WO2018033620A1 - Composition notamment pour l'impression ou le revêtement comprenant des polymères de polyuréthane - Google Patents

Composition notamment pour l'impression ou le revêtement comprenant des polymères de polyuréthane Download PDF

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Publication number
WO2018033620A1
WO2018033620A1 PCT/EP2017/070921 EP2017070921W WO2018033620A1 WO 2018033620 A1 WO2018033620 A1 WO 2018033620A1 EP 2017070921 W EP2017070921 W EP 2017070921W WO 2018033620 A1 WO2018033620 A1 WO 2018033620A1
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Prior art keywords
diols
substrate
group
mol
electrochromic
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PCT/EP2017/070921
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English (en)
Inventor
Maximilian HEMGESBERG
Nikolaus Nestle
Ralf NÖRENBERG
Felicia BOKEL
Szilard Csihony
Original Assignee
Basf Se
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Publication date
Priority claimed from EP16184752.0A external-priority patent/EP3284764A1/fr
Priority claimed from EP16184742.1A external-priority patent/EP3284799A1/fr
Application filed by Basf Se filed Critical Basf Se
Publication of WO2018033620A1 publication Critical patent/WO2018033620A1/fr

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    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • composition especially for printing or coating comprising polyurethane polymers
  • the present invention relates to a composition especially for printing or coating and to the use of certain polyurethane polymers as rheological modifiers in compositions for printing or coating.
  • the invention also relates to a process for producing a layer assembly comprising an electrochromic layer and to an article comprising such layer assembly.
  • Layers having controllable alteration of light transmission are used in devices or applications like optical filters, windows, films, opthalmic lenses, actinometers, molecular sensors, photochromic inks, paints or fibers, variable transmission filters, optical information storage systems, optoelectronic systems and reversible holographic systems.
  • Controllable alteration of light transmission is achieved by incorporating a compound having electrochromic and photochromic properties into a layer or coating disposed on a surface of a substrate.
  • the substrate is electronically conductive, or comprises an electronically conductive surface capable of applying an electric field to the layer comprising the compound having electrochromic and photochromic properties.
  • Said electronically conductive surface of the substrate is herein also referred to as an electrode.
  • the layer comprising said compound having electrochromic and photochromic properties is usually sandwiched between a first electrode and a second electrode.
  • a layer comprising said compound having electrochromic and photochromic properties is herein also referred to as an electrochromic layer.
  • a compound having electrochromic and photochromic properties is capable of transitioning between an optically transparent (“light”) state and a colored (“dark”) state responsive to application of light in the UV and/or short wavelength-VIS range, or application of an electric voltage. More specifically, a compound having electrochromic and photochromic properties may darken (reach said 'dark state') when exposed to light in the UV and/or VIS range, and may lighten ("fade", achieve said 'light state") when exposed to an electric charge ('electro-fading'). Such a compound having electrochromic and photochromic properties is also referred to as an auto-darkening material, see e.g. WO 2013/152425. Certain compounds having electrochromic and photochromic properties fade upon expo- sure to selected wavelengths of visible (VIS) light ("photofade”, “photobleach”), without sacrificing the ability to be electrofaded when restored to a darkened state.
  • VIS visible
  • WO 2013/152425 discloses a composition (referred to as a "switching material") comprising one or more compounds having electrochromic and photochromic properties dispersed homogeneously through the switching material, one or more polymers, and an electrolyte comprising a salt and a solvent portion comprising one or more solvents.
  • WO 2013/152425 also discloses an article (referred to as a "switchable film") comprising a first and optionally a second substantially transparent substrate; a first and a second electrode disposed on the surface of at least one of the substrates; and a switching material as defined above disposed between the first and the optional second substrate and in contact with the first and the second electrode, and WO 2013/152425 also discloses a laminate assembly comprising said switchable film laminated between a first and a second sheet of glass.
  • the function of the polymer in the composition (referred to as a "switching material") according to WO 2013/152425 includes
  • - modulating the rheology of the composition in order to aid in handling said composition and facilitate processing said composition into a layer on a substrate rendering the composition in a suitable shape (e.g. cast, extruded, coated or molded), i.e. in the form of a layer on a surface of a substrate.
  • a suitable shape e.g. cast, extruded, coated or molded
  • Selection of the one or more polymers depends on several factors including chemical stability, compatibility with the other constituents of the composition (said salts and said solvent portion of the electrolyte and said compounds having electrochromic and photochromic properties, see above) and the constituents of the substrates (including the electronically conducting materials at the surfaces of said substrates), stability against electrical voltage and against light irradiation in the UV and/or VIS range, rheological behavior, optical properties, glass transition temperature and many others.
