CN110709556A

CN110709556A - Low temperature coloring method

Info

Publication number: CN110709556A
Application number: CN201880037229.9A
Authority: CN
Inventors: 史蒂芬·马丁·布尔金肖
Original assignee: University of Leeds
Current assignee: University of Leeds; University of Leeds Innovations Ltd
Priority date: 2017-06-02
Filing date: 2018-05-31
Publication date: 2020-01-17
Also published as: US20200157737A1; WO2018220375A1; BR112019025309A2; MA48954A; EP3631078A1

Abstract

The present invention relates to a method for coloring a polymeric substrate at low temperatures. The method comprises the following steps: the polymeric substrate to be coloured is subjected to a colouring liquid comprising a solvent in which the colouring agent has a high solubility, and then a solvent, generally water, in which the colouring agent has a low solubility is added.

Description

Low temperature coloring method

Technical Field

The present invention relates to a process for coloring a polymeric substrate at low temperatures. The method comprises the following steps: the polymeric substrate to be coloured is subjected to a colouring liquid (colouring liquid) comprising a solvent in which the colourant has a high solubility, and then a solvent, typically water, in which the colourant has a low solubility is added. The process is particularly suitable for dyeing polyester fibers and polyester fiber blends with disperse dyes.

Background

Most of the textiles produced in the world todayThe product (textile product) comprises polyester. In particular, in 2015, poly (ethylene terephthalate) (PES) accounted for 90.6x 10⁶T world textile fiber requirement 58.5% (53.1X 10)⁶T). The excellent success and long-lasting popularity of PES fibers can be attributed to their generally excellent textile properties and high chemical resistance, coupled with the ability of polyester fibers to be manufactured in almost any physical form, including blending with other similar fibers, according to different application requirements. In the latter case, the primary use of polyester fibers is in combination with cotton fibers. In such polyester-cotton blend materials (polycotton blend materials), the cotton component provides comfort, absorbency, etc., while the polyester component imparts strength, resiliency, and stain resistance.

Polyester fibers dyed with only disperse dyes provide a wide color gamut and generally exhibit very good fastness properties on polyester. Disperse dyes belong to a variety of chemical classes, mainly anthraquinones, (AQ) and azos, as exemplified by c.i. disperse red 60 and c.i. disperse blue 165.

The water solubility of disperse dyes is generally low. However, the solubility increases significantly with increasing temperature, as exemplified by c.i. disperse red 121: 3.30.00033 gL at 25 DEG C^-1(ii) a 0.0088gL at 130 DEG C^-1. This is of great importance for their application to polyester fibres under High Temperature (HT) dyeing conditions.

The solubility of disperse dyes is greatly increased in the presence of commercially available dispersants, a feature which forms the basis of the finishing process (finishing process) for preparing the dyes in the commercially available form and the application method (application method) for applying them to polyester fibers under the water immersion process. Commercially available disperse dyes typically contain up to 60 mass% of dispersant, which adds significantly to the cost of the dye. Dispersants (including, for example, lignosulfonates or formaldehyde polycondensates or aryl sulphonic acids) are not particularly environmentally friendly. The removal and disposal of such materials from dyed textile fibers at the end of dyeing greatly increases the cost, energy efficiency and environmental risk of commercial dyeing.

Since the diffusion rate of dye in PES fiber is very low at temperatures up to commercial boiling (i.e., 98 ℃), it is most common to achieve commercially acceptable disperse dye dyeing rates by using high temperatures in the region of 130-. Currently, most polyester fibers are dyed using this impregnation process at temperatures of 130 ℃ - & 140 ℃. Because dyeing requires such high temperatures, the dyeing process consumes a large amount of energy, and the machines used for dyeing must be capable of operating at pressures >1 atmosphere; therefore, these machines are often very expensive.

PES fiber contains small amounts of oligomers, mainly cyclic tri (ethylene terephthalate), and small amounts of other oligomeric compounds. Such compounds migrate to the surface of the fiber during the HT dyeing process and deposit on the surface of the fiber and machinery during cooling, thereby reducing the visual depth (visual depth) of the shade brightness (shade brilliance) of the dyeing; the removal of these compounds from the dyeing machine is another problem of dip dyeing. Removal of oligomers, except for excess dye and dispersant, is typically accomplished using a reductive scavenging process, in which Na is used₂S₂O₄And nonionic surfactants, typically heat treatment. This process adds additional time to the process and adds additional materials and energy. It also produces environmentally unacceptable effluents including Na₂S₂O₄And in the case of azo disperse dyes, aromatic amine by-products are also formed.

Another limitation of HT dyeing methods is that many fabrics, especially natural (e.g. wool, silk) and more sensitive man-made (e.g. polyurethane )

) Is unstable under high temperature conditions. In the case of polyester combined with these materials (woven together as a blend or joined together as part of a garment), others must be usedA more inefficient dyeing process, which can result in significant differential color intensity (differential color intensity) of the individual fabrics in the blend, or a pre-dyed fabric must be blended, which is a complex and expensive process. This means that for blends or garments made of more than one different material, the fibres must be dyed separately before they can be woven together or joined together.

When PES was first introduced in the 1950 s, the preferred staining method used was support staining, in which a support, typically a solid organic compound of low molar mass (e.g. o-phenylphenol), was included in the aqueous staining solution. This carrier aids in fabric dyeing and allows the use of lower temperatures than HT dyeing, typically 98 ℃. However, carriers often have detectable odors, they often impair the light fastness of the dyed material and also cause environmental problems, so that in today's business HT dyeing processes dominate and the use of carrier dyeing steadily declines.

Disperse dyes are much more soluble in organic solvents than in water. However, organic solvents are not effective for disperse dyeing because the dye has a greater affinity for the solvent than for the fiber. Therefore, when the disperse dye is applied from an organic solvent, the dye absorption amount on the fiber is low, and thus the shadow depth that can be achieved using a high-temperature aqueous dyeing technique cannot be reproduced using a dyeing solution based on an organic solvent.

Not only in polyester dyeing where the dyeing can be improved. Dyeing processes for wool, silk and polyamide fibers are typically carried out at high temperatures, often requiring specific pH values for successful application, resulting in the need to use additional chemicals to control pH. This method can also be time consuming. For example, dyeing with vat dye (vat dye) is a complex, time consuming, multi-stage process involving multiple pH changes and requiring the use of strong reducing agents that are environmentally problematic.

In addition, dyeing aids are commonly used to assist the aqueous dip dyeing process. The assistance provided by a given dyeing assistant is typically related to a specific aspect of the dyeing, such as wetting, dye levelling (dye leveling), fiber protection, and the like. Thus, many different types of dyeing auxiliaries are commonly used in aqueous dye applications, such as dispersants, chelants, lubricants, and the like. For example, as noted above, the dyeing process for polyester fibers typically utilizes dispersants and surfactants, which are added to the dye bath to aid in dye dispersion and levelling. In addition, the pH at which dyeing is carried out is usually adjusted to within a prescribed range, for example, slightly acidic (pH 4.5-6.0), although the disperse dye selected is suitable for use at a high pH (pH 9.5). Since aqueous dyebaths typically contain a large variety of auxiliary agents, the wastewater produced during the dip dyeing process may contain various auxiliary chemicals; in fact, at the end of dyeing, it is intended to remove from the dyed material many of the auxiliaries used in dip dyeing (such as dispersants used in polyester dyeing), meaning that these chemicals will be present in the waste water resulting from the dyeing process. Although many strategies have been explored to treat dyeing wastewater (effluent) containing residual dyeing auxiliaries, no single treatment method is effective for all auxiliaries or all types of dye/fiber systems. An additional advantage of certain embodiments of the present invention is that the number and amount of dyeing aids used in the dyeing process can be reduced, thereby saving chemical costs and providing environmental advantages.

Although the process of the present invention has been developed for dyeing fibrous substrates, the inventors have found that they can be applied more generally to other polymeric substrates.

