WO2019149914A1 - Binder composition, colourant composition and coloured substrate - Google Patents

Binder composition, colourant composition and coloured substrate Download PDF

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Publication number
WO2019149914A1
WO2019149914A1 PCT/EP2019/052553 EP2019052553W WO2019149914A1 WO 2019149914 A1 WO2019149914 A1 WO 2019149914A1 EP 2019052553 W EP2019052553 W EP 2019052553W WO 2019149914 A1 WO2019149914 A1 WO 2019149914A1
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WO
WIPO (PCT)
Prior art keywords
colour
colourant
composition
attire
binder
Prior art date
Application number
PCT/EP2019/052553
Other languages
French (fr)
Inventor
Lauren BOWKER
Original Assignee
TheUnseen Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TheUnseen Limited filed Critical TheUnseen Limited
Publication of WO2019149914A1 publication Critical patent/WO2019149914A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0004—General aspects of dyeing
    • D06P1/0016—Dye baths containing a dyeing agent in a special form such as for instance in melted or solid form, as a floating film or gel, spray or aerosol, or atomised dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/004—Dyeing with phototropic dyes; Obtaining camouflage effects
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
    • D06P1/48—Derivatives of carbohydrates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/54—Substances with reactive groups together with crosslinking agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6138—Polymerisation products of glycols, e.g. Carbowax, Pluronics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6424—Compounds containing isocyanate or isothiocyanate groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65118—Compounds containing hydroxyl groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/001—Special chemical aspects of printing textile materials

Definitions

  • This invention relates to a binder composition for binding a colourant, particularly an encapsulated colour-change component, to a substrate and the use of the binder composition, a colourant composition for applying a colour coating to a substrate.
  • the invention relates particularly to a binder for applying a colour-change component to sports attire such as a garment or footwear.
  • Pigments, dyes and colour-change components may be applied to a substrate as a coating and provide a fixed colour or provide a dynamic change in colour as a response to changing prevailing conditions for example temperature, exposure to UV, pressure experienced, or time.
  • Known colour-change materials include leuco-dyes and liquid crystals, for example thermochromic cholesteric or chiral nematic liquid crystals. Such materials may be encapsulated through a variety of means and materials, for example via complex coacervation with gum arabic and gelatin.
  • Thermochromic colour change components reversibly change between different coloured states or a coloured and colourless state when subjected to a change in temperature of a sufficient magnitude.
  • a coated material will typically retain colour until a certain temperature for retention of the complete coloured state is reached.
  • the composition will then progressively change colour or become colourless as the temperature increases or decreases until it has completely changed colour. This process may be reversible or irreversible.
  • Thermochromic materials having standard colour-change schemes and bandwidths, that is a difference in temperature at which colour-change occurs from one colour to another colour and in reverse from the second colour to the first, are commercially available, for example from LCR Hallcrest.
  • thermochromic colour-change components typically preserves the thermochromic mechanism of the encapsulated material.
  • the colour-change component is stabilised in a binder system within the capsule.
  • Thermochromic encapsulated colour- change components have been incorporated into or coated on textiles for many years. For example, in 1989, the Generra Sportswear Company in Seattle developed the Hypercolor brand using encapsulated leuco-dyes and a cross-linked binder system which. In the field of textiles, this system may be known as a“pigment wash” system. Numerous attempts have been made to develop suitable combinations of textiles and colour-change components with limited success.
  • Colour-change compositions may be applied to a wide range of substrates including ceramics, ceramic-matrix composites, man-made and natural polymers, polymer-matrix composites, metals, metal-matrix composites and the like.
  • a wide range of colourants including colour-change compositions and processes for their application to a fabric or yarn substrate are known.
  • the coating is suitably relatively thick and may have physical properties which may differ from those of the substrate which may adversely impact the physical characteristics and“feel” of the coated substrate.
  • encapsulated colour-change components may provide relatively low colour intensity thus requiring a higher level of colour-change component to achieve a desired intensity.
  • the flexibility and durability of the substrate may be impaired as a consequence.
  • Some known binder formulations for adhering pigments to fabrics are flexible and durable but these typically contain solvent concentrations which may damage an encapsulated colour-change component, diminish the colour intensity and degrade the colour and thermochromic activity over time.
  • Colour change compositions may also need to comply with appropriate safety standards, for example Manufacturing Restricted Substances List regulations, for example a formaldehyde content of not more than 0.2 parts per million.
  • the invention provides a binder composition comprising:
  • a colourant composition comprising a colourant to a substrate.
  • the binder composition is able to carry a colourant or colourant composition so as to apply the colourant or colourant composition to the substrate at the time the binder composition is applied to the substrate.
  • the invention further provides in a second aspect, the use of a binder composition comprising a binder comprising a polyurethane derived from a polymer with free hydroxyl end groups, a blocked isocyanate cross-linker and a processing lubricant in a colourant composition comprising a colourant component, to adhere the colourant component to a substrate.
  • 'blocked isocyanate refers to a molecule containing one or more isocyanate moieties where one or more of those moieties have been covalently reacted with a group to provide a protecting group for the isocyanate moiety to render the group“blocked”.
  • the protecting group may be removed under certain reaction conditions, for example subjecting the“blocked isocyanate” to a particular elevated temperature dependent on the blocking group such that the unblocked isocyanate moiety may then react as required.
  • the binder composition provides a substrate with a coloured coating, for example a film or fabric with favourable properties including brightness of colour, a resistance to rubbing, washing, and a soft and flexible coating.
  • the binder composition forms a coating which provides the requisite durability and flexibility required for a range of substrates and applications.
  • the binder composition is flexible and durable but without requiring a significant level of solvent which reduces the risk of interference with the structure or function of the encapsulated material.
  • a novel colour composition having a colourant component and a polyurethane binder system enables the colourant component to be bound to a substrate to provide a coloured substrate and a desirable combination of physical and other performance characteristics.
  • the invention provides a colourant composition adapted to be bound to a substrate, preferably a fabric, wherein the colourant composition comprises a colourant component and a binder composition comprising a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate cross-linker and a processing lubricant.
  • a binder composition comprising a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate cross-linker and a processing lubricant.
  • the invention provides a coloured fabric comprising a fabric having a colourant composition bound to the fabric wherein the colourant composition comprises a colourant component and a binder composition comprising a polyurethane, preferably an aliphatic polyurethane, derived from a polymer with free hydroxyl end groups, a cross-linker preferably a blocked isocyanate crosslinker and a processing lubricant.
  • the colourant composition comprises a colourant component and a binder composition comprising a polyurethane, preferably an aliphatic polyurethane, derived from a polymer with free hydroxyl end groups, a cross-linker preferably a blocked isocyanate crosslinker and a processing lubricant.
  • the invention provides a method of providing a fabric which comprises applying to a fabric a colourant, composition comprising a colourant component and a binder composition which comprises a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate crosslinker and a processing lubricant.
  • a colourant composition
  • a binder composition which comprises a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate crosslinker and a processing lubricant.
  • the colourant may be a pigment, colour-change component or other material capable of imparting colour to a substrate.
  • the colourant comprises a colour-change component, especially an encapsulated colour-change component,
  • Encapsulated colourants may be relatively large and difficult to adhere to a substrate where the substrate and the encapsulate are of similar orders of magnitude in size.
  • the binder composition of the invention enables encapsulated colourants to be bound to such substrates, despite the relatively thick coatings typically necessary to accommodate the capsule size.
  • the composition when applied to the substrate suitably provides intense colours, contrast between different colours and responsive colour-change and adherence to the substrate and a desired level of colourfastness during laundering, as regards resistance to rubbing and resistance.
  • the colour-change composition is suitably dermatologically acceptable in view of its likely contact with the skin of a subject.
  • the term“static colour” refers to a colour produced using colour change component that will not change colour as a result of molecular or physical transformation and which may or may not have iridescent refractive colour shifts
  • changing colour and “dynamic colour” refer to colour- change component which exhibits a reversible colour change in response to stimuli.
  • single colour change refers to a colour-change component which exhibits a one-time colour change that may be activated from one colour to the next by a trigger but which is not reversible.
  • single colour set refers to a colour-change component which shows a colour-change that is triggered but that then stays until a second trigger deactivates it back to the first colour.
  • the term “tuned colour” refers to a colour-change component or components which have been formulated to change colour in response to a particular set of parameters in a pre-determined manner consistent with a design concept.
  • the term“translucent” means a light transmittance of between 1 % and 99% of a range or ranges of light with wavelengths between 390 to 700 nm.
  • the colourant composition preferably comprises one or more colour-change components.
  • the composition may additionally comprise a pigment or other material which does not change colour in addition to a colour-change component.