  • the polymer in the composition referred to as a "switching material” is preferably selected from the group of polyols, more specifically from the group of polyvinylacetals, most preferably from the group of polyvinylbutyrals (PVB).
  • Polyvinyl butyral is obtained by acidic hydrolysis (e.g. using hydrochloric acid) of polyvinyl acetate and subsequent (at least partial) acetalization of the obtained polyvinyl alcohol with butanal (butyraldehyde).
  • the obtained product often contains residues of hydrochloric acid and/or acetic acid.
  • polyvinylbutyrals exhibit some drawbacks, e.g. insufficient stability especially in contact with solvents typically present in the solvent portion of the electrolyte of the "switching material" disclosed in WO 2013/152425.
  • Degradation of the polyvinyl butyral in the electrochromic layer does not only result in reduced stability and reduced performance of said layer.
  • degradation products of polyvinyl butyral and residual acid and/or aldehydes, such as 2-ethylhexanal, present in the polyvinyl butyral may cause corrosion of electronically conductive materials (e.g., transparent conducting oxides or metallic electronic conductive materials) of the electrodes, resulting in impairment of electronic conductivity and reduced light transmission due to the formation of colored reaction products.
  • electronically conductive materials e.g., transparent conducting oxides or metallic electronic conductive materials
  • composition especially for printing or coating comprising the following constituents
  • (B2-1 ) a portion of first diols having a molecular weight in the range of from 50 g/mol to ⁇ 500 g/mol, preferably from 50 g/mol to 490 g/mol
  • fraction of (B1 ) diisocyanate monomers is 20 wt.-% to 80 wt.-%
  • colorants selected from the group consisting of dyes and pigments wherein said colorants are preferably compounds having electrochromic and pho- tochromic properties
  • constituents (B) and (C) are dissolved or dispersed in said liquid phase (A).
  • a further aspect of the present invention relates to the use of a polyurethane polymer as defined above as a rheological modifier in a composition according to the present invention.
  • a polyurethane polymer (B) as defined above as a rheological modifier in a composition for printing or coating of a colored or electrochromic layer as defined above results in improved rheological properties of said composition and accordingly superior quality of the layer formed from a composition according to the present invention (i.e. the layer obtainable by the process of the present invention), especially in case of electrochromic layers.
  • a rheological behavior exhibiting thixotropy or shear thinning is desirable, allowing the composition to flow sufficiently to form a uniform layer when applied to a surface of a substrate, and then to resist further flow, thus remaining as a layer on said surface of said substrate.
  • the above-defined polyurethane polymers (B) act as rheological modifiers in such manner that shear thinning or thixotropy is imparted to the composition.
  • a composition according to the present invention comprises a liquid phase (A), wherein one or more of the above-defined polyurethane polymers (B) and one or more colorants (C) are dispersed or dissolved.
  • concentration ranges see below, the constituents (B) and (C) as defined above are not considered as constituents of the liquid phase (A) as defined above.
  • the colorants (C) are selected from the group consisting of dyes and pigments.
  • a dye is a colorant which in the composition according to the invention is present in dissolved form.
  • a pigment is a colorant which in the composition according to the invention is present in the form of dispersed particles.
  • Preferred colorants are compounds having electrochromic and photochromic properties.
  • the term "compounds having electrochromic and photochromic properties" is generally defined above, for further details see below. Those compounds belong either to the group of dyes or to the group of pigments, depending on whether they are present in the composition according to the present invention in dissolved form or in dispersed form.
  • the liquid phase (A) of the above-defined composition comprises one or more liquids having a boiling point of 120 °C or less.
  • the liquid phase (A) of the above-defined composition consists of one or more liquids having a boiling point of 120 °C or less.
  • Said liquids having a boiling point of 120 °C or less merely act as a vehicle for applying the composition to a surface of a substrate, preferably by means of a printing or coating technique, especially by means of screen printing and stencil printing, and do not from a permanent constituent of the layer formed by applying a composition according to the present invention on a surface of a substrate (i.e. the layer obtainable by the process of the present invention).
  • Said liquids having a boiling point of 120 °C or less are preferably selected from the group consisting of methoxy-2-methylpropane, tetrahydrofurane, 2-methyl-tetrahydrofurane, 1 ,4-dioxane, toluene, ethanol, methanol, iso-propanol, ethylacetate, methylacetate, acetone, acetonitrile and butanone.