Disclosure of Invention

In a first aspect of the invention, there is provided a method of colouring a polymeric substrate, the method comprising:

a) subjecting the polymeric substrate to a tinting liquid at a temperature T1, T1 being less than 100 ℃, the tinting liquid comprising at least one colorant dissolved in a first solvent system to provide a polymeric substrate wetted with tinting liquid;

b) adding a second solvent system to the polymeric substrate wetted with the tinting liquid without raising the temperature above temperature T2, T2 being less than 100 ℃, to provide a tinted polymeric substrate wetted with a mixture of the first and second solvent systems; and

c) separating the dyed polymeric substrate from the mixture of the first and second solvent systems and any remaining colorant;

wherein the or each colourant is more soluble in the first solvent system than in the second solvent system.

The polymeric substrate may be a fibrous substrate. The colorant may be a dye. The inventors have found that greater depth of coloration can be achieved using the same amount of colorant when using the above method compared to using the HT disperse dyeing method. This greater depth of coloration is achieved at lower temperatures than in conventional HT processes, and without the use of dispersants. Thus, the method of the first aspect may be less energy consuming, less costly and pose less risk to the environment than known HT methods. This is also a low temperature process which can be carried out on or in the presence of sensitive natural and man-made fibres. Without wishing to be bound by theory, it is believed that adding the second solvent system to the colorant solution in the first solvent system reduces the solubility of the colorant in the solvent. This, in turn, results in a molecular dispersion by which the colorant may be absorbed into the fiber and is actually more advantageous than the dispersion formed in the HT dyeing process.

The inventors have also found that the process of the present invention, when applied to the acid dyeing of certain substrates, provides effective dyeing at lower temperatures and faster rates than conventional processes without the use of added dyeing aids.

The lower temperatures used allow for the simultaneous coloration of more than one polymer type. The process is applicable not only to disperse dyes, but also to other types of colorants, including acid dyes, direct dyes, reactive dyes, and vat dyes. The inventors have demonstrated that more than one polymer (e.g. fabric) type can be dyed at a time using the method of the present invention, with different colorants being used simultaneously to colour different polymers (e.g. fabrics).

In a second aspect of the invention, there is provided a polymeric (e.g. fibrous) substrate obtainable (e.g. obtained) by a process according to the first aspect.

Method of producing a composite material

The total amount of the second solvent system can be added as a single portion to the polymeric (e.g., fibrous) substrate wetted with the tinting liquid. It may be added continuously over a predetermined period of time. It may be added in portions. Thus, the total amount of the second solvent system may be added in a predetermined number of equal sized portions at predetermined separate time intervals. The inventors have found that the addition of the second solvent system in portions provides the most effective coloration. Without wishing to be bound by theory, it is believed that the batch addition provides a more controlled formation of molecular dispersion of the colorant (e.g., dye). In certain embodiments, the inventors have observed that the colorant is 100% absorbed into the substrate, leaving no colorant in the resulting mixture of the first solvent system and the second solvent system.

A second solvent system is added to promote precipitation of the colorant from the tinting liquid. Typically, in the case where the polymer substrate is a fibrous substrate, such precipitation will occur within the fibrous substrate.

The number of equally sized portions of the second solvent system may be in the range of 2 to 10, for example in the range of 3 to 6.

After the addition of the second solvent system, the dyed polymeric (e.g., fibrous) substrate wetted with the mixture of the first and second solvent systems may be maintained at a temperature T3 for a predetermined period of time, T3 being less than 100 ℃.

Typically, the colored (e.g., dyed) polymeric (e.g., fibrous) substrate wetted with the mixture of the first and second solvent systems is cooled or cooled to a temperature T4 before separating the colored (e.g., dyed) polymeric (e.g., fibrous) substrate from the mixture of the first and second solvent systems and any remaining dye.

The total staining (e.g. staining) time may be less than 3 hours. The total staining (e.g. staining) time may be less than 90 minutes. The total staining (e.g. staining) time may be less than 45 minutes. The total staining (e.g. staining) time may be less than 20 minutes. The total tinting (e.g., dyeing) time is the period of time from the first addition of the second solvent system to the cooling of the dyed polymeric (e.g., fibrous) substrate wetted by the mixture of the first solvent system and the second solvent system.

The step of subjecting the polymeric (e.g., fibrous) substrate to the coloring liquid can comprise spraying the coloring liquid onto the substrate (e.g., fibrous) substrate. The step of subjecting the polymeric (e.g., fibrous) substrate to the tinting liquid can include placing the substrate into the tinting liquid.

The step of adding the second solvent system to the polymeric (e.g., fibrous) substrate wetted with the tinting liquid may include spraying the second solvent system onto the polymeric (e.g., fibrous) substrate wetted with the tinting liquid. The step of adding the second solvent system to the polymeric (e.g., fibrous) substrate wetted with the tinting liquid may include adding the second solvent system to the tinting liquid in which the substrate is located.

The method may comprise the steps of: a colorant (e.g., a dye) is dissolved in a first solvent system to form a colored liquid.

The coloring liquid may not contain a dispersant. Typical dispersants include anionic polyelectrolyte compounds (and mixtures thereof), such as lignosulfonates or formaldehyde condensates, or aryl sulfonic acids (e.g., disodium methylene bis naphthalene sulfonate, sodium oleyl p-anisidine sulfonate). The staining solution may not contain a carrier. Typical carriers include, for example, o-dichlorobenzene, 1,2, 4-trichlorobenzene, dimethyl phthalate, diallyl phthalate, o-phenylphenol, p-phenylphenol, biphenyl, 1-methylnaphthalene, ethylene carbonate, and propylene carbonate. Thus, the coloring liquid may consist essentially of at least one colorant (e.g., a dye, such as a disperse dye) dissolved in a first solvent system (e.g., a polar organic solvent). Thus, where the present invention comprises the step of dissolving a colorant (e.g., a dye) in a first solvent system to form a colored liquid, the dissolved colorant (e.g., dye) can be substantially pure (e.g., greater than 90% pure or greater than 95% pure). The inventors have found that excellent colour strength can be obtained using the process of the invention without a dispersant or carrier.

The second solvent system may not comprise a dispersant. The second solvent system may not comprise a carrier. Thus, the second solvent system may consist essentially of the one or more solvents that form the second solvent system.

Alternatively, the colouring liquid and/or the second solvent system may comprise at least one additive selected from: dispersants, carriers, stabilizers, surfactants, antioxidants, pH adjusters/buffers, lubricants, softeners, hydrotropes (hydrotropes), wetting agents and migrating agents. The tinting liquid and/or the second solvent system may comprise at least one additive selected from the group consisting of: stabilizers, surfactants, antioxidants, pH adjusters/buffers, lubricants, softeners, hydrotropes, wetting agents and migratory agents.

T1 and T2 may be the same. T1, T2, and T3 may be the same.

T1 may be higher than 70 ℃. T1 may be higher than 80 ℃. T1 may be higher than 90 ℃.

T2 may be higher than 70 ℃. T2 may be higher than 80 ℃. T2 may be higher than 90 ℃.

T3 may be higher than 70 ℃. T3 may be higher than 80 ℃. T3 may be higher than 90 ℃.

T4 may be below 70 ℃. T4 may be below 60 ℃. T1 may be 25 ℃ to 70 ℃. T2 may be from 25 ℃ to 70 ℃. T2 may be from 25 ℃ to 70 ℃. With the process of the present invention, certain types of colorants, in particular dyes for coloring natural fibers (e.g. wool, silk and cotton), can be effectively used at temperatures below 70 ℃.

The process may be carried out at a pressure of about 1 atm. The process may be carried out at a pressure of 0.9atm to 1.5 atm. The process may be carried out at elevated pressures, for example pressures greater than 1atm and up to 5 atm.

The weight ratio of the polymeric (e.g., fibrous) substrate to the first solvent system can be from 4:1 to 1: 4. The weight ratio of the polymeric (e.g., fibrous) substrate to the first solvent system can be from 3:1 to 1: 3. The weight ratio of the polymeric (e.g., fibrous) substrate to the first solvent system can be from 2:1 to 1: 2.5. The weight ratio of the polymeric (e.g., fibrous) substrate to the first solvent system can be from 1:1 to 1:2. The weight ratio of the polymeric (e.g., fibrous) substrate to the first solvent system can be from 1:0.1 to 1: 15.

