothing.         The method according to any one of the above claims, wherein the weight ratio of the dried solid particles to the dried substrate is 0.1: 1 to 20: 1.         The method according to any one of the above claims, wherein the step comprises, before the agitating the composition including the substrate, the solid particles, the colorant, and a liquid medium, the colorant in the absence of the solid particles Dissolved and / or dispersed in a liquid medium.         The method according to any one of the above claims, further comprising the steps of: i. Separating the substrate from the solid particles; ii. Using the solid particles in a toner transfer method according to any one of the above claims reuse.         The method of any one of the preceding claims, wherein at least 20 weight percent of the initial amount of colorant is transferred to the substrate.         The method of any one of the preceding claims, wherein after transferring the colorant to the substrate, the solid particles contain an initial amount of colorant of not more than 1 weight percent.         The method of any of the above claims, wherein the liquid medium is aqueous.         A method as in any above, wherein the liquid comprises at least 50 weight percent water.         The method according to any one of the above claims, wherein the composition further comprises one or more of the following components: a chelating agent, a lubricant, an anti-wrinkle agent, a pretreatment agent, a leveling agent, a dispersant, a defoaming agent, Slurries, mercerizing agents, optical brighteners, salts, buffers, biocides, acids, bases, surfactants, organic solvents, fixative catalysts, enzymes and / or anti-redeposition agents.         The method of any one of the above claims, further comprising one or more of the following steps: a) bleaching the substrate; b) washing the substrate; c) cleaning the substrate; d) fixing the toner Color to the substrate; e) extract the liquid medium; f) separate the substrate from the solid particles; g) dry the substrate; h) iron or flatten the substrate; i) the substrate Material stitching, gluing, forming and / or cutting; j) surface treating the substrate.         A cellulose substrate obtained or obtainable by a method according to any one of the above claims.