  • a composition according to the present invention comprises a liquid phase (A) consisting of one or more liquids having a boiling point of 120 °C or less, wherein one or more of the above-defined polyurethane polymers (B) and one or more colorants (C) selected from the group consisting of dyes and pigments are dispersed or dissolved.
  • A liquid phase
  • B polyurethane polymers
  • C colorants
  • Such compositions are useful for forming a colored layer by means of a printing or coating technique, especially screen printing or stencil printing.
  • a composition according to the present invention further comprises
  • R is hydrogen or methyl
  • R 2 is selected from the group consisting of
  • linear and branched unsubstituted alkyl groups having 1 to 22 carbon atoms, preferably 2 to 22 carbon atoms
  • composition according to the present invention further comprises
  • a preferred composition according to the present invention comprises
  • (A-2) optionally one or more liquids having a boiling point of 120 °C or less
  • (B2-1 ) a portion of first diols having a molecular weight in the range of from 50 g/mol to ⁇ 500 g/mol, preferably from 50 g/mol to 490 g/mol
  • fraction of (B1 ) diisocyanate monomers is 20 wt.-% to 80 wt.-%
  • constituents (B), (C) and (D) are dissolved or dispersed in said liquid phase (A).
  • a preferred composition as defined above comprises a liquid phase (A) as defined above, wherein one or more of the above-defined polyurethane polymers (B), and one or more compounds (C) having electrochromic and photochromic properties and one or more electrolytes (D) are dispersed or dissolved.
  • Compounds having electrochromic and photochromic properties (C) and electrolytes (D) are usually dissolved in said liquid phase (A).
  • concentration ranges see below, the constituents (B), (C) and (D) as defined above are not considered as constituents of the liquid phase (A) as defined above.
  • Said preferred compositions according to the present invention are particularly suitable for forming a layer having a controllable alteration of light transmission as described above, i.e. an electrochromic layer.
  • the constituents of the above-defined preferred composition according to the present invention are now described in more detail.
  • the liquid phase (A) of the above-defined preferred composition comprises (A-1 ) one or more liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more and optionally (A-2) one or more liquids having a boiling point of 120 °C or less.
  • the liquid phase (A) of the above-defined preferred composition comprises
  • (A-2) one or more liquids having a boiling point of 120 °C or less.
  • liquid phase (A) of the above-defined preferred composition consists of
  • (A-1 ) one or more liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more.
  • liquid phase (A) does not contain any liquids (A-2) having a boiling point of 120 °C or less.
  • liquid phase (A) of the above-defined preferred composition consists of
  • (A-2) one or more liquids having a boiling point of 120 °C or less.
  • the one or more liquids (A-1 ) having a melting point of -20 °C or less and a boiling point of 150 °C or more remain in said electrochromic layer.
  • the liquids (A-1 ) allow dissolution of the one or more electrolytes (D) present in the preferred composition according to the present invention (as defined above) and in the layer formed from a preferred composition according to the present. Accordingly, said liquids (A-1 ) having a melting point of -20 °C or less and a boiling point of 150 °C or more may be considered as playing a role similar or corresponding to the "solvent portion" of the composition (switching material) disclosed in WO 2013/152425.
  • Selection of the one or more liquids (A-1 ) depends on several factors including chemical stability, compatibility with the other constituents of the composition (polymers, electrolytes and said compounds having electrochromic and photochromic properties, see above) and the constituents of the substrates (including the electronically conducting materials at the surfaces of said substrates), stability against electrical voltage and against light irradiation in the UV and/or VIS range, capability of dissolving electrolytes, dielectric constant.
  • said liquid phase (A) comprises said liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more in the form of a mixture (A-1 ) consisting of
  • alkyl-cyclohexylacetates wherein said alkyl group is selected from the group consisting of alkyls having 1 to 9, preferably 1 to 4 carbon atoms, preferably 4-tertbutylcyclohexylacetat
  • dialkyl esters of 1 ,2-cyclohexanedicarboxylic acid wherein said alkyl groups are selected from the group consisting of alkyls having 1 to 4 carbon atoms, preferably 1 ,2-cyclohexanedicarboxylic acid diethylester
  • glycerol triesters of carboxylic acids having 3 to 6 carbon atoms preferably glycerol triesters of propionic acid and butyric acid tri-alkyl acetylcitrates, wherein said alkyl groups are selected from the group consisting of alkyls having 1 to 4 carbon atoms, preferably tri-n-ethylacetylcitrate and tri-n-butylacetylcitrate
  • the total weight fraction of said compounds (2) and (3) is 50 wt.-% or more, preferably 60 wt.-% or more, more preferably 70 wt.-% or more, most preferably 80 wt.-% or more, based on the total weight of said mixture (A-1 ).