The ratio of the polymeric (e.g., fibrous) substrate to the total amount of the second solvent system can be 3:1 to 1: 15. The weight ratio of the polymeric (e.g., fibrous) substrate to the total amount of the second solvent system can be from 2:1 to 1: 10. The weight ratio of the polymeric (e.g., fibrous) substrate to the total amount of the second solvent system can be from 1:1 to 1: 4.

The weight ratio of the polymeric (e.g., fibrous) substrate to the total amount of the first and second solvent systems can be from 1:1 to 1: 20. The weight ratio of the polymeric (e.g., fibrous) substrate to the total amount of the first and second solvent systems can be from 1:1 to 1: 10. The weight ratio of the polymeric (e.g., fibrous) substrate to the total amount of the first and second solvent systems can be from 1:2 to 1: 5.

The amount of colorant (e.g., dye) used can be 0.5% to 10% by mass of the polymeric substrate (e.g., 0.5% to 10% by mass of the fiber). The amount of colorant (e.g., dye) used can be 1% to 5% by mass of the polymeric substrate (e.g., 1% to 5% by mass of the fiber).

Typically, the total volume of the first solvent system to which the polymeric (e.g., fibrous) substrate is subjected is less than the total volume of the second solvent system to which the polymeric (e.g., fibrous) substrate is subjected. The ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 1:2 to 1: 20. The ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 1:3 to 1: 15. The ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 30:70 to 10: 90.

The tinting process may be followed by reductive scavenging, rinsing and optional further treatment depending on the nature of the substrate (e.g., whether the substrate is a single component blend or a multi-component blend of fibers) and the requirements of the end use. Exemplary further treatments include softening, heat setting, and the like.

Solvent system

The process of the present invention involves the use of two solvent systems. The colorant (e.g., dye) is more soluble in the first solvent system than in the second solvent system.

The first solvent system should be capable of dissolving at least one colorant.

The first solvent system may be supercritical CO₂. The first solvent system may be a surfactant (e.g., a polyethoxylated fatty acid and/or fatty acid ester, or a mixture thereof) or an aqueous solution of a surfactant.

Preferably, however, the first solvent system may comprise an organic solvent or a mixture of two or more organic solvents. The first solvent system may be an organic solvent or a mixture of two or more organic solvents. The first solvent system may be an organic solvent. The first solvent system may comprise a mixture of two or more organic solvents. Where the first solvent system comprises an organic solvent or a mixture of two or more organic solvents, the inventors have demonstrated that the presence of water can be tolerated in the first solvent system, but typically the first solvent system can comprise water, but typically the water comprises less than 50% (e.g., less than 10%) of the total weight of the first solvent system. Thus, the first solvent system may comprise less than 5% (e.g., less than 1%) water. The first solvent system may comprise a mixture of water and an organic solvent.

The first solvent system may be an organic solvent having a molecular weight below 200, or a mixture of two or more organic solvents each having a molecular weight below 200. The first solvent system may be an organic solvent having a molecular weight below 175, or a mixture of two or more organic solvents each having a molecular weight below 175. The first solvent system may be an organic solvent having a molecular weight below 150, or a mixture of two or more organic solvents each having a molecular weight below 150. The first solvent system may be an organic solvent having a molecular weight below 120 or a mixture of two or more organic solvents each having a molecular weight below 120. The first solvent system may be an organic solvent having a molecular weight below 100, or a mixture of two or more organic solvents each having a molecular weight below 100. The first solvent system may be an organic solvent having a molecular weight below 80, or a mixture of two or more organic solvents each having a molecular weight below 80. The first solvent system may be an organic solvent having a molecular weight greater than 80, or a mixture of two or more organic solvents each having a molecular weight greater than 80.

The first solvent may be an organic solvent that is liquid at 25 ℃ and 1atm, or a mixture of two or more organic solvents that are liquid at 25 ℃ and 1atm, respectively. The first solvent may be an organic solvent that is liquid at 0 ℃ and 1atm, or a mixture of two or more organic solvents that are liquid at 0 ℃ and 1atm, respectively.

The first solvent system may be selected from: non-polar organic solvents (examples include pentane, hexane, benzene, toluene, dichloromethane, cyclohexane, heptane, CCl₄Etc.), polar aprotic solvents (e.g., acetone, methyl tert-butyl ketone, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, diethyl ether, ethyl acetate, dimethyl sulfoxide, diethylene glycol diethyl ether, ethylene glycol diacetate, etc.) and protic polar solvents (e.g., ethanol, methanol, propanol, isopropanol, ethylene glycol, glycerol, triethylene glycol monomethyl ether, dipropylene glycol methyl ether, 1-methoxy-2-propanol, etc.) or mixtures thereof. The first solvent system may comprise a polar organic solvent or a mixture of two or more polar organic solvents. The first solvent system may be a polar organic solvent or a mixture of two or more polar organic solvents. The first solvent system may comprise a polar aprotic organic solvent or a mixture of two or more polar aprotic organic solvents. The first solvent system may be an ether group containing organic solvent or a mixture of two or more ether group containing organic solvents. The first solvent system may be an organic solvent comprising an ether group and a hydroxyl group, or a mixture of two or more organic solvents comprising an ether group and a hydroxyl group. The first solvent system may be a polar aprotic organic solvent or a mixture of two or more polar aprotic organic solvents. The first solvent system may comprise an organic solvent containing carbon, hydrogen, oxygen, nitrogen and sulfur, or a mixture of two or more organic solvents containing carbon, hydrogen, oxygen, nitrogen and sulfur. The first solvent system may comprise an organic solvent comprising carbon, hydrogen and oxygen, or a mixture of two or more organic solvents comprising carbon, hydrogen and oxygen.

The first solvent system may comprise acetone. The first solvent system may be acetone. The first solvent system may be a mixture of acetone and one or more other polar organic solvents, for example a mixture of acetone and ethanol.

The first solvent system may comprise DMSO. The first solvent system may be DMSO. The first solvent system may be a mixture of DMSO with one or more other polar organic solvents, for example a mixture of DMSO with ethanol, or a mixture of DMSO with acetone.

The first solvent system may comprise glycerol. The first solvent system may be glycerol. The first solvent system may be a mixture of glycerol and one or more other polar organic solvents, for example a mixture of acetone and glycerol.

The first solvent system may comprise a solvent selected from the group consisting of ethylene glycol diacetate, triethylene glycol monomethyl ether, dipropylene glycol methyl ether, and 1-methoxy-2-propanol. The first solvent system may be a solvent selected from the group consisting of ethylene glycol diacetate, triethylene glycol monomethyl ether, dipropylene glycol methyl ether, and 1-methoxy-2-propanol, or mixtures thereof.

The first solvent system may comprise a solvent selected from the group consisting of glycerol, ethylene glycol diacetate, triethylene glycol monomethyl ether, dipropylene glycol methyl ether, and 1-methoxy-2-propanol. The first solvent system may be a solvent selected from glycerol, ethylene glycol diacetate, triethylene glycol monomethyl ether, dipropylene glycol methyl ether, and 1-methoxy-2-propanol, or mixtures thereof.

The second solvent system should be one in which the colorant (e.g., dye) is poorly soluble. The second solvent system may be an organic solvent in which the colorant (e.g., dye) is less soluble than the colorant (e.g., dye) in the first solvent system. Typically, the second solvent system comprises water. The second solvent system may be water or an aqueous solution. The second solvent system may be water or a mixture of an aqueous solution and an organic solvent. The second solvent system may be water. The second solvent may comprise a mixture of two or more organic solvents.

Where the second solvent system is an aqueous solution, it may be a solution of an electrolyte, a solution of an acid, a solution of a base, or a solution of a buffer, or a solution of a mixture of an electrolyte and an acid, base, or buffer.

Suitable electrolytes include NaCl, Na₂SO₄Ammonium sulfate, and other electrolytes commonly used in dye applications by dyeing.

Suitable bases include Na₂CO₃、NaHCO₃、K₂CO₃KOH, NaOH, and other bases commonly used in dye applications by dyeing. Suitable acids include acetic acid, formic acid, and other acids commonly used in dye applications by dyeing.

Suitable buffers include those based on citrate, phosphate, acetate and other buffers commonly used in dye applications by dyeing.