  • the colour-change component(s) or pigment may provide static colour, dynamic colour, a single colour-change, a single colour set or tuned colour.
  • the colour-change component may be disposed within the capsule, the shell of the capsule, or provided as a component of a coating on the capsule.
  • the colour-change may occur due to stimuli from a person, such as body temperature or from external factors for example a change in wind-chill, temperature or moisture, either ambient temperature or humidity.
  • a person such as body temperature or from external factors for example a change in wind-chill, temperature or moisture, either ambient temperature or humidity.
  • colour-change is stimulated by contact with the body of a person wearing a fabric comprising the colour-change composition or pressure for example due to wind resistance.
  • the colour-change composition binds to the substrate, preferably fabric, and provides a desired combination of characteristics including vivid colours and, where applicable, colour-change, washfastness, rubfastness and lightfastness and resistance to degradation due to UV light.
  • the substrate is a fabric
  • the composition according to the invention advantageously provides a desirable“feel” for the subject or wearer of the fabric and does not feel coated.
  • the composition suitably does not alter the feel of the fabric as compared to the feel of the fabric without the printed colour composition to a degree perceptible by the subject.
  • Colour intensity may be measured through the use of the CIELab colour space, wherein different colours may be compared with respect to mathematical constants for determining lightness (L), hue (H), and chroma (C) which is concerned with the purity of the hue. Different hues have different maximum available chroma values due to the range of colours discernible by the human eye.
  • the present invention enables colour intensities of greater than above 50%, preferably above 80 % of the available chroma values for any particular hue to be obtained.
  • the colour change is noticeable to the human eye and, preferably there is a change in DE value of at least 1.
  • washfastness is retained after 50 washes in a representative domestic, automatic washing machine as part of a representative or typical load.
  • Rubfastness is suitably determined by measuring colour brightness and material properties when subjected to hard rubbing.
  • Adequate lightfastness is suitably provided if colour brightness and colour- change/thermochromic sensitivity is retained upon exposure to UV light according to the test method set out below in the examples.
  • the invention provides a sports product comprising a fabric formed into a garment which fabric is coated with a colourant, preferably a colour-change, composition bound to the fabric, wherein the composition comprises a colourant, and a binder composition comprising a binder which preferably comprises an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker preferably a blocked isocyanate cross-linker and a processing lubricant.
  • a sports product comprising a fabric formed into a garment which fabric is coated with a colourant, preferably a colour-change, composition bound to the fabric, wherein the composition comprises a colourant, and a binder composition comprising a binder which preferably comprises an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker preferably a blocked isocyanate cross-linker and a processing lubricant.
  • the sports product is preferably a garment, footwear or other item of attire, for example a sprint suit, T-shirt singlet garment.
  • the composition of the invention is particularly useful when applied to a garment or item of attire which fits closely to the body of the subject.
  • the garment closely contacts the skin, for example skin-tight, so that body heat warms different areas of the garment to provide colour-change in use in some parts of the garment but not in others or to provide different colour-change in different parts of the garment.
  • high performance sports-wear examples include track and field sprint-suits and singlets, winter sports racing attire, especially ski-suits and attire for bobsleigh, luge and other winter sports, cycling suits especially for use in track cycling and time-trialling, swimsuits and other attire for high performance water-based sports.
  • Compositions of the invention may also be employed with lingerie, leisure-wear, sports attire for general wear, for example sports-style wear, yoga and the like.
  • sports footwear in which the invention may be employed include specialist shoes for sports including indoor use and outdoor use for example footwear for football, rugby, hockey, running, American football, cricket, baseball, tennis, basketball, golf, athletics spikes, winter sports footwear, sports style trainers and personalised athletic footwear.
  • the invention may also be used in other fields including in fashion, healthcare applications, automotive or transport applications and in interior, architecture and construction fields.
  • the binder and its colour-change component may for example be used to create garments and accessories that change colour seasonally or with changing light, for example day and night.
  • composition of the invention may be tuned and applied to a carrier, for example a bandage or dressing that would provide an external indication of a change of temperature assisting in monitoring the healing of a wound such as a chronic wound.
  • a carrier for example a bandage or dressing that would provide an external indication of a change of temperature assisting in monitoring the healing of a wound such as a chronic wound.
  • the substrate will suitably comprise a fabric which is non-toxic, comfortable, tight fitting and able to communicate temperature accurately and not be in direct contact with the wound.
  • the composition of the invention may be used to create colour shifting trims in vehicles that change colour according to the season, locations or in response to changing stimuli for example temperature and UV in the interior of the vehicle and linked to systems to provide automated control of temperature or the like.
  • the composition may provide an aesthetic function or, for example a safety function indicating extremes of temperature within a vehicle interior.
  • composition of the invention may be used to create textiles for buildings and interiors that communicate to an observer information about UV levels, weather, temperature and for example be linked to temperature or humidity control systems to provide automated climate control and for aesthetic purposes, for example to provide colour-change seasonally or in different light conditions, for example day and night.
  • the colour-change of the composition may be tailored according to the desired colour-changes and intended use.
  • a single colour-change for example from black to another colour including black to white, black to yellow or gold may be provided.
  • multiple colour-change for example from black to red to green to blue to black may be provided as the temperature or water/moisture level changes.
  • a“colour-change” compound or composition we include any material, for example a dye, pigment or encapsulated component or composition which, in response to an external parameter such as heat, light, moisture, pressure or the like, especially heat, is capable of a visual change from a first colour to a second or subsequent further colour, for example a third or fourth colour or between clear or transparent and coloured.
  • the colour-change component comprises an encapsulated liquid crystal.
  • a substrate or fabric may be coloured in a base colour and the colour-change composition is then applied to the substrate.
  • the colour-change composition has a coloured state and a transparent state such that the base colour is visible when the colour-change component is in the transparent state and, when in the coloured state, presents a colour to an observer based on the coloured state or a combination of the coloured state and the base colour.
  • Use of two or more colour-change component may allow multiple colour-changes or a succession of colours to be observed in response to changing stimulus, for example temperature, advantageously offering a wide range of product design opportunities.
  • the substrate may also comprise one or more a non-colour-change component as desired.
  • One or more colour-change components may be employed which change colour at different temperatures to provide one or more colour changes.
  • the temperature at which colour-change occurs may be tuned as desired. Where there are multiple colour-change components, the temperature range or bandwidth over which a particular colour appears or transitions from one colour to another may be tuned.
  • the invention provides a substrate, especially a fabric, having multiple colour-changes which occur at different temperatures.
  • Known binder compositions may be opaque or translucent or white such that the underlying colour is perceived by an observer as less vivid or a pastel shade.
  • the binder composition of the invention may be translucent but is preferably transparent such that the base colour of the substrate is visible when the colour-change compound is in its transparent state. Where the colour-change component comprises a liquid crystal, the binder is transparent.
  • the binder may be matte or pearlescent in appearance.
  • the present binder composition suitably allows the underlying colour to be visible in a vivid manner, thereby providing an intense and striking visual effect.
  • the colourant may comprise a static colourant, that is a fixed colour and not susceptible to colour-change, and/or a colour-change component, preferably a leuco-dye or an encapsulated dye as described herein.
  • Encapsulated liquid crystal colour-change components are preferred as providing a transparent state.
  • Leuco-dyes while suitable for use in the present invention may undergo colour-change from white to a colour.
  • the underlying colour of the fabric may appear less vivid due to the white state rather than a transparent state.
  • the binder composition may comprise a pigment which may enhance the vividness of the colour.
  • a binder composition according to the invention in its various aspects comprises or is suitably for use with a colour-change composition comprising an encapsulated liquid-crystal colour-change compound.
  • the substrate to which the colour-change composition is applied may be a fabric or a textile, a polymer including a polymer matrix composite, a metal including alloys and metal matrix composites, a ceramic including ceramic matrix composites.
  • the substrate comprises a fabric or textile
  • the fabric comprises a natural fibre, a synthetic fibre or a combination thereof.
  • the fabric may be woven, knitted or in any suitable form.
  • suitable natural fibres include cotton, wool, linen, silk and combinations thereof.
  • suitable synthetic fibres include polyester, polyamide, nylon, olefin, acetate, acrylic, rayon, modal, aramid, for example Kevlar® a registered trademark of Du Pont, Inc. and polyamide polyurethane blends for example as used in elastane-containing synthetic textiles.
  • Further examples of suitable fabrics include Carvico and Jersey Lomellina.
  • the fabric is designed and intended to be stretched and to recover to its original shape whilst being worn.