  • the weight fraction of said compounds (1 ) is 50 wt.-% or less, preferably 40 wt.-% or less, more preferably 30 wt.-% or less, most preferably 20 wt.-% or less, based on the total weight of said mixture (A-1 ).
  • each generic alkyl group listed herein is meant to include all possible isomers (straight-chain and branched), and in cases where an above-mentioned compound exists in the form of two or more stereoisomers, said compound includes each of those stereoisomers as well as mixtures thereof, including racemic mixtures.
  • said mixture (A-1 ) consists of
  • the weight fraction of said compound (2) is 50 wt.-% or more, preferably 60 wt.-% or more, more preferably 70 wt.-% or more, most preferably 80 wt.-% or more, based on the total weight of said mixture (A-1 ).
  • the weight fraction of said compounds (1 ) is 50 wt.-% or less, preferably 40 wt.-% or less, more preferably 30 wt.-% or less, most preferably 20 wt.-% or less, based on the total weight of said mixture (A-1 ).
  • said mixture (A-1 ) consists of
  • the weight fraction of said compound (2) is 50 wt.-% or more, preferably 60 wt.-% or more, more preferably 70 wt.-% or more, most preferably 80 wt.-% or more, based on the total weight of said mixture (A-1 ).
  • the weight fraction of said compounds (1 ) is 50 wt.-% or less, preferably 40 wt.-% or less, more preferably 30 wt.-% or less, most preferably 20 wt.-% or less, based on the total weight of said mixture (A-1 ).
  • said mixture (A-1 ) consists of
  • the weight fraction of said compounds (2) is 50 wt.-% to 80 wt.-%, preferably 60 wt.-% to 70 wt.-%, and
  • the weight fraction of said compounds (3) is 10 wt.-% to 30 wt.-%, preferably 15 wt.-% to 25 wt.-%,
  • the weight fraction of said compounds (1 ) is 5 wt.-% to 40 wt.-%, preferably 5 wt.-% to 25 wt.-%, in each case based on the total weight of said mixture (A-1 ).
  • said mixture (A-1 ) consists of
  • the weight fraction of said compound (2) is 50 wt.-% to 80 wt.-%, preferably 60 wt.-% to 70 wt.-%, and
  • the weight fraction of said compound (3) is 10 wt.-% to 30 wt.-%, preferably 15 wt.-% to 25 wt.-%,
  • the weight fraction of said compounds (1 ) is 5 wt.-% to 40 wt.-%, preferably 5 wt.-% to 25 wt.-%, in each case based on the total weight of said mixture (A-1 ).
  • polymeric substrates especially those comprising polyethylene terephthalate, which tend to swell in the presence of organic liquids, exhibit a surprisingly low tendency to swell when coated with a composition according to the invention comprising one of said preferred mixtures (A-1 ).
  • the tendency to swell is estimated from the weight increase of the polymeric substrate after 1 hour of storing said substrate in the solvent at 120 °C.
  • Said one or more liquids (A-2) having a boiling point of 120 °C or less merely act as a vehicle for applying the composition to a surface of a substrate, preferably by means of a printing or coating technique, especially by means of screen printing and stencil printing, and do not remain in the layer formed from a composition according to the present invention (i.e. the layer obtainable by the process of the present invention, see below).
  • More specifically said liquids (A-2) serve the purpose of facilitating processing of a composition according to the present invention, e.g. by reducing the viscosity and improving the coatability.
  • liquids (A-2) having a boiling point of 120 °C or less may be considered as playing a role similar or corresponding to the "sacrificial solvent" which may be present in the composition (switching material) disclosed in WO 2013/152425.
  • said liquids (A-2) having a boiling point of 120 °C or less are preferably selected from the group consisting of methoxy-2-methylpropane, tetrahydrofurane, 2-methyl- tetrahydrofurane, 1 ,4-dioxane, toluene, ethanol, methanol, iso-propanol, ethylacetate, methylacetate, acetone, acetonitrile and butanone.