The electrolyte is particularly useful when a reactive dye, vat dye or direct dye is used.

Bases are particularly useful when reactive dyes are used.

The first solvent system may be miscible with the second solvent system. Thus, where the second solvent system is or comprises water, the first solvent system may be water-miscible.

Both the first solvent system and the first solvent system are typically selected so that the polymeric (e.g., fibrous) substrate is insoluble in either the first solvent system or the second solvent system.

Typically, the total volume of the first solvent system to which the polymeric (e.g., fibrous) substrate is subjected is less than the total volume of the second solvent system to which the polymeric (e.g., fibrous) substrate is subjected. The ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 1:1.1 to 1: 10. The ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 1:2 to 1: 20. The ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 1:3 to 1: 15. The ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 30:70 to 10: 90.

Base material

The polymeric substrate may comprise organic or inorganic derived natural, artificial and/or synthetic polymers including polypeptides, polysaccharides, hydrocarbons, elastomers, thermosets and thermoplastics, for example, but not limited to, polymers such as collagen, keratin, cellulose, alginate, polysulfides, polyamides, polylactic acid, polyvinyl chloride, polyacrylonitrile, polyethylene, polypropylene, polystyrene, polyurethane, aramid and polyimide.

The polymeric substrate may take any solid physical form including powder, granules, sheets, films, fibers or any irregular shape. The polymer substrate may be in the form of a moulded plastics material such as an automobile bumper or a pair of spectacles. The polymer substrate may be a 3D printed object.

The polymeric substrate may comprise more than one type of polymer. The polymeric substrate may comprise two or more polymers that are present together in various mixtures formed by physical blending, mixing, dissolving, precipitating, molding, or interconnection of 3D printed parts, and the like.

The inventors have found that the method of the present invention can be used to simultaneously colour different polymers using different types and kinds of colourants.

The polymeric substrate may be a fibrous substrate, such as a yarn, a fabric, a garment, or a portion of a garment.

The fibrous substrate may comprise synthetic or natural fibers or mixtures thereof. The fibrous substrate may comprise fibers selected from the group consisting of: polyesters, polyamides, polyurethanes, polyalkylenes, polyacrylonitriles, wool, silk, natural or regenerated cellulose, cellulose esters, hair, polyvinyl chloride, carbon or mixtures thereof.

Exemplary polyesters include poly (ethylene terephthalate) (PES), poly (butylene terephthalate) (PBT), poly (trimethylene terephthalate) (PTT). Exemplary polyurethanes include

Exemplary polyamides include nylon.

The fibrous substrate may be or may comprise polyamide fibres, for example nylon fibres.

The fibrous substrate may comprise polyester fibers or polyester and a material selected from cotton, wool, silk and polyurethane (e.g., polyurethane

) A mixture of fibers of (a). The fibrous substrate may comprise PES fibers or PES fibers with a material selected from cotton, wool, silk and polyurethane (e.g., polyurethane)

) A mixture of fibers of (a). The fibrous substrate may be polyester. The fibrous substrate may be PES. The fibrous substrate may comprise polyester and a material selected from cotton, wool, silk and polyurethane (e.g., polyurethane)

) A mixture of fibers of (a). The fibrous substrate may comprise PES with a material selected from cotton, wool, silk and polyurethane (e.g.

) A mixture of fibers of (a).

The fibrous substrate may comprise silk or wool fibers.

The fibrous substrate may comprise polyester fibers and at least one other type of fiber selected from cotton, regenerated cellulose, wool, silk, polyamide, other polyesters, polyvinyl chloride, polyacrylonitrile, mohair (mohair), cashmere (Cashmere), and polyurethane. The fibrous substrate may comprise a material which is a blend of polyester fibers and at least one fiber of another type selected from the group consisting of cotton, regenerated cellulose, wool, silk, polyamide, other polyesters, polyvinyl chloride, polyacrylonitrile, mohair, cashmere and polyurethane. The fibrous substrate may be a material which is a blend of polyester fibres with at least one fibre selected from cotton, regenerated cellulose, wool, silk, polyamide, other polyesters, polyvinyl chloride, polyacrylonitrile, mohair, cashmere and polyurethane. Alternatively, the fibrous substrate comprises a first material comprising polyester fibers and a second material comprising at least one fiber selected from the group consisting of cotton, regenerated cellulose, wool, silk, polyamide, other polyesters, polyvinyl chloride, polyacrylonitrile, mohair, cashmere and polyurethane. The fibrous substrate may be a one-piece garment such as a sports shoe (train) or pair of sports shoes, a shirt or coat, a dress, trousers, skirt, T-shirt, etc.

The fibrous substrate may comprise polyester fibers and at least one other type of fibers selected from cotton, wool, silk, mohair, cashmere and polyurethane. The fibrous substrate may comprise a material that is a blend of polyester fibers and at least one fiber of another type selected from the group consisting of cotton, wool, silk, mohair, cashmere, and polyurethane. The material of the fibrous substrate may be a blend of polyester fibers and at least one fiber selected from cotton, wool, silk, mohair, cashmere and polyurethane. Alternatively, the fibrous substrate may comprise a first material comprising polyester fibers and a second material comprising at least one fiber selected from the group consisting of cotton, wool, silk, mohair, cashmere and polyurethane.

As mentioned above, the inventors have found that the method of the present invention can be used to simultaneously colour different polymers using different types and kinds of colourants. In particular, the method of the present invention can be used to simultaneously color (e.g., dye) different fibers with different types and kinds of colorants (e.g., dyes). This offers the following possibilities: by judicious choice of fabric, a hybrid fabric can be created in which a pattern is designed into the weave of the fabric, and different fibers in the weave can be dyed simultaneously and selectively to different colors. Likewise, an integral garment (e.g., a shoe, such as a sports shoe or pair of sports shoes) formed from two or more different materials may be dyed immediately after formation, and the various materials may be dyed to different colors simultaneously. This would allow custom dyeing of entire garments in distribution warehouses or stores (bespoke dyeing) according to the color preferences chosen by the purchaser.

Coloring agent

The at least one colorant may comprise at least one pigment.

The at least one colorant may comprise at least one dye.

The at least one colorant may be a single dye. The at least one colorant may be a mixture of two or more dyes.

Suitable dyes include disperse dyes, solvent dyes, vat dyes, sulfur dyes, mordant dyes (mordant dye), acid dyes, direct dyes, and reactive dyes. Disperse dyes, solvent dyes, vat dyes, sulfur dyes, mordant dyes, acid dyes, direct dyes, and reactive dyes that may be used in the process of the present invention include color indexes such as those published by the Society of Dyers and Colorists (SDC) and American Association of Textile chemistry and pigments (AATCC)^TMAll dyes of the class (1). In certain embodiments, disperse dyes, solvent dyes, vat dyes, sulfur dyes, mordant dyes, acid dyes, direct dyes, and reactive dyes that may be used in the methods of the present invention may include Color Index as of day 1/5 in 2017^TMAll dyes of the class (1).

The at least one dye may comprise a disperse dye. The single dye may be a disperse dye.

The at least one dye may comprise an acid dye (e.g., a non-metallized acid dye or a pre-metallized acid dye). The single dye may be an acid dye (e.g., a non-metallized acid dye or a pre-metallized acid dye).

The at least one dye may include a vat dye. The single dye may be a vat dye.

The at least one dye may include a reactive dye. The single dye may be a reactive dye.

The at least one dye may comprise a direct dye. The single dye may be a direct dye.

The at least one pigment may include a pigment selected from the group consisting of organic pigments, inorganic pigments, and metallic pigments.

Where the polymeric (e.g., fibrous) substrate to be colored comprises different polymers (e.g., different fibers), a mixture of two or more types or types of colorants (e.g., dyes) can be used. For example, where the fibrous substrate comprises polyester fibers (e.g., PES) and natural fibers (e.g., cotton, silk, or wool), a mixture of disperse dyes (to dye the polyester fibers) and reactive dyes (to dye the natural fibers) may be used. Alternatively, a mixture of disperse dyes (dyeing polyester) and direct dyes (dyeing natural fibers) may be used. In a further alternative, a mixture of disperse dyes (dyeing polyester fibers) and acid dyes (dyeing natural fibers) may be used. In a further example, where the fibrous substrate comprises polyester fibers (e.g., PES), cotton fibers, and wool or silk fibers, a mixture of disperse dyes (to dye polyester fibers), reactive dyes (to dye cotton fibers), and acid dyes (to dye wool or silk fibers) may be used.