  • the colourant printed on the fabric and bound thereto by a binder typically lacks the elasticity of the fabric itself. Upon stretching, the body of colourant and binder material may undergo fracture leading to fissures known as“white crack”. Upon recovery of the fabric to its original shape, discontinuities may remain visible and give an undesirable aesthetic appearance.
  • the colourant composition may be advantageously applied to an elastic fabric and be appropriately bound whilst retaining the desired and physical performance characteristics and elasticity of the fabric.
  • the invention provides a coloured, preferably colour-change, attire comprising an elastic fabric comprising a colourant composition bound to the fabric wherein the colourant composition comprises a colourant component, and a binder composition comprising a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate cross-linker and a processing lubricant.
  • a binder composition comprising a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate cross-linker and a processing lubricant.
  • the elastic fabric is suitable for use as a functional sports fabric or textile, preferably having an elongation of at least 30%, especially an elongation of at least 50%, preferably at least 80% and especially at least 150% desirably at least 200%.
  • % elongation we mean that the colour-change fabric is stretched to at least the specified % elongation and then returns return to its unstretched size and shape within 2 minutes.
  • the elastic fabric comprises a synthetic elastomer as a textile fibre.
  • the synthetic elastomer comprises a pure polyether/urea copolymer or a polyurethane/polyether copolymer.
  • Examples of synthetic elastomers include Elastane, Spandex, Lycra, Elaspan, Aceporta, Creora, INVIYA, and the like.
  • An elastic fabric may comprise a synthetic elastomer and a conventional fibre, for example polyamide and polyester.
  • the elastic fabric or fibre comprises elastane for example Spandex®, a registered trademark of Dupont, Inc. RadiciSpandex S-17B polyether-based Spandex/elastane filament is a particularly suitable example.
  • the elastic fibre may be present in the fabric at a conventional or known level, for example 15% as a proportion of the fibres in the fabric.
  • Thin fabrics for example thin elastic fabrics used in sportswear and which are designed to conform snugly to a body shape of the wearer, may not readily lend themselves to printing with encapsulated colour-change components.
  • Thin fabrics present less substrate for the binder to bind to than thicker materials which may limit the loading of the colour-change component on a thin fabric. This may result in a lesser intensity of colour and a heavy or otherwise compromised feel to the fabric.
  • composition of the invention may be readily applied to a very thin fabric, thereby allowing its use with high performance, elastic fabrics.
  • a thin fabric may typically have a thickness of 5 to 50 microns.
  • the invention also provides a method of providing a colour-change effect in a colour-treated attire, especially elastic attire, adapted to be worn by a subject wherein the colour-treated attire comprises a colour-change composition according to the invention wherein the colour of the attire in one area of the attire differs to the colour of the attire in a different area of the attire and the colour in at least one area is changeable in response to an external stimulus.
  • the external stimulus is selected from body temperature of the subject, pressure experienced by the subject due to movement and water.
  • different parts of the attire are subject to different levels of stimulus during movement of the subject.
  • the different levels of stimulus are suitably provided by the attire being in contact with different parts of the body at different temperatures.
  • the surface temperature of the attire suitably differs from area to area of the attire.
  • the attire conforms to contours of the body of the subject wherein the colour-change in different areas of the attire is dependent upon contact with different areas of the body of the subject during movement, for example during running and especially sprinting,
  • the invention is especially suitable for use with an elastic fabric adapted to be worn in a close-fitting manner to the body of a subject.
  • Changes in body temperature or differences in body temperature in different areas of contact between the fabric and the body may also provide a different colour-change effect for example in medical applications including wound dressings, bandages and the like.
  • the colour-change composition may comprise any known encapsulated colour-change component selected from a leuco dye and a liquid crystal, for example a chiral liquid crystal mixture.
  • a combination of leuco dyes and liquid crystals may be employed to provide multiple, for example 2, 3, 4, 5 or 6, colour changes. Combinations of colour-change materials are suitably mixed together.
  • the colour-change compound comprises an encapsulated liquid crystal.
  • Encapsulated leuco dyes change colour as a result of the leuco material melting within the capsules above a certain temperature, at which point a reversible reaction occurs producing or eliminating a colour.
  • Colour-change in encapsulated liquid crystals occurs as a result of the temperature effecting a change in the chiral liquid crystal structure for example chiral nematic and chiral cholesteric crystals.
  • Encapsulated liquid crystals are preferred, suitably an encapsulated thermochromic slurry, comprising from 30 to 50% solids, for example 40%.
  • liquid crystal and/or leuco-dye may be employed.
  • the liquid crystal suitably comprises a cholesteric or a chiral nematic liquid crystal.
  • Chiral nematic liquid crystals provide bright, strong colour effects with high reflectance.
  • Cholesteric- type liquid crystals typically provide colour effects which are less intense than chiral nematic liquid crystals but are of lower cost and may be suited to larger volume markets.
  • a mixture of chiral nematic and cholesteric liquid crystals may be employed to optimise product performance and cost.
  • the liquid crystal suitably comprises only chiral nematic liquid crystals.
  • the liquid crystal is suitably encapsulated using known techniques and materials, for example cross-linked gum Arabic and gelatin, at known levels.
  • the encapsulate wall material comprises a polymer or a combination of polymers.
  • the wall material preferably comprises from 1 to 30%, more preferably 5 to 25%, for example 8% or 20% by weight of wall material based on the weight of the encapsulated liquid crystal.
  • encapsulated liquid crystals may be employed including cholesterol-like chiral organics including cholesteryl carbonate esters, and chiral nematic liquid crystals. Suitable encapsulated liquid crystals are available from a range of sources including LCR Hallcrest.
  • the encapsulated liquid crystal is suitably incorporated into the composition as an aqueous slurry comprising from 10 to 90%, preferably 15 to 80% and especially 20 to 70% of the encapsulated liquid crystal in water, for example a 40% or 50% slurry of the encapsulated liquid crystal in water.
  • the colourant component is preferably present at a level of 20 to 70%, more preferably 30 to 65% and especially 30 to 50%, for example 32% and 40% by weight of the colourant composition.
  • the colourant composition may be non-iridescent or iridescent other appearances may be provided, for example matte, pearlescent, gloss and iridescent according to the desired effect.
  • Iridescence suitably provides structural refraction of incident light to provide a shimmering effect of multiple colours or a rainbow of colours and arises due to the colourant composition forming a film or coating when applied to the attire substrate and having suitable refractive characteristics.
  • the colourant component may be encapsulated using any known material for example cross-linked gum Arabic and gelatin, polyvinyl alcohol and melamine formaldehyde at levels suitable for the prevailing industry standard.
  • the encapsulate wall material comprises a polymer or a combination of polymers.
  • the wall material comprises a combination of gum arabic and polyvinyl alcohol.
  • the wall material preferably comprises from 1 to 30%, more preferably 5 to 25%, for example 8% or 20% by weight of wall material based on the weight of the colourant composition.
  • formaldehyde and/or paraformaldehyde may be employed and carried into the encapsulated product.
  • paraformaldehyde and formaldehyde are removed during production of the colourant composition.
  • the colourant composition contains less than 0.2% by weight of formaldehyde and paraformaldehyde and desirably is substantially free of these materials.
  • the binder composition suitably provides a polymer film or coating on or in the attire or substrate to bind the colourant component to the substrate or attire.
  • the binder has a soft feel to the touch and being able to be elongated to at least 30%, preferably 50%, desirably at least 80%, for example at least 200%.
  • the binder comprises a polyurethane, preferably an aliphatic polyurethane with free hydroxyl end groups.
  • the binder is selected from a polyurethane polyether and a polyester based polyurethane.
  • the binder comprises a polyurethane polyether.
  • suitable binders include the IMPRAFIX range of products available from Covestro Chemicals, for example IMPRAFIX1794.
  • the binder is suitably present at a level of 10 to 50%, preferably 20 to 40% by weight of the colour-change composition.
  • the cross-linker is water-based.
  • the cross-linker must be able to cross-link the binder and suitably comprises an aliphatic diisocyanate, preferably a blocked aliphatic diisocyanate.
  • the blocked isocyanate has a deblocking temperature of at least 80°C, preferably at least 100°C, more preferably in the range 100 to 180°C.
  • Suitable blocked isocyanates include the EDOLAN range of cross-linker products available from Tanatex Chemicals, for example EDOLAN SN, EDOLAN GS and diethyl malonate which deblock at 100-120C, 3,5-dimethylpyrazole which deblocks at 110-120C, methylethylketoxime which deblocks at 120-140C, and caprolactam which deblocks at 160- 180C.
  • the cross-linker is suitably present at a level of 5 to 30%, preferably 10 to 20% by weight of the colourant composition.