  • composition according to the present invention comprises
  • (B1 ) diisocyanate monomers is 20 wt.-% to 80 wt.-%
  • the weight fractions of said diisocyanate monomers (B1 ), first diols (B2-1 ) and second diols (B2-2) represent the weight fractions of the corresponding building units formed from said diisocyanate monomers (B1 ), first diols (B2-1 ) and second diols (B2-2) in said polyurethane polymer (B).
  • Suitable polyurethane polymers are commercially available. As known by the skilled person, polyurethane polymers are obtainable by polyaddition of diisocyanate monomers with diols. Said first diols (B2-1 ) are also referred to as chain extending agents or chain extenders. For further details see e.g. WO 2014/060342.
  • said diisocyanate monomers (B1 ) are selected from the group consisting of 4,4-methylene dicyclohexyl diisocyanate and 1 ,6-hexamethylene diisocyanate.
  • said first diols (B2-1 ) are selected from the group consisting of 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol and hydroquinone- bis(hydroxyethyl)ether.
  • said second diols (B2-2) are selected from the group consisting of polyether diols, polyolefine diols and polyester diols.
  • said constituent (B) is a mixture of polyurethane molecules which are polyadducts of the same diisocyanate monomers (B), first diols (B2-1 ) and second diols (B2-2), but have different molecular weight. More preferably,
  • diisocyanate monomers (B1 ) are selected from the group consisting of 4,4- methylene dicyclohexyl diisocyanate and 1 ,6-hexamethylene diisocyanate and
  • said first diols (B2-1 ) are selected from the group consisting of 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol and hydroquinone-bis(hydroxyethyl)ether and
  • said second diols (B2-2) are selected from the group consisting of
  • Polyetherdiols are also referred to as poly(alkyleneglycole)s.
  • said second diols (B2-2) are selected from the group consisting of polyetherdiols selected from the group consisting of
  • polytetrahydrofuranes also referred to as poly(tetramethylenglycol)s
  • polyolefine diols selected from the group consisting of
  • polybutadiene diols molecules consisting of a chain of 1 ,2-linked butadiene units, wherein said chain is terminated by -(Ch ⁇ OH groups)
  • polyester diols selected from the group consisting of
  • random polyester condensates which are polycondensation products of C 2 - C-I2 aliphatic dicarboxylic acids and diols selected from the group consisting of C2-C12 aliphatic diols, poly(ethyleneglycol)s, poly(propyleneglycol)s and diols of copolymers of ethylene oxide and propylene oxide polycarbonate diols.
  • said polytetrahydrofuranes have 10 to 40 -(CH 2 )4-0- units.
  • the number of -(CH 2 )2-0- groups is 1 1 to 75.
  • the number of -CH(CH 3 )-CH 2 -0- groups is 8 to 60.
  • said diols of copolymers of ethylene oxide and propylene oxide have a structure according to formula (I)
  • n is an integer from 9 to 1 10 and R is H or methyl.
  • n is an integer of from 20 to 90, i.e. the polyethylene chain has 20 to 90 ethylene units.
  • n is an integer of from 10 to 40, i.e. the polybutadiene chain has 10 to 40 1 ,2-linked butadiene units
  • n is an integer of from 6 to 22.
  • random polyester diols have a structure according to formula (II)
  • R is selected from the group consisting of
  • s is an integer selected from 4 to 20
  • each R 4 independently from each further R 4 is selected from the group consisting of H and CH 3 p is an integer selected from 5 to 40
  • each R 2 independently from each further R 2 is selected from the group consisting of (CH 2 ) q wherein q is an integer selected from 0 to 10
  • each R 3 independently from each further R 3 is selected from the group consisting of
  • s is an integer selected from 4 to 24
  • each R 4 is independently from each fur- ther R 4 selected from the group consisting of H and CH 3 .
  • each R 4 is independently from each fur- ther R 4 selected from the group consisting of H and CH 3 .
  • each R independently from each other R is selected from the group consisting of -C m H 2m - wherein m is an integer selected from 4 to 6,
  • n is an integer selected from 3 to 29.
  • polycarbonate diols wherein the groups R are -[(CH 2 )4]- and -[(CH 2 )6]- (also referred to as "polycarbonate diols based on butane diol and hexane diol", see WO 2013/1901 18)
  • polycarbonate diols wherein the groups R are -[(CH 2 ) 5 ]- and -[(CH 2 ) 6 ]- (also referred to as "polycarbonate diols based on pentane diol and hexane diol", see WO 2013/1901 18)
  • polycarbonate diols wherein the groups R are -[(CH 2 ) 5 ]- and -[(CH 2 ) 6 ]-.