The invention may be further described in the following numbered paragraphs:

1. a method of dyeing a fibrous substrate, the method comprising:

a) subjecting the fibrous substrate to a dye liquor at a temperature T1, T1 being below 100 ℃, said dye liquor comprising at least one dye dissolved in a first solvent system to provide a fibrous substrate wetted with the dye liquor;

b) adding a second solvent system to the fibrous substrate wetted with the dye liquor without raising the temperature above the temperature T2, T2 being less than 100 ℃, to provide a dyed fibrous substrate wetted with a mixture of the first solvent system and the second solvent system; and

c) separating the dyed fibrous substrate from the mixture of the first and second solvent systems and any remaining dye;

wherein the or each dye is more soluble in the first solvent system than in the second solvent system.

2. A method according to paragraph 1, wherein the step of adding the second solvent system comprises adding the second solvent system to the mixture of the fibrous substrate and the dye liquor part by part.

3. The method according to paragraph 1 or paragraph 2, wherein the second solvent system comprises water.

4. A method according to paragraph 3, wherein the second solvent system is water.

5. A method according to any preceding paragraph, wherein the first solvent system and the second solvent system are miscible.

6. A method according to any preceding paragraph, wherein the first solvent system is an organic solvent or a mixture of one or more organic solvents.

7. A method according to paragraph 6, wherein the first solvent system is a polar organic solvent or a mixture of polar organic solvents.

8. A method according to paragraph 7, wherein the first solvent system is acetone.

9. The method according to any preceding paragraph, wherein the fibrous substrate comprises fibers selected from the group consisting of: polyester, nylon, polyurethane, wool, silk, cotton or mixtures thereof.

10. A method according to paragraph 10, wherein the fibrous substrate comprises polyester fibers or a mixture of polyester and fibers selected from the group consisting of cotton, wool, silk and polyurethane.

11. The method according to any preceding paragraph, wherein the ratio of the total volume of the first solvent system to the total volume of the second solvent system may be from 1:2 to 1: 20.

12. The method according to paragraph 11, wherein the ratio of the total volume of the first solvent system to the total volume of the second solvent system can be from 30:70 to 10: 90.

13. The method according to any preceding paragraph, wherein the weight ratio of the fibrous base material to the first solvent system is from 3:1 to 1: 3.

14. A method according to any preceding paragraph, wherein the at least one dye is a disperse dye.

15. A method according to any preceding paragraph, wherein the method comprises dissolving at least one dye in a first solvent system to form a dye liquor.

16. A method according to any preceding paragraph, wherein the dye liquor does not comprise a dispersant.

17. A fibrous substrate obtainable according to the method of any preceding paragraph.

Drawings

Embodiments of the invention are further described below with reference to the accompanying drawings, in which:

FIG. 1 shows the High Temperature (HT) PES staining method used for comparison in the following examples;

FIG. 2 illustrates a reduction clearing (reduction clearing process) method for an embodiment;

FIG. 3 provides a general description of the controlled precipitation staining method of the present invention;

FIG. 4 shows the color intensity of 2% omf staining on PES achieved using the controlled precipitation method of the invention; teratop yellow HL-G150%; 120 minutes at 98 ℃;

FIG. 5 shows the color intensity of 2% omf staining on PES achieved using the controlled precipitation method of the invention; teratop yellow HL-G150%; 30 ', 60 ' and 90 ' at 98 ℃;

FIG. 6 shows the color intensity of 2% omf staining on PES achieved using the controlled precipitation method of the invention at 98 ℃ for 20 minutes; teratop yellow HL-G150%;

FIG. 7 shows the color intensity of 2% omf staining on PES achieved using the controlled precipitation method of the invention at 85 ℃ for 120 minutes; teratop yellow HL-G150%;

FIG. 8 shows the color intensity of 2% omf staining on PES (Terato blue HL-G150%: left and Terato pink HL-G150%: right) achieved at 98 ℃ for 20 minutes using the controlled precipitation method of the present invention;

FIG. 9 shows a dyeing method used in the dyeing methods described in examples 3, 4 and 5;

FIG. 10 shows the color intensity of a 2% omf dyeing of crude Terato yellow HL-G150% on a fabric composite comprising a polyester fabric attached to a scoured (scurred) PA 66 fabric;

FIG. 11 shows the color intensity of 2% omf staining of commercial Terate yellow HL-G150% on PES as a function of staining temperature using DMSO as solvent.

Detailed Description

The organic solvent is an organic compound that is liquid at room temperature and atmospheric pressure. Generally, an organic solvent is a compound containing both carbon and hydrogen atoms. One exception is carbon tetrachloride. The organic solvent may also comprise oxygen, nitrogen, chlorine, fluorine or sulfur.

In this specification, the term "wetted" refers to the polymeric (e.g. fibrous) substrate being contacted with a liquid (e.g. a dye liquor or a mixture of a first solvent system and a second solvent system). It may refer to soaking a substrate (e.g. a fibrous substrate) in a liquid, e.g. saturated with liquid (saturated). It may refer to coating a substrate (e.g., a fibrous substrate) in a liquid. It may refer to immersing a substrate (e.g., a fibrous substrate) in a liquid. Other techniques that may be used include spraying, soaking, vaporizing, absorbing (inhibition), and the like.

In the case where the colorant molecules have been absorbed into the substrate (e.g., into the fibers), the polymeric (e.g., fibrous) substrate is described as "colored". Throughout the description and claims of this specification, the words "comprise" and "contain" and variations thereof mean "including but not limited to", and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The invention is not limited to the details of any of the foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

Examples

General procedure

Material

Refined (sized) poly (ethylene terephthalate) (PES) fabric (120 gm)^-2) Refined, bleached and mercerized (mercerised) woven cotton fabric (180 gm)^-2) And scouring PA 66 Fabric (116 gm)^-2) Obtained from Whaleys (Bradford, UK). Commercial and crude (i.e., synthetic) grade samples of the three disperse dyes, namely, Terato yellow HL-G150%, Terato blue HL-G150%, and Terato pink HL-G150%, were kindly provided by Huntsman (Switzerland). Commercial dyes were used in this work to reflect commercial dyeing practices, while equivalent crude grade dyes were also used to determine whether PES could be dyed using dispersant-free disperse dyes. Three dyes were arbitrarily selected for use as representative of modern commercial disperse dyes. The three dyes were all shaded with 2% omf depth as this provided typical light/medium depth dyeing.

Samples of polysorbate 20, polysorbate 60, polysorbate 80, lecithin and Superclean were obtained from Sigma-Aldrich. All other chemicals were of the general grade.

Based on the measured values of the relative dye content for each pair of commercial and crude grade dye samples, the amount of crude grade dye used for dyeing was adjusted so that the shade depth obtained (i.e., 2% omf) was the same as that ensured using the commercial grade dye.

Comparative general method

The High Temperature (HT) staining method used for comparison in this work is shown in figure 1.

PES fabrics (5g or 10g) were dyed using commercial and crude grade disperse dyes according to the procedure shown in FIG. 1. At the end of the dyeing, the dyed sample is taken out of the bath, squeezed to remove the excess dye liquor and rinsed in water according to the procedure shown in figure 1. The stained sample was then squeezed again and subjected to the reductive elimination procedure shown in figure 2. At the end of the reduction clean-up process, the sample was removed, squeezed to remove excess liquid and rinsed with cold water as shown in fig. 2. The cleared dye was squeezed down and allowed to dry outdoors.

General procedure of the invention

The controlled precipitation method of the present invention is shown generally in fig. 3.

Example 1 development of a Process Using disperse dyes, PES and acetone

Using a₁；a₂；a₃；a₄＝10cm³Water; t is t₁＝30’；t₂＝30’；a₃＝30’；a₄30'; the process shown in fig. 3 was carried out at 98 ℃.

Disperse dyes are dissolved in a given volume (in this case 10 cm)³) And then applying the resulting solution to PES fibers.