  • the processing lubricant may provide several functions and suitably aids application of the composition to the substrate and may act as a co-solvent to maintain the colourant composition as a homogeneous mix or suspension during application to the substrate.
  • the lubricant suitably also aids deposition of the colourant composition onto the surface fibre as a coating and penetration of the composition into the substrate, especially in a fabric.
  • the lubricant may also lubricate the applicator used in the application process, for example a printing process, thereby aiding uniformity of deposition.
  • the process lubricant comprises a glycol-based stabiliser, preferably an alkylene glycol for example polyethylene glycol and polypropylene glycol.
  • suitable processing lubricants include glycerol, hydrophilic aliphatic polyureas, preferably having a molecular weight from 1 to 1000, hydrophilic siloxanes, preferably having a molecular weight from 1 to 1000, gum Arabic, gelatin, xantham gum, guar gum, alginate, carrageen, locust bean gum, pectin and starch.
  • Polyethylene glycol having a molecular weight from 1 to 1000 and polypropylene glycol having a molecular weight from 1 to 1000 are preferred.
  • the process lubricant is present in the dye composition at a level of 1 to 15%, preferably 5 to10 % by weight of the composition.
  • composition of the invention may also to be applied to very thin, lightweight functional and performance fabrics.
  • the colourant composition suitably further comprises an aqueous solvent.
  • the aqueous solvent is selected from water and a mixture of water and a polar organic solvent.
  • polar organic solvents include alcohols, for example isopropanol.
  • the solvent is suitably free of organic solvent.
  • an organic co-solvent preferably constitutes a minor component of the solvent and is not present at such a level where it disrupts the encapsulation wall of the colourant composition.
  • the colourant composition suitably further comprises a UV stabiliser.
  • the UV stabiliser suitably imparts lightfastness and resistance to degradation from exposure to UV.
  • Any known UV stabilisers that are compatible with the colourant encapsulate may be employed.
  • Preferred UV stabilisers include hindered amine light stabilisers (HALS), for example LOWLITE 18 available from Chempoint Ltd and the Tinuvin range of HALS available from BASF.
  • HALS hindered amine light stabilisers
  • Colourant compounds which have a coloured state and a colourless state are especially suitable for use in the invention.
  • Colour-change may occur over a temperature range and over a period of time, thereby providing a gradual change of colour.
  • the components of the colourant composition are suitably mixed together under ambient conditions to provide a colourant composition, preferably an encapsulated thermochromic liquid crystal slurry suitable for application to the substrate.
  • the dye composition is then suitably applied to a substrate, preferably a fabric, using a known film-forming, printing or coating process, for example spray coating, spin coating painting, dyeing, screen-printing, relief printing such as letterpress printing, planographic printing such as lithography and offset lithography and intaglio printing processes such as gravure printing.
  • the process comprises screen printing the composition onto the fabric.
  • a mesh size of 30t and 50t or 70t with between 1 and 6 pulls is employed in a suitable screen printing process to apply the composition to the fabric.
  • the invention provides a method of producing a coloured fabric, preferably a colour-change fabric applying comprising applying a colour-change composition according to the invention to a fabric in a coating process.
  • thermochromic fabric samples are exposed to UV light as per the conditions laid out in ISO105-X12, for 0.5 hours, 1 hour, 3 hours, 6 hours and 12 hours.
  • the exposed samples are then compared to an unexposed reference sample of thermochromic fabric, placed on an identical surface at a temperature 5 degrees below or lower than the red start temperature of the thermochromic (the temperature transition between the smectic and cholesteric phase of the liquid crystal) or, where a leuco dye is being tested, the temperature at which the dye changes colour.
  • the samples are then all increased in temperature to an identical temperature above their clearing point (the temperature transition between the cholesteric and isotropic phases of the liquid crystal) or, for leuco dyes, the colour-change point.
  • the samples are then left to cool, moving from blue, to green, to red, and again to black.
  • the colour intensity of the blue is noted, and compared to the reference sample.
  • the ink is given a score according to the highest length exposure time to which the blue colour of the reference sample adequately compares.
  • the blue colour of the reference is comparable to the 6 hour sample, but not the 12 hour sample, and the time taken for each of these to move through their cholesteric phases was 105 % and 1 15 % of the time taken for the reference sample, respectively.
  • the ink is given a score of 6-105, corresponding to the exposure time to which it is still comparable to the reference sample with respect to colour, and the corresponding effect on thermochromic phase shift as a result of exposure.
  • a colour-change having the following composition is suitable for applying to a sports fabric such as elastane containing fabric known for use in the manufacture of sports fabrics,:
  • thermochromic crystal slurry 30-65 wt%
  • Aliphatic polyurethane with exposed diol ends (binder polymer, for example from the EDOLAN SN range, a trade mark of Tanatex Chemicals) 20 - 40 wt. %
  • Blocked aliphatic diisocyanate (cross linker for binder polymer for example from the IMPRAFIX range, a trademark of Covestro Chemicals) 10 - 20 wt. %
  • Stabilizer for example a screen print lubricant, thickener, slurry stabilizer for example propylene glycol or ethylene glycol 5-10 wt%
  • thermochromic liquid crystal slurry suitable for application to a sports fabric.
  • a composition as described in Example 1 is applied to a fabric containing an elastic polyurethane component (Elastane), for example SPANDEX a trademark of Du Pont.
  • Elastane an elastic polyurethane component
  • the process involves screen printing using a mesh size of 30t to 70t with between 1 and 6 pulls.
  • composition coats the fabric, binds to the fabric and provides a desired combination of characteristics including:
  • the colour-change fabric should stretch to at least 80% elongation and return to its unstretched size and shape within 2 minutes and have a soft, non-tacky feeling as determined by survey evidence.
  • Example 3 Testing of colour-change items of attire The relationship between garment temperature with ambient temperature, skin temperature, and garment humidity, during an experiment to mimic a 100 m sprint were evaluated.
  • An elastane-containing sprint suit comprising 85% polyamide and 15 % elastane (skin-tight) and a singlet (relatively loose fitting) were tested worn by the subject in order to allow garment and skin temperatures to be tested to determine changes in temperature with changing conditions.
  • Temperature change at various locations on the garment provided an indication of the required temperature-change range for a colour-change composition to provide a colour-change effect in a garment in use.
  • Example 4 Example 4
  • the difference in thermal profile between the sprint suit and the singlet enables a colour- change effect to be tailored using the looseness of the garment to control where skin contact occurs and hence to modulate the colour-change effect.

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Abstract

A binder composition and a colourant composition containing the binder composition are provided. The binder comprises a polyurethane derived from a water-soluble aliphatic polymer with free hydroxyl end groups and a blocked isocyanate crosslinker, mixed with a processing lubricant for use in adhering a colourant composition comprising a colourant component to a substrate. The colourant component may be an encapsulated colour-change compound and the substrate an elastic thin fabric formed into a garment which provides colour-change when worn.

Description

BINDER COMPOSITION, COLOURANT COMPOSITION AND COLOURED SUBSTRATE
This invention relates to a binder composition for binding a colourant, particularly an encapsulated colour-change component, to a substrate and the use of the binder composition, a colourant composition for applying a colour coating to a substrate. The invention relates particularly to a binder for applying a colour-change component to sports attire such as a garment or footwear.
Pigments, dyes and colour-change components may be applied to a substrate as a coating and provide a fixed colour or provide a dynamic change in colour as a response to changing prevailing conditions for example temperature, exposure to UV, pressure experienced, or time. , Known colour-change materials include leuco-dyes and liquid crystals, for example thermochromic cholesteric or chiral nematic liquid crystals. Such materials may be encapsulated through a variety of means and materials, for example via complex coacervation with gum arabic and gelatin.
Thermochromic colour change components reversibly change between different coloured states or a coloured and colourless state when subjected to a change in temperature of a sufficient magnitude. As the temperature changes, a coated material will typically retain colour until a certain temperature for retention of the complete coloured state is reached. The composition will then progressively change colour or become colourless as the temperature increases or decreases until it has completely changed colour. This process may be reversible or irreversible. Thermochromic materials, having standard colour-change schemes and bandwidths, that is a difference in temperature at which colour-change occurs from one colour to another colour and in reverse from the second colour to the first, are commercially available, for example from LCR Hallcrest.
With thermochromic colour-change components, encapsulation typically preserves the thermochromic mechanism of the encapsulated material. The colour-change component is stabilised in a binder system within the capsule. Thermochromic encapsulated colour- change components have been incorporated into or coated on textiles for many years. For example, in 1989, the Generra Sportswear Company in Seattle developed the Hypercolor brand using encapsulated leuco-dyes and a cross-linked binder system which. In the field of textiles, this system may be known as a“pigment wash” system. Numerous attempts have been made to develop suitable combinations of textiles and colour-change components with limited success. Colour-change compositions may be applied to a wide range of substrates including ceramics, ceramic-matrix composites, man-made and natural polymers, polymer-matrix composites, metals, metal-matrix composites and the like.