  • Polyurethane polymers which are polyadducts of
  • (B1 ) diisocyanate monomers preferably the above-described preferred diisocyanate monomers (B1 )
  • polyurethane polymers (B) for the present invention.
  • Those polyurethane polymers are commercially available and are described e.g. in WO 2013/1901 18.
  • said polyurethane polymers (B) have a weight average molecular weight in the range of from 25000 g/mol to 1000000 g/mol as determined by gel permeation chromatography.
  • said polyurethane polymers (B) are thermoplastic polyurethane polymers.
  • said polyurethane polymers (B) are linear polyurethane polymers.
  • Preferred polyurethane polymers (B) are those wherein two or more of the above-defined preferred features are combined.
  • a preferred composition according to the present invention as defined above comprises (C) one or more compounds having electrochromic and photochromic properties.
  • a compound (C) is a compound which has both, photochromic properties as defined above and electrochromic properties as defined above.
  • the photochromic properties of said compound (C) consist in the capability of reversibly darkening, i.e. decreasing the transmission of said compound (C) for visible light, when said compound (C) is exposed to light comprising wavelengths of 525 nm or less (a range including UV light, and some short-wavelength portion of visible light). Furthermore, the photochromic properties of some preferred compounds (C) include the capability of reversibly fading, i.e. increasing the transmission of said compound (C) for visible light, when said compound (C) is exposed to light having longer wave lengths in the visible range (preferably up to 750 nm).
  • the electrochromic properties of said compound (C) consist in the capability of reversibly fading, i.e. increasing the transmission of said compound (C) for visible light, when said compound (C) is exposed to an electric charge (electrofading).
  • electrofading is achieved either by cathodic reduction or by anodic oxidation.
  • Said compounds (C) are preferably selected from the group consisting of hexatrienes, diarylethenes, dithienylcyclopentenes and fulgides. Suitable compounds are commercial- ly available. Examples of suitable diarylethene compounds are disclosed e.g. in US 7,777,055, WO 2010/142019, WO 2013/044371 and WO 2013/152425.
  • composition according to the present invention as defined above comprises
  • electrolytes denotes a substance which is capable of dissociating into mobile ions.
  • electrolytes when dissolved in said liquids (A-1 ), are at least partly dissociated into mobile ions, which migrate to the electrodes between which the electrochromic layer is disposed, to form an electrical double-layer at the electrode/electrochromic layer interface when an electric field is applied.
  • said electrolytes (D) may be considered as playing a role similar or corresponding to the "salts" of the composition (referred to as a switching material) disclosed in WO 2013/152425.
  • Preferred electrolytes (D) are selected from the group consisting of
  • cations selected from the group consisting of tetraalkyl ammonium, 1-alkyl-3-methyl imidazolium, 1 -alkyl-1 -methyl pyrrolidinium and 1 -alkyl-1 -methyl piperidinium, wherein said alkyl is selected from the group consisting of methyl, ethyl, n-propyl and n-butyl, and anions selected from the group consisting of tetrafluoroborate, tetracyanoborate, hexafluorophosphate, bis(fluoromethyl)sulfonylimide, bis(trifluoromethylsulfonyl)imide and tris(pentafluoroethyl)trifluorophosphate.
  • the compounds (D) as defined above are ionic liquids. Such compounds are commercially available. Preferred compounds (D) are selected from the group consisting of 1-ethyl-3- methylimidazolium bis(fluoromethyl)sulfonylimide, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate and 1-ethyl-3-methylimidazolium tetrafluoroborate.
  • composition according to the present invention further comprises
  • R 2 is selected from the group consisting of linear and branched unsubstituted alkyl groups having 1 to 22 carbon atoms, preferably 2 to 22 carbon atoms
  • alkyl-substituted cycloalkyl groups having 4 to 22 carbon atoms, and optionally one or more further monomers having polymerizable double bonds which are not (meth)acrylate monomers
  • CHR CH-(CO)-OR 2 dissolved or dispersed in said liquid phase (A).
  • composition according to the present invention comprises
  • (A-2) optionally one or more liquids having a boiling point of 120 °C or less
  • (B1 ) diisocyanate monomers is 20 wt.-% to 80 wt.-%
  • (B2-1 )said first diols is 5 wt.-% to 35 wt.-%
  • (B2-2)said second diols is 5 wt.-% to 60 wt.-%
  • R is hydrogen or methyl
  • R 2 is selected from the group consisting of