When the bath temperature reached 98 ℃, a volume of water (10 cm) was added³) And continuing to dye within a certain time, and adding 10cm³And (3) water. This process was continued until the final bath volume was 50cm³Corresponding to a liquid ratio of 1: 10. Thus, the ratio of water to acetone gradually increases from 0:100 at the beginning of the dyeing to 80:20 at the end of the dyeing during the length of the dyeing process.

Without wishing to be bound by theory, the purpose of the gradual introduction of water into the acetone dye solution is to gradually force the disperse dye out of solution in a controlled manner, thereby achieving increased dye-fiber substantivity (dye-fiber substantivity) in a controlled and measurable manner, and thereby increasing dye absorption.

The total staining time at 98 ℃ was 120 minutes according to the procedure described above. Figure 4 shows that with this method the dyeings obtained show a very high colour strength, much higher than that ensured at 130 ℃ using commercial grade dyes and conventional HT dyeing methods. Visual inspection showed that the dye precipitation method of the present invention not only provided a deeper shade depth than the HT method, but significantly, ensured greater dye bath exhaustion levels.

Thus, the higher color intensity of the 120 min 98 ℃ stain (fig. 4) can be attributed to the greater degree of dye exhaustion achieved. The fact that the residual dye bath is substantially free of unspent disperse dyes offers significant cost and environmental potential. In other words, to obtain a color intensity comparable to that achieved using commercial grade dyes using the conventional 2% omf dyeing process at 130 ℃ (i.e. f @_kValue-50), if the controlled precipitation dyeing method of the invention is used, less disperse dye is required (i.e., -1.25% omf dyeing) because almost 100% dye exhaustion is achieved. Furthermore, because the crude fraction disperse dyes are used in the precipitation dyeing process of the present invention, the spent dye bath will be substantially free of dye and zero dispersant and leveling agent as compared to the residual dye bath produced by conventional HT dyeing processes.

Attempts to reduce the dyeing duration at 98 ℃; for this purpose, in FIG. 3, a₁、a₂、a₃And a₄＝10cm³Total time for water and commercial boiling was 90, 60 and 30 minutes (in all cases, a)₁＝a₂＝a₃＝a₄). As shown in fig. 5, reducing the dyeing time at 98 ℃ did not affect the color yield of the resulting dyeing; a comparison of fig. 4 and 5 shows that the color yield is the same for all four stains.

When the total time for commercial boiling is further reduced to 20 minutes (i.e. a)₁、a₂、a₃And a₄＝10cm³Water and a₁＝a₂＝a₃＝a₄5') the color intensity of the dyed fabric was similar to dyeing times of 30, 60, 90 and 120 minutes (fig. 6). However, with further reduction of the dyeing time at commercial boil, the color intensity of the dyeing is reduced.

When the dyeing temperature was reduced from 98 ℃ to 85 ℃, it was found (fig. 7) that although the color intensity of 120 minutes dyeing was performed was the same as that achieved at 98 ℃, the dyeing color intensity was lower with the shorter dyeing times of 60 minutes and 90 minutes at 85 ℃. Visual inspection revealed no dye in the residual dye bath obtained after 120 minutes at 85 ℃, as observed when dyeing was carried out at commercial boil.

When two other disperse dyes (i.e., Terato blue HL-G150% and Terato pink HL-G150%) were applied to PES at 98 ℃ for 20 minutes using the precipitation dyeing method of the present invention, the color intensity of the dyeing was compared with the color intensity ensured using the HT dyeing method (i.e., at 130 ℃), as shown in FIG. 8.

It is clear that for each dye, a higher intensity of color dyeing was obtained at 98 ℃ using the precipitation dyeing method of the invention (fig. 8), and that for the HT dyeing method a much higher degree of exhaustion of the dye was observed.

Example 2 fastness

Table 1 shows that the 2% omf dyeings obtained using the three commercial grades of dye show very good wash fastness at 60 ℃ when applied using the HT method (i.e. 130 ℃), as expected; visual inspection also showed that the shade depth of the dyeing was impressive after the wash fastness test. The results given in table 1 also show that, using crude grade samples of the three dyes, the corresponding dyeings produced using the precipitation dyeing process of the invention at 98 ℃ for 20 minutes show substantially the same high level of wash fastness. The latter finding is impressive when it is recalled that the color intensity of the 98 ℃ dyeing is much higher than that of its 130 ℃ dyeing. Thus, as expected, the mode of application of the disperse dyes (i.e. the difference in dyeing temperature, dyeing duration and acetone) had no effect on the wash fastness (wash fastness).

TABLE 1 fastness of 2% omf dyeing on PES produced at 98 ℃ for 20 minutes using the HT method (commercial grade dye at 130 ℃) and the precipitation method of the invention, according to ISO 105-C06/C2S (60 ℃)

When the above procedure is followed but polyester fabric previously soaked with water and squeezed to remove excess water is used, the colour strength of the dyeing obtained at 98 ℃ for 20 minutes is comparable to that achieved using dry polyester fabric.

Example 3 other fabrics and other kinds of dyes

The method of the present invention can also be used to dye other substrates with other dye types. The following examples describe the dyeing of wool, silk and polyamide substrates with acid dyes and disperse dyes.

The general method used in this example is shown in fig. 9. A Roaches Pyrotec S staining machine was used. 0.1g of commercial dye was dissolved in 10cm³In acetone, and then the resulting solution was placed at 300cm³Into a volume of dyeing tube, 5g of fabric was then placed. The sealed dyed tube was heated to 85 ℃ and then 10cm³The water of (a) is injected into the dyeing tube. As shown in FIG. 9, a total of 40cm was reinjected at intervals³And (3) water. The total staining time at 85 ℃ was 20 minutes.

Using the dyeing process of the present invention, non-metallized acid dyes (Erionyl Red A-2BF (huntsman)) and 1:2 pre-metallized acid dyes (Supralan yellow 4GL (Dystar); Lanaset yellow 2R (huntsman)) and Neutrilan yellow A-3R (Yorkshire)) were applied to wool, silk and PA fabrics. In addition, commercial and crude grade disperse dye Terato yellow HL-G150% (Huntsman) samples were applied to wool, PA and wool fibers.

Silk and wool were successfully dyed with the non-metallised dye Erionyl red a-2BF at 80 ℃ for 20 minutes. Color measurement L34.3 a 63.4b 58.1.

Compared to conventional methods for dyeing wool using this dye type, which are typically carried out at higher temperatures (wool: 98 ℃) and under acidic conditions for 60-90 minutes, the novel dyeing method is advantageous because it allows the fibers to be dyed at lower temperatures of 85 ℃ (for wool) in a short time (i.e., 20 minutes) without the need to adjust the pH, thus saving time, energy and chemicals.

Silk and wool were successfully dyed using the novel dyeing method at 85 ℃ for 20 minutes using the 1:2 metal complex dye Supralan yellow 4GL and the color measurement L ═ 83.8a ═ 6.9b ═ 116.5. Again, the novel dyeing method allows the dyeing of the fibers at 85 ℃ in a short time (i.e. 20 minutes) without the use of pH adjustment, saving time, energy and chemicals, compared to the conventional methods for dyeing wool with such dye types, which are usually carried out at higher temperatures (wool: 98 ℃) and under acidic conditions for 60-90 minutes.

The novel dyeing process also allows wool and silk to be dyed using the 1:2 metal complex dye Neutrilan yellow a-3R (color measurement L ═ 48.7a ═ 34.5b ═ 8.1) and Lanaset yellow 2R at 85 ℃ for 20 minutes. Again, the new dyeing method allows the dyeing of the fibres at 85 ℃ in a short time (i.e. 20 minutes) compared to the conventional methods for dyeing wool with such dye types, which are usually carried out at higher temperatures (for wool) and under acidic conditions for 60-90 minutes, thus saving time, energy and chemicals.

Using the novel dyeing process, commercial samples (i.e., with dispersant) and crude grade samples (i.e., without dispersant) of 150% of the disperse dye, terrato yellow HL-G, were successfully applied to scour wool and silk as well as PA fibers at 85 ℃ for 20 minutes.