A wide range of colourants including colour-change compositions and processes for their application to a fabric or yarn substrate are known. A need remains to provide coloured attire having an acceptable combination of desired properties such as intensity and vividness of colour, UV stability and lightfastness, reflectivity, adequate binding of the composition to the substrate to ensure resilience to physical processes to which the colour-change substrate will be subjected including repeated washing, rubbing, UV exposure and appropriate feel qualities such as a soft, pleasant feel and lack of tackiness, especially if the attire is to be worn by a subject next to the skin.
However, adhering a colour-change component to a substrate presents a number of challenges, especially where the colour-change component is encapsulated. To accommodate the comparatively large size of the capsule, the coating is suitably relatively thick and may have physical properties which may differ from those of the substrate which may adversely impact the physical characteristics and“feel” of the coated substrate.
Furthermore, encapsulated colour-change components may provide relatively low colour intensity thus requiring a higher level of colour-change component to achieve a desired intensity. The flexibility and durability of the substrate may be impaired as a consequence.
Some known binder formulations for adhering pigments to fabrics are flexible and durable but these typically contain solvent concentrations which may damage an encapsulated colour-change component, diminish the colour intensity and degrade the colour and thermochromic activity over time.
Colour change compositions may also need to comply with appropriate safety standards, for example Manufacturing Restricted Substances List regulations, for example a formaldehyde content of not more than 0.2 parts per million.
A need remains to provide a binder composition which adequately adheres an encapsulated colour-change component to a substrate whilst providing desired aesthetic characteristics and physical properties and feel.
We have now found that the aforementioned problems may be reduced or avoided by providing a novel polyurethane binder composition to bind an encapsulated colourant to a substrate.
In a first aspect, the invention provides a binder composition comprising:
i) a polyurethane binder derived from a polymer with free hydroxyl end groups;
ii) an isocyanate, preferably a blocked isocyanate crosslinker; and
iii) a processing lubricant
for use in adhering a colourant composition comprising a colourant to a substrate.
Suitably, the binder composition is able to carry a colourant or colourant composition so as to apply the colourant or colourant composition to the substrate at the time the binder composition is applied to the substrate.
The invention further provides in a second aspect, the use of a binder composition comprising a binder comprising a polyurethane derived from a polymer with free hydroxyl end groups, a blocked isocyanate cross-linker and a processing lubricant in a colourant composition comprising a colourant component, to adhere the colourant component to a substrate.
The term 'blocked isocyanate” refers to a molecule containing one or more isocyanate moieties where one or more of those moieties have been covalently reacted with a group to provide a protecting group for the isocyanate moiety to render the group“blocked”. The protecting group may be removed under certain reaction conditions, for example subjecting the“blocked isocyanate” to a particular elevated temperature dependent on the blocking group such that the unblocked isocyanate moiety may then react as required.
The binder composition provides a substrate with a coloured coating, for example a film or fabric with favourable properties including brightness of colour, a resistance to rubbing, washing, and a soft and flexible coating. The binder composition forms a coating which provides the requisite durability and flexibility required for a range of substrates and applications. Advantageously, the binder composition is flexible and durable but without requiring a significant level of solvent which reduces the risk of interference with the structure or function of the encapsulated material.
We have further found that a novel colour composition having a colourant component and a polyurethane binder system enables the colourant component to be bound to a substrate to provide a coloured substrate and a desirable combination of physical and other performance characteristics.
In a third aspect, the invention provides a colourant composition adapted to be bound to a substrate, preferably a fabric, wherein the colourant composition comprises a colourant component and a binder composition comprising a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate cross-linker and a processing lubricant.
In a fourth aspect, the invention provides a coloured fabric comprising a fabric having a colourant composition bound to the fabric wherein the colourant composition comprises a colourant component and a binder composition comprising a polyurethane, preferably an aliphatic polyurethane, derived from a polymer with free hydroxyl end groups, a cross-linker preferably a blocked isocyanate crosslinker and a processing lubricant.
In a further aspect, the invention provides a method of providing a fabric which comprises applying to a fabric a colourant, composition comprising a colourant component and a binder composition which comprises a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate crosslinker and a processing lubricant.
In compositions according to the invention, the colourant may be a pigment, colour-change component or other material capable of imparting colour to a substrate. Preferably, the colourant comprises a colour-change component, especially an encapsulated colour-change component,
Encapsulated colourants may be relatively large and difficult to adhere to a substrate where the substrate and the encapsulate are of similar orders of magnitude in size. The binder composition of the invention enables encapsulated colourants to be bound to such substrates, despite the relatively thick coatings typically necessary to accommodate the capsule size.
The composition when applied to the substrate suitably provides intense colours, contrast between different colours and responsive colour-change and adherence to the substrate and a desired level of colourfastness during laundering, as regards resistance to rubbing and resistance. The colour-change composition is suitably dermatologically acceptable in view of its likely contact with the skin of a subject. As employed herein, the term“static colour” refers to a colour produced using colour change component that will not change colour as a result of molecular or physical transformation and which may or may not have iridescent refractive colour shifts
As employed herein, the terms“changing colour” and “dynamic colour” refer to colour- change component which exhibits a reversible colour change in response to stimuli.
As employed herein, the term“single colour change” refers to a colour-change component which exhibits a one-time colour change that may be activated from one colour to the next by a trigger but which is not reversible.
As employed herein, the term“single colour set” refers to a colour-change component which shows a colour-change that is triggered but that then stays until a second trigger deactivates it back to the first colour.
As employed herein, the term “tuned colour” refers to a colour-change component or components which have been formulated to change colour in response to a particular set of parameters in a pre-determined manner consistent with a design concept.
As employed herein, the term“translucent” means a light transmittance of between 1 % and 99% of a range or ranges of light with wavelengths between 390 to 700 nm.
The colourant composition preferably comprises one or more colour-change components. The composition may additionally comprise a pigment or other material which does not change colour in addition to a colour-change component. The colour-change component(s) or pigment may provide static colour, dynamic colour, a single colour-change, a single colour set or tuned colour.
Where encapsulated, the colour-change component may be disposed within the capsule, the shell of the capsule, or provided as a component of a coating on the capsule.
The colour-change may occur due to stimuli from a person, such as body temperature or from external factors for example a change in wind-chill, temperature or moisture, either ambient temperature or humidity. Preferably, colour-change is stimulated by contact with the body of a person wearing a fabric comprising the colour-change composition or pressure for example due to wind resistance.
Advantageously, the colour-change composition binds to the substrate, preferably fabric, and provides a desired combination of characteristics including vivid colours and, where applicable, colour-change, washfastness, rubfastness and lightfastness and resistance to degradation due to UV light. Where the substrate is a fabric, the composition according to the invention advantageously provides a desirable“feel” for the subject or wearer of the fabric and does not feel coated. The composition suitably does not alter the feel of the fabric as compared to the feel of the fabric without the printed colour composition to a degree perceptible by the subject.
Colour intensity may be measured through the use of the CIELab colour space, wherein different colours may be compared with respect to mathematical constants for determining lightness (L), hue (H), and chroma (C) which is concerned with the purity of the hue. Different hues have different maximum available chroma values due to the range of colours discernible by the human eye. The present invention enables colour intensities of greater than above 50%, preferably above 80 % of the available chroma values for any particular hue to be obtained. Suitably, the colour change is noticeable to the human eye and, preferably there is a change in DE value of at least 1.
Preferably, washfastness is retained after 50 washes in a representative domestic, automatic washing machine as part of a representative or typical load. Rubfastness is suitably determined by measuring colour brightness and material properties when subjected to hard rubbing. Adequate lightfastness is suitably provided if colour brightness and colour- change/thermochromic sensitivity is retained upon exposure to UV light according to the test method set out below in the examples.
In a further aspect, the invention provides a sports product comprising a fabric formed into a garment which fabric is coated with a colourant, preferably a colour-change, composition bound to the fabric, wherein the composition comprises a colourant, and a binder composition comprising a binder which preferably comprises an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker preferably a blocked isocyanate cross-linker and a processing lubricant.
Suitably, the sports product is preferably a garment, footwear or other item of attire, for example a sprint suit, T-shirt singlet garment. The composition of the invention is particularly useful when applied to a garment or item of attire which fits closely to the body of the subject. In one embodiment, the garment closely contacts the skin, for example skin-tight, so that body heat warms different areas of the garment to provide colour-change in use in some parts of the garment but not in others or to provide different colour-change in different parts of the garment. Examples of high performance sports-wear in which the invention may be employed include track and field sprint-suits and singlets, winter sports racing attire, especially ski-suits and attire for bobsleigh, luge and other winter sports, cycling suits especially for use in track cycling and time-trialling, swimsuits and other attire for high performance water-based sports. Compositions of the invention may also be employed with lingerie, leisure-wear, sports attire for general wear, for example sports-style wear, yoga and the like.
Examples of sports footwear in which the invention may be employed include specialist shoes for sports including indoor use and outdoor use for example footwear for football, rugby, hockey, running, American football, cricket, baseball, tennis, basketball, golf, athletics spikes, winter sports footwear, sports style trainers and personalised athletic footwear.
The invention may also be used in other fields including in fashion, healthcare applications, automotive or transport applications and in interior, architecture and construction fields.
In fashion applications, the binder and its colour-change component may for example be used to create garments and accessories that change colour seasonally or with changing light, for example day and night.
In healthcare applications, the composition of the invention may be tuned and applied to a carrier, for example a bandage or dressing that would provide an external indication of a change of temperature assisting in monitoring the healing of a wound such as a chronic wound. The substrate will suitably comprise a fabric which is non-toxic, comfortable, tight fitting and able to communicate temperature accurately and not be in direct contact with the wound.
In automotive of transport applications, the composition of the invention may be used to create colour shifting trims in vehicles that change colour according to the season, locations or in response to changing stimuli for example temperature and UV in the interior of the vehicle and linked to systems to provide automated control of temperature or the like. The composition may provide an aesthetic function or, for example a safety function indicating extremes of temperature within a vehicle interior.
In interior design, architecture and construction, the composition of the invention may be used to create textiles for buildings and interiors that communicate to an observer information about UV levels, weather, temperature and for example be linked to temperature or humidity control systems to provide automated climate control and for aesthetic purposes, for example to provide colour-change seasonally or in different light conditions, for example day and night.
Where the colourant comprises a colour-change compound, the colour-change of the composition may be tailored according to the desired colour-changes and intended use. A single colour-change, for example from black to another colour including black to white, black to yellow or gold may be provided. Alternatively, multiple colour-change, for example from black to red to green to blue to black may be provided as the temperature or water/moisture level changes.
In referring to a“colour-change” compound or composition, we include any material, for example a dye, pigment or encapsulated component or composition which, in response to an external parameter such as heat, light, moisture, pressure or the like, especially heat, is capable of a visual change from a first colour to a second or subsequent further colour, for example a third or fourth colour or between clear or transparent and coloured. In a preferred embodiment, the colour-change component comprises an encapsulated liquid crystal.
A substrate or fabric may be coloured in a base colour and the colour-change composition is then applied to the substrate. Suitably, the colour-change composition has a coloured state and a transparent state such that the base colour is visible when the colour-change component is in the transparent state and, when in the coloured state, presents a colour to an observer based on the coloured state or a combination of the coloured state and the base colour. Use of two or more colour-change component may allow multiple colour-changes or a succession of colours to be observed in response to changing stimulus, for example temperature, advantageously offering a wide range of product design opportunities.
The substrate may also comprise one or more a non-colour-change component as desired. One or more colour-change components may be employed which change colour at different temperatures to provide one or more colour changes. By selecting appropriate colour- change components, the temperature at which colour-change occurs may be tuned as desired. Where there are multiple colour-change components, the temperature range or bandwidth over which a particular colour appears or transitions from one colour to another may be tuned.
The invention provides a substrate, especially a fabric, having multiple colour-changes which occur at different temperatures. Known binder compositions may be opaque or translucent or white such that the underlying colour is perceived by an observer as less vivid or a pastel shade. The binder composition of the invention may be translucent but is preferably transparent such that the base colour of the substrate is visible when the colour-change compound is in its transparent state. Where the colour-change component comprises a liquid crystal, the binder is transparent. The binder may be matte or pearlescent in appearance.
The present binder composition suitably allows the underlying colour to be visible in a vivid manner, thereby providing an intense and striking visual effect. The colourant may comprise a static colourant, that is a fixed colour and not susceptible to colour-change, and/or a colour-change component, preferably a leuco-dye or an encapsulated dye as described herein. Encapsulated liquid crystal colour-change components are preferred as providing a transparent state. Leuco-dyes while suitable for use in the present invention, may undergo colour-change from white to a colour. The underlying colour of the fabric may appear less vivid due to the white state rather than a transparent state.
The binder composition may comprise a pigment which may enhance the vividness of the colour.
In preferred embodiments, a binder composition according to the invention in its various aspects comprises or is suitably for use with a colour-change composition comprising an encapsulated liquid-crystal colour-change compound.
The substrate to which the colour-change composition is applied may be a fabric or a textile, a polymer including a polymer matrix composite, a metal including alloys and metal matrix composites, a ceramic including ceramic matrix composites. Preferably, the substrate comprises a fabric or textile
Preferably, the fabric comprises a natural fibre, a synthetic fibre or a combination thereof. The fabric may be woven, knitted or in any suitable form. Examples of suitable natural fibres include cotton, wool, linen, silk and combinations thereof. Examples of suitable synthetic fibres include polyester, polyamide, nylon, olefin, acetate, acrylic, rayon, modal, aramid, for example Kevlar® a registered trademark of Du Pont, Inc. and polyamide polyurethane blends for example as used in elastane-containing synthetic textiles. Further examples of suitable fabrics include Carvico and Jersey Lomellina.
A particular problem arises with fabrics which are elastic and printed with a colourant due to a difference in elasticity of the fabric and the composition which forms the printed body of colour. The fabric is designed and intended to be stretched and to recover to its original shape whilst being worn. However, the colourant printed on the fabric and bound thereto by a binder typically lacks the elasticity of the fabric itself. Upon stretching, the body of colourant and binder material may undergo fracture leading to fissures known as“white crack”. Upon recovery of the fabric to its original shape, discontinuities may remain visible and give an undesirable aesthetic appearance.
We have found that the colourant composition may be advantageously applied to an elastic fabric and be appropriately bound whilst retaining the desired and physical performance characteristics and elasticity of the fabric.
In another aspect, the invention provides a coloured, preferably colour-change, attire comprising an elastic fabric comprising a colourant composition bound to the fabric wherein the colourant composition comprises a colourant component, and a binder composition comprising a binder comprising a polyurethane, preferably an aliphatic polyurethane derived from a polymer with free hydroxyl end groups, a cross-linker, preferably a blocked isocyanate cross-linker and a processing lubricant..
Suitably, the elastic fabric is suitable for use as a functional sports fabric or textile, preferably having an elongation of at least 30%, especially an elongation of at least 50%, preferably at least 80% and especially at least 150% desirably at least 200%.
By “% elongation” we mean that the colour-change fabric is stretched to at least the specified % elongation and then returns return to its unstretched size and shape within 2 minutes.
Preferably, the elastic fabric comprises a synthetic elastomer as a textile fibre. Suitably, the synthetic elastomer comprises a pure polyether/urea copolymer or a polyurethane/polyether copolymer. Examples of synthetic elastomers include Elastane, Spandex, Lycra, Elaspan, Aceporta, Creora, INVIYA, and the like. An elastic fabric may comprise a synthetic elastomer and a conventional fibre, for example polyamide and polyester.
In a preferred embodiment, the elastic fabric or fibre comprises elastane for example Spandex®, a registered trademark of Dupont, Inc. RadiciSpandex S-17B polyether-based Spandex/elastane filament is a particularly suitable example.
The elastic fibre may be present in the fabric at a conventional or known level, for example 15% as a proportion of the fibres in the fabric. Thin fabrics, for example thin elastic fabrics used in sportswear and which are designed to conform snugly to a body shape of the wearer, may not readily lend themselves to printing with encapsulated colour-change components. Thin fabrics present less substrate for the binder to bind to than thicker materials which may limit the loading of the colour-change component on a thin fabric. This may result in a lesser intensity of colour and a heavy or otherwise compromised feel to the fabric.
We have found that the composition of the invention may be readily applied to a very thin fabric, thereby allowing its use with high performance, elastic fabrics. A thin fabric may typically have a thickness of 5 to 50 microns.
In another aspect, the invention also provides a method of providing a colour-change effect in a colour-treated attire, especially elastic attire, adapted to be worn by a subject wherein the colour-treated attire comprises a colour-change composition according to the invention wherein the colour of the attire in one area of the attire differs to the colour of the attire in a different area of the attire and the colour in at least one area is changeable in response to an external stimulus.