Example 4 blend of fibers

The method of the invention can also be used to dye combinations of different types of fibres. The following examples describe the dyeing of polyester/cotton blends as well as polyester/nylon blends with disperse dyes.

The general method used in this example is shown in fig. 9. A Roaches Pyrotec S staining machine was used. The appropriate amount of crude fraction disperse dye to give a 2% omf shade was dissolved in 10cm³In acetone, and then the resulting solution was placed at 300cm³Into a volume of dyeing tube, a fabric composite comprising 2.5g of polyester fabric attached to 2.5g of scoured, bleached and mercerized woven cotton fabric was then placed. The sealed dyed tube was heated to 98 ℃ and then 10cm³Water was injected into the dye tube. As shown in FIG. 9, a total of 40cm was reinjected at intervals³And (3) water. The total staining time at 85 ℃ was 20 minutes.

2% omf dyeing of the crude grade (i.e. without dispersant) disperse dyes Terato yellow HL-G150%, Terato blue HL-G150% and Terato pink HL-G150% was successfully achieved using the novel dyeing process at 98 ℃ for 20 minutes. The polyester component is fully dyed, whereas the cotton fabric is not colored. This is expected based on the relative hydrophobicity of cotton and polyester fibers and the different substantivity (substantivity) exhibited by the corresponding disperse dyes for the fibers.

Following the above procedure, a 2% omf dyeing was obtained using a fabric composite comprising 2.5G of polyester fabric attached to 2.5G of scoured PA 66 fabric, using a crude grade disperse dye, terratop yellow HL-G150%.

As shown in fig. 10, both polyester and nylon 66 fabrics were dyed, but as expected, the shade depth of the polyester was higher due to the greater hydrophobicity of the polyester material and the corresponding greater substantivity of the dye to the polyester fiber.

Example 5 solvent mixture

The first solvent may comprise a mixture of two or more organic solvents or a mixture of water and an organic solvent.

The general procedure used in this example is shown in FIG. 9, with a mixed solvent system replacing acetone, as described below. A Roaches Pyrotec S staining machine was used. Dissolving crude fraction disperse dye Teratop yellow HL-G150% in 10cm³Acetone and 2cm³Water in a mixture. Placing the obtained solution at 300cm³To a volume of dyeing tubes, polyester fabric was subsequently added. The sealed dyed tube was heated to 98 ℃ and then 10cm³Water was injected into the dye tube. Injecting 40cm at intervals³And (3) water. The total staining time at 98 ℃ was 20 minutes.

The color intensity of the resulting dye was very similar to that obtained when acetone alone was used as the first solvent.

When the above procedure was used but the crude fraction disperse dye Terato yellow HL-G was 150% dissolved in 4cm³Acetone and 6cm³In a mixture of ethanol, successful staining was achieved.

Example 6-othersSolvent(s)

Although acetone is an excellent solvent for crude fraction disperse dyes, other solvents with higher boiling points have also been investigated. These solvents have a higher boiling point than acetone, thereby reducing the risk of fire.

Different amounts (5, 10 and 20 cm) were used³) DMSO (G) dissolve 2% omf commercial Terato yellow HL-G and add varying amounts of water (45, 40 and 30 cm) in portions³) To achieve 1:10LR as a whole. The color strength of the dyed polyester is shown in fig. 11.

As is evident from fig. 11, the color intensity values obtained are lower compared to PES stained with acetone, which is attributable to the lower solubility of the dye in DMSO. However, as shown in fig. 11, higher color intensity staining was achieved by increasing the amount of DMSO used. Although these dyeings do not show the high colour strength of the acetone process, they still provide benefits in terms of a low temperature process, have lower energy usage and are capable of simultaneously dyeing PES and non-PES fibres.

PES was stained with 2% omf shade depth of crude Terato yellow HL-G using various other high boiling solvents, i.e., Ethylene Glycol Diacetate (EGD), triethylene glycol monomethyl ether (TGM), dipropylene glycol methyl ether (DME), and 1-methoxy-2-propanol.

Using the controlled precipitation dyeing method shown in FIG. 3, each of the above-mentioned solvents (10 cm) was used³) And 4 additions of water (40 cm in total)³Water; total 1:10LR) PES fabric samples were dyed at 95 ℃ with a total dyeing time of 20 minutes at 95 ℃.

Color measurement data (light source D)₆₅(ii) a Including specular reflection; no UV is contained; 10 degree standard observer

Triethylene glycol monomethyl ether (TGM) L ═ 88.9a ═ 30.5b ═ 95.3

Ethylene Glycol Diacetate (EGD) L ═ 86.1a ═ 19.1b ═ 80.1

Each of the four solvents is capable of dissolving the crude fraction disperse dye and can be used in the precipitation dyeing process.

Example 7 Vat dye

To study the new typesWhether the precipitation dyeing process is applicable to the application of vat dyes, indigo is chosen. Using the controlled precipitation dyeing method shown in FIG. 3, acetone was used as a solvent (10 cm)³) And 4 additions of water (40 cm total)³Water; total 1:10LR) PES fabric samples were dyed at 95 ℃ with a total dyeing time of 20 minutes at 95 ℃.

It was found that using the precipitation dyeing process, vat dyes can be applied from acetone.

This result is achieved without reducing agents or adjusting the pH.

L*＝55.9a*＝-6.3b*＝-10.9

Example 8 one-pot dyeing of fiber mixtures with mixtures of various dyes (one) pot dyeing)

The novel precipitation staining method may offer the following potential: the fiber blends are dyed simultaneously in the same dye bath using different types of dyes without/with a very reduced amount of dye bath auxiliaries.

For this example, a fabric sample (2.5g) was dyed using the controlled precipitation dyeing method shown in fig. 3, using acetone as the main solvent, and using added water or a solution of inorganic electrolyte or base, and electrolyte/base, at different temperatures for a total dyeing time of 20 minutes. The amounts are given in the examples below.

PES/Cotton Using reactive dyes and disperse dyes

Duractive black B (c.i. reactive black 5) and crude Teratop yellow HL-G were dissolved in acetone. Using the controlled precipitation dyeing method shown in FIG. 3, 4 additions of a) water or b) containing 15gl^-1Na₂CO₃And 50gl^-1NaCl solution (1:10LR total), PES fabric and cotton fabric were dyed together at 95 ℃ for a total dyeing time of 20 minutes.

It was found that hydrophobic PES and hydrophilic cotton substrates can be dyed in the same dye bath at 95 ℃ for 20 minutes using a mixture of a nonionic disperse dye and an anionic reactive dye. As expected, the use of electrolytes and bases to favor the absorption of reactive dyes ensures color yield.

Since it is now known that exhaustion of reactive dyes on cotton can be increased by using a low liquid ratio without adding inorganic electrolyte, 10cm is also used twice³Addition of (1:6LR) containing 15gl^-1Na₂CO₃Dyeing with the solution of (1); the shadow depth of the reactive dye on the cotton component was increased compared to the results obtained at 1:10 LR.

Samples of PES fabric and cotton fabric were applied with commercial Novacron Red FN-2BL and crude Teratop yellow HL-G in acetone. Adding 10cm³Comprising 15gl^-1Na₂Solution of CO 4 times (1:10 LR); the total staining time was 20 minutes at 95 ℃. It was found that PES and cotton substrates can be dyed by the precipitation method using a mixture of disperse and reactive dyes in the same dye bath at 95 ℃ for 20 minutes.

Color measurement

PES L*＝75.8a*＝18.9b*＝116.5

Cotton L ═ 52.9a ═ -4.3b ═ -19.8

PES/Cotton Using direct dyes and disperse dyes

C.i. direct red 81 and crude terrato yellow HL-G were dissolved in acetone. Using the controlled precipitation dyeing method shown in FIG. 3, 4 additions of water or 20 gl-containing solutions were used^-1Samples of PES fabric and cotton fabric were dyed with a solution of NaCl (1:10LR total) at 95 ℃ for a total dyeing time of 20 minutes.

Color measurement

PES L*＝73.1a*＝16.1b*＝117.6

Cotton L ═ 41.1a ═ 66.9b ═ 19.4

Also twice using 10cm³Staining was performed by adding (1:6LR) water.