Suitably, the external stimulus is selected from body temperature of the subject, pressure experienced by the subject due to movement and water.
Preferably, different parts of the attire are subject to different levels of stimulus during movement of the subject. The different levels of stimulus are suitably provided by the attire being in contact with different parts of the body at different temperatures. The surface temperature of the attire suitably differs from area to area of the attire.
In one embodiment, the attire conforms to contours of the body of the subject wherein the colour-change in different areas of the attire is dependent upon contact with different areas of the body of the subject during movement, for example during running and especially sprinting,
Accordingly, the invention is especially suitable for use with an elastic fabric adapted to be worn in a close-fitting manner to the body of a subject.
Changes in body temperature or differences in body temperature in different areas of contact between the fabric and the body may also provide a different colour-change effect for example in medical applications including wound dressings, bandages and the like.
The colour-change composition may comprise any known encapsulated colour-change component selected from a leuco dye and a liquid crystal, for example a chiral liquid crystal mixture. A combination of leuco dyes and liquid crystals may be employed to provide multiple, for example 2, 3, 4, 5 or 6, colour changes. Combinations of colour-change materials are suitably mixed together. Preferably, the colour-change compound comprises an encapsulated liquid crystal.
Encapsulated leuco dyes change colour as a result of the leuco material melting within the capsules above a certain temperature, at which point a reversible reaction occurs producing or eliminating a colour. Colour-change in encapsulated liquid crystals occurs as a result of the temperature effecting a change in the chiral liquid crystal structure for example chiral nematic and chiral cholesteric crystals. Encapsulated liquid crystals are preferred, suitably an encapsulated thermochromic slurry, comprising from 30 to 50% solids, for example 40%.
Any commercially available liquid crystal and/or leuco-dye may be employed.
The liquid crystal suitably comprises a cholesteric or a chiral nematic liquid crystal. Chiral nematic liquid crystals provide bright, strong colour effects with high reflectance. Cholesteric- type liquid crystals typically provide colour effects which are less intense than chiral nematic liquid crystals but are of lower cost and may be suited to larger volume markets. A mixture of chiral nematic and cholesteric liquid crystals may be employed to optimise product performance and cost. In a preferred embodiment, the liquid crystal suitably comprises only chiral nematic liquid crystals.
The liquid crystal is suitably encapsulated using known techniques and materials, for example cross-linked gum Arabic and gelatin, at known levels. Suitably, the encapsulate wall material comprises a polymer or a combination of polymers. The wall material preferably comprises from 1 to 30%, more preferably 5 to 25%, for example 8% or 20% by weight of wall material based on the weight of the encapsulated liquid crystal.
Any known encapsulated liquid crystals may be employed including cholesterol-like chiral organics including cholesteryl carbonate esters, and chiral nematic liquid crystals. Suitable encapsulated liquid crystals are available from a range of sources including LCR Hallcrest.
The encapsulated liquid crystal is suitably incorporated into the composition as an aqueous slurry comprising from 10 to 90%, preferably 15 to 80% and especially 20 to 70% of the encapsulated liquid crystal in water, for example a 40% or 50% slurry of the encapsulated liquid crystal in water.
The colourant component is preferably present at a level of 20 to 70%, more preferably 30 to 65% and especially 30 to 50%, for example 32% and 40% by weight of the colourant composition.
The colourant composition may be non-iridescent or iridescent other appearances may be provided, for example matte, pearlescent, gloss and iridescent according to the desired effect. Iridescence suitably provides structural refraction of incident light to provide a shimmering effect of multiple colours or a rainbow of colours and arises due to the colourant composition forming a film or coating when applied to the attire substrate and having suitable refractive characteristics.
The colourant component may be encapsulated using any known material for example cross-linked gum Arabic and gelatin, polyvinyl alcohol and melamine formaldehyde at levels suitable for the prevailing industry standard. Suitably, the encapsulate wall material comprises a polymer or a combination of polymers. In one embodiment, the wall material comprises a combination of gum arabic and polyvinyl alcohol. The wall material preferably comprises from 1 to 30%, more preferably 5 to 25%, for example 8% or 20% by weight of wall material based on the weight of the colourant composition.
Certain safety regulations found in Europe for example REACH, CIRS and CPTA, aim to reduce the level of formaldehyde and paraformaldehyde to provide environmentally cleaner materials. During encapsulation, formaldehyde and/or paraformaldehyde may be employed and carried into the encapsulated product. Preferably, paraformaldehyde and formaldehyde are removed during production of the colourant composition. Suitably, the colourant composition contains less than 0.2% by weight of formaldehyde and paraformaldehyde and desirably is substantially free of these materials.
The binder composition suitably provides a polymer film or coating on or in the attire or substrate to bind the colourant component to the substrate or attire.
Suitably, the binder has a soft feel to the touch and being able to be elongated to at least 30%, preferably 50%, desirably at least 80%, for example at least 200%. The binder comprises a polyurethane, preferably an aliphatic polyurethane with free hydroxyl end groups. In a preferred embodiment, the binder is selected from a polyurethane polyether and a polyester based polyurethane. In a more preferred embodiment, the binder comprises a polyurethane polyether. Examples of suitable binders include the IMPRAFIX range of products available from Covestro Chemicals, for example IMPRAFIX1794.
The binder is suitably present at a level of 10 to 50%, preferably 20 to 40% by weight of the colour-change composition.
Preferably the cross-linker is water-based. The cross-linker must be able to cross-link the binder and suitably comprises an aliphatic diisocyanate, preferably a blocked aliphatic diisocyanate. Suitably, the blocked isocyanate has a deblocking temperature of at least 80°C, preferably at least 100°C, more preferably in the range 100 to 180°C. Examples of suitable blocked isocyanates include the EDOLAN range of cross-linker products available from Tanatex Chemicals, for example EDOLAN SN, EDOLAN GS and diethyl malonate which deblock at 100-120C, 3,5-dimethylpyrazole which deblocks at 110-120C, methylethylketoxime which deblocks at 120-140C, and caprolactam which deblocks at 160- 180C.
The cross-linker is suitably present at a level of 5 to 30%, preferably 10 to 20% by weight of the colourant composition.
The processing lubricant may provide several functions and suitably aids application of the composition to the substrate and may act as a co-solvent to maintain the colourant composition as a homogeneous mix or suspension during application to the substrate. The lubricant suitably also aids deposition of the colourant composition onto the surface fibre as a coating and penetration of the composition into the substrate, especially in a fabric. The lubricant may also lubricate the applicator used in the application process, for example a printing process, thereby aiding uniformity of deposition.
Suitably, the process lubricant comprises a glycol-based stabiliser, preferably an alkylene glycol for example polyethylene glycol and polypropylene glycol. Examples of other suitable processing lubricants include glycerol, hydrophilic aliphatic polyureas, preferably having a molecular weight from 1 to 1000, hydrophilic siloxanes, preferably having a molecular weight from 1 to 1000, gum Arabic, gelatin, xantham gum, guar gum, alginate, carrageen, locust bean gum, pectin and starch. Polyethylene glycol having a molecular weight from 1 to 1000 and polypropylene glycol having a molecular weight from 1 to 1000 are preferred. Suitably, the process lubricant is present in the dye composition at a level of 1 to 15%, preferably 5 to10 % by weight of the composition.
The composition of the invention may also to be applied to very thin, lightweight functional and performance fabrics.
The colourant composition suitably further comprises an aqueous solvent. Preferably the aqueous solvent is selected from water and a mixture of water and a polar organic solvent. Examples of polar organic solvents include alcohols, for example isopropanol. Where the colourant component comprises liquid crystal, the solvent is suitably free of organic solvent. Where present, an organic co-solvent preferably constitutes a minor component of the solvent and is not present at such a level where it disrupts the encapsulation wall of the colourant composition.
The colourant composition suitably further comprises a UV stabiliser. The UV stabiliser suitably imparts lightfastness and resistance to degradation from exposure to UV. Any known UV stabilisers that are compatible with the colourant encapsulate may be employed. Preferred UV stabilisers include hindered amine light stabilisers (HALS), for example LOWLITE 18 available from Chempoint Ltd and the Tinuvin range of HALS available from BASF.
Colourant compounds which have a coloured state and a colourless state are especially suitable for use in the invention.
Colour-change may occur over a temperature range and over a period of time, thereby providing a gradual change of colour.