Color measurement

PES L*＝78.4a*＝35.8b*＝111.9

Cotton L52.3 a 61.6b 11.2

It was found that PES and cotton fibers can be dyed simultaneously using a mixture of disperse and direct dyes in the same dye bath at 95 ℃ for 20 minutes; as expected, the use of electrolytes that favor dye absorption ensures color yield, and the use of low liquid ratios (i.e., 1:6) without the addition of inorganic electrolytes improves direct dye adsorption.

PES/wool Using non-metallized and Pre-metallized acid dyes together with disperse dyes

Along with the crude (i.e., without adjuvant) Teratop yellow HL-G, commercial samples of a) the non-metallized acid dye Erionyl Red A-2BF or b) the 1:2 pre-metallized acid dye Neutrilan yellow A-3R were dissolved in acetone. Samples of PES and wool fabrics were dyed at 85 ℃ for a total dyeing time of 20 minutes using the controlled precipitation dyeing method shown in figure 3, with 4 additions of water (total 1:10 LR).

It was found that PES and wool fibres can be dyed simultaneously in the same dyebath at 85 ℃ for 20 minutes using a mixture of disperse dyes with non-metallized or pre-metallized acid dyes without all dyeing auxiliaries. Depending on the type of acid dye used, the wool textile component is dyed red or yellow and the polyester textile component is dyed yellow.

PES/silk using non-metallized acid dyes and pre-metallized acid dyes along with disperse dyes

Along with the crude (i.e., without adjuvant) Teratop yellow HL-G, commercial samples of a) the non-metallized acid dye Erionyl Red A-2BF or b) the 1:2 pre-metallized acid dye Neutrilan yellow A-3R were dissolved in acetone. Samples of PES fabric and silk fabric were dyed using the controlled precipitation dyeing method shown in figure 3 with 4 additions of water (total 1:10LR) at 85 ℃ for a total dyeing time of 20 minutes.

It was found that PES and wool fibres can be dyed simultaneously in the same dyebath at 85 ℃ for 20 minutes using a mixture of disperse dyes and non-metallized or pre-metallized acid dyes without all dyeing auxiliaries. Depending on the type of acid dye used, the silk fabric component is dyed red or yellow and the polyester fabric component is dyed yellow.

PES/Cotton/wool Using non-metallized acid dyes and reactive dyes along with disperse dyes

Along with crude Terato yellow HL-G, commercial samples of the non-metallized acid dyes Erionyl Red A-2BF and Duractive Black B were dissolved in acetone. Samples of PES fabric, wool fabric and cotton fabric were dyed with 4 additions of water (1:10LR total) at 85 ℃ for a total dyeing time of 20 minutes using the controlled precipitation dyeing method shown in figure 3.

The cotton fabric component was dyed blue, the wool fabric red and the polyester fabric component yellow.

The results show that PES fibres, wool fibres and cotton fibres can be dyed simultaneously to different colours in the same dyebath at 85 ℃ for 20 minutes using a mixture of disperse dyes, reactive dyes and non-metallised acid dyes without all dyeing auxiliaries.

Example 8 one-pot dyeing of solid objects

This example describes the results obtained from dyeing 3D printed nylon 12(PA12) using disperse dye (Dianix blue-ACE) at atmospheric pressure, boiling (98 ℃) using two different solvent systems. The obtained stained samples were compared in terms of shade depth and the process conditions (i.e. temperature used, solvent system) employed.

The dyed substrate was a white solid, 3D printed nylon 12 part.

The dyes used in this experiment were commercial grade and used without purification; dianix blue ACE manufactured by Dystar.

In the lamp cabinet at D₆₅Photographs of all samples were recorded using a Samsung Galaxy S6+ cell phone camera under light source.

All dyeings are made by placing the dye, substrate and solvent in a container placed on a hot plate and heated to the desired treatment temperature. The temperature of the dye bath was measured using a glass mercury thermometer.

Solvent System 1 (Water)

Following the procedure shown in FIG. 12A, staining with 10:1LR yielded 2% omf (Dianix blue-ACE). At the end of the staining, the samples were rinsed thoroughly in running tap water and dried in the open air. A photograph of the stained sample is shown in fig. 12B.

Solvent system 2 (Water: Glycerol; 80:20)

Following the procedure shown in FIG. 12C, 2% omf (Dianix blue-ACE) was produced using 10:1LR (liquid containing water: glycerol; 80: 20). At the end of the staining, the samples were rinsed thoroughly in running tap water and dried in the open air. A photograph of the stained sample is shown in fig. 12D.

By visual inspection of the stained samples, it is clear that the samples obtained using the glycerol: water solvent system have the highest shade depth (compare fig. 12B and 12D).

Claims

1. A method of coloring a polymeric substrate, the method comprising:

a) subjecting the polymeric substrate to a tinting liquid at a temperature T1, T1 being less than 100 ℃, the tinting liquid comprising at least one colorant dissolved in a first solvent system to provide a polymeric substrate wetted by the tinting liquid;

c) separating the pigmented polymeric substrate from the mixture of the first and second solvent systems and any remaining colorant;

wherein the colorant or colorant dye is more soluble in the first solvent system than in the second solvent system.

2. The method of claim 1, wherein the step of adding the second solvent system comprises adding the second solvent system part by part to a mixture of the polymer substrate and the tinting liquid.

3. The method of claim 1 or 2, wherein the second solvent system comprises water.

4. The method of claim 3, wherein the second solvent system is water.

5. The method of any preceding claim, wherein the first solvent system and the second solvent system are miscible.

6. The method of any preceding claim, wherein the first solvent system is an organic solvent or a mixture of one or more organic solvents.

7. The method of claim 6, wherein the first solvent system is a polar organic solvent or a mixture of polar organic solvents.

8. The method of claim 7, wherein the first solvent system comprises acetone.

9. The method of claim 7, wherein the first solvent system comprises a solvent selected from the group consisting of glycerol, Ethylene Glycol Diacetate (EGD), Triethylene Glycol Monomethyl (TGM), dipropylene glycol methyl ether (DME), and 1-methoxy-2-propanol.

10. The method of any preceding claim, wherein the polymeric substrate is a fibrous substrate.

11. The method of claim 10, wherein the fibrous substrate comprises fibers selected from the group consisting of: polyester, nylon, polyurethane, wool, silk, cotton or mixtures thereof.

12. The method of claim 11, wherein the fibrous substrate comprises polyester fibers.

13. The method of claim 12, wherein the fibrous substrate comprises polyester fibers and at least one fiber selected from the group consisting of cotton, regenerated cellulose, wool, silk, polyamide, different polyesters, polyvinyl chloride, polyacrylonitrile, mohair, cashmere, and polyurethane.

14. The method of claim 13, wherein the fibrous substrate comprises a material that is a blend of polyester fibers and at least one fiber selected from the group consisting of cotton, regenerated cellulose, wool, silk, polyamide, different polyesters, polyvinyl chloride, polyacrylonitrile, mohair, cashmere, and polyurethane.

15. The method of claim 14, wherein the fibrous substrate comprises a first material comprising polyester fibers and a second material comprising at least one fiber selected from the group consisting of cotton, regenerated cellulose, wool, silk, polyamide, a different polyester, polyvinyl chloride, polyacrylonitrile, mohair, cashmere, and polyurethane.

16. The method of claim 15, wherein the fibrous substrate is a one-piece garment.

17. The method of any one of the preceding claims, wherein the ratio of the total volume of the first solvent system to the total volume of the second solvent system is from 1:2 to 1: 20.

18. The method of claim 16, wherein the ratio of the total volume of the first solvent system to the total volume of the second solvent system is from 30:70 to 10: 90.

19. The method of any preceding claim, wherein the weight ratio of the polymeric substrate to the first solvent system is from 3:1 to 1: 3.

20. The method of any preceding claim, wherein the at least one colorant is at least one dye.

21. The method of claim 20, wherein the at least one dye is a disperse dye.

22. The method of any preceding claim, wherein the method comprises dissolving the at least one colorant in the first solvent system to form the tinting liquid.

23. The method of any of the preceding claims, wherein the tinting liquid does not comprise a dispersant.

24. A polymer or fibrous substrate obtainable according to the method of any one of the preceding claims.