The components of the colourant composition are suitably mixed together under ambient conditions to provide a colourant composition, preferably an encapsulated thermochromic liquid crystal slurry suitable for application to the substrate. The dye composition is then suitably applied to a substrate, preferably a fabric, using a known film-forming, printing or coating process, for example spray coating, spin coating painting, dyeing, screen-printing, relief printing such as letterpress printing, planographic printing such as lithography and offset lithography and intaglio printing processes such as gravure printing. In a preferred embodiment, the process comprises screen printing the composition onto the fabric. By way of example, preferably a mesh size of 30t and 50t or 70t with between 1 and 6 pulls is employed in a suitable screen printing process to apply the composition to the fabric.
All percentages and ratios used herein are by weight of the total binder or colourant composition as appropriate and all measurements made are at 25° C, unless otherwise designated.
In a further embodiment, the invention provides a method of producing a coloured fabric, preferably a colour-change fabric applying comprising applying a colour-change composition according to the invention to a fabric in a coating process.
The invention is illustrated by the following non-limiting examples. All percentages and parts are parts by weight unless otherwise stated
Examples
Test Method - UV Stability
Printed thermochromic fabric samples are exposed to UV light as per the conditions laid out in ISO105-X12, for 0.5 hours, 1 hour, 3 hours, 6 hours and 12 hours. The exposed samples are then compared to an unexposed reference sample of thermochromic fabric, placed on an identical surface at a temperature 5 degrees below or lower than the red start temperature of the thermochromic (the temperature transition between the smectic and cholesteric phase of the liquid crystal) or, where a leuco dye is being tested, the temperature at which the dye changes colour. The samples are then all increased in temperature to an identical temperature above their clearing point (the temperature transition between the cholesteric and isotropic phases of the liquid crystal) or, for leuco dyes, the colour-change point. The samples are then left to cool, moving from blue, to green, to red, and again to black.
The colour intensity of the blue is noted, and compared to the reference sample. The ink is given a score according to the highest length exposure time to which the blue colour of the reference sample adequately compares.
The time taken for the samples to move through their cholesteric phases is also recorded, and each sample given a % score, using the time taken for the reference sample as 100%. This percentage score is then added to score the ink achieves.
For example, the blue colour of the reference is comparable to the 6 hour sample, but not the 12 hour sample, and the time taken for each of these to move through their cholesteric phases was 105 % and 1 15 % of the time taken for the reference sample, respectively. Thus the ink is given a score of 6-105, corresponding to the exposure time to which it is still comparable to the reference sample with respect to colour, and the corresponding effect on thermochromic phase shift as a result of exposure.
Example 1 - Colour-change composition
A colour-change having the following composition is suitable for applying to a sports fabric such as elastane containing fabric known for use in the manufacture of sports fabrics,:
Encapsulated thermochromic crystal slurry 30-65 wt%
Aliphatic polyurethane with exposed diol ends (binder polymer, for example from the EDOLAN SN range, a trade mark of Tanatex Chemicals) 20 - 40 wt. %
Blocked aliphatic diisocyanate, (cross linker for binder polymer for example from the IMPRAFIX range, a trademark of Covestro Chemicals) 10 - 20 wt. %
Stabilizer (for example a screen print lubricant, thickener, slurry stabilizer for example propylene glycol or ethylene glycol) 5-10 wt%
The components above are mixed together under ambient conditions to provide a encapsulated thermochromic liquid crystal slurry suitable for application to a sports fabric.
Example 2 - Production of colour-change item of attire
A composition as described in Example 1 is applied to a fabric containing an elastic polyurethane component (Elastane), for example SPANDEX a trademark of Du Pont. The process involves screen printing using a mesh size of 30t to 70t with between 1 and 6 pulls.
The composition coats the fabric, binds to the fabric and provides a desired combination of characteristics including:
washfastness - retention of colour brightness after 50 washes in a standard automatic washing machine as part of a standard load;
rubfastness - retention of colour brightness and material properties with hard rubbing as set out in ISO105-X12;
lightfastness - retention of colour brightness and colour-change/thermochromic sensitivity upon exposure to UV light according to the test method set out below.
The colour-change fabric should stretch to at least 80% elongation and return to its unstretched size and shape within 2 minutes and have a soft, non-tacky feeling as determined by survey evidence.
Example 3 - Testing of colour-change items of attire The relationship between garment temperature with ambient temperature, skin temperature, and garment humidity, during an experiment to mimic a 100 m sprint were evaluated. An elastane-containing sprint suit comprising 85% polyamide and 15 % elastane (skin-tight) and a singlet (relatively loose fitting) were tested worn by the subject in order to allow garment and skin temperatures to be tested to determine changes in temperature with changing conditions. Temperature change at various locations on the garment provided an indication of the required temperature-change range for a colour-change composition to provide a colour-change effect in a garment in use. Example 4
Comparison of sprint suit with singlet
In this experiment, the garment temperatures between the singlet and the sprint suit were compared. The singlet was at a lower initial temperature, as determined by thermal imaging, at the beginning of the experiment as compared to that of the sprint suit. This is probably due to the singlet being of looser fit than the sprint suit but demonstrates that the invention is applicable to garments having a different closeness of fit to the subject.
The difference in thermal profile between the sprint suit and the singlet enables a colour- change effect to be tailored using the looseness of the garment to control where skin contact occurs and hence to modulate the colour-change effect.

Claims

1. A binder composition comprising:
i) a polyurethane binder derived from a polymer with free hydroxyl end groups;
ii) an isocyanate cross-linker;
iii) a processing lubricant
for use in adhering a colourant composition comprising a colourant component to a substrate.
2. A binder composition according to claim 1 wherein the polymer with free hydroxyl end groups comprises an aliphatic polymer.
3. A binder composition according to claim 1 or claim 2 wherein the said polymer comprises a copolymer comprising polyether moieties and polyester moieties
4. A binder composition according to any one of the preceding claims wherein the polyurethane binder is present at a level of 10 to 50%,
5. A binder composition according to any one of the preceding claims wherein the cross- linker comprises an aliphatic molecule with two or more‘blocked’ isocyanate groups.
6. A binder composition according to any one of the preceding claims wherein the blocked isocyanate has a deblocking temperature of at least 80°C.
7. A binder composition according to any one of the preceding claims wherein the cross- linker is present at a level of 5 to 30% by weight of the composition.
8. A binder composition according to any one of the preceding claims wherein the processing lubricant is selected from a glycol-based compound, glycerol, hydrophilic aliphatic polyureas, hydrophilic siloxanes, gum Arabic, gelatin, xantham gum, guar gum, alginate, carrageen, locust bean gum, pectin and starch.
9. A binder composition according to any one of the preceding claims wherein the process lubricant is present at a level of 1 to 15% by weight of the composition.
10. A binder composition according to any one of the preceding claims wherein the binder is transparent.
1 1. A binder composition according to any one of the preceding claims wherein the binder is elastic and capable of elongation to at least 30%.
12. A colourant composition adapted to be bound to a substrate wherein the composition comprises an encapsulated colourant component and a binder composition as defined in any one of claims 1 to 11.
13. A colourant composition according to claim 12 comprising a colourant component selected from a leuco dye and a liquid crystal.
14. A colourant composition according to claim 12 or claim 13 which is iridescent
15. Use of a binder composition as defined in any one of claims 1 to 11 in a colourant composition comprising a colourant component to adhere the colourant component to a substrate.
16. Coloured attire comprising a fabric having a colourant composition according to any one of claim 12 to 14 bound to the fabric.
17. Coloured attire according to claim 16 wherein the fabric is elastic and has an elongation of at least 30%.
18. Coloured attire according to claim 16 or claim 17 wherein the elastic fabric comprises a synthetic elastomer and a fibre selected from polyamide, polyester, polyurethane and mixtures thereof.
19. Coloured attire according to any one of claims 16 to 18 wherein the fabric has a thickness of 5 to 50 microns.
20. Coloured attire according to any one of claims 16 to 19 wherein the fabric is formed into a garment, a singlet, or footwear.
21. A method of providing an elastic fabric with a colourant appearance which comprises applying to an elastic fabric a colourant composition according to any one of claims 12 to 14 wherein the colourant composition comprises an encapsulated colourant compound.
22. A method of providing a colour-change effect in a colour-treated attire adapted to be worn by a subject wherein the colour-treated attire comprises a colour-change composition according to any one of claims 12 to 14 wherein the colour of the attire in one area of the attire differs to the colour of the attire in a different area of the attire and the colour in at least one area is changeable in response to an external stimulus.
23. A method according to claim 22 wherein the external stimulus is selected from body temperature of the subject, pressure experienced by the subject due to movement and water.
24. A method according to claim 22 or claim 23 wherein different parts of the attire are subject to different levels of stimulus during movement of the subject.
25. A method according to claim 24 wherein the different levels of stimulus are provided by the attire being in contact with different parts of the body at different temperature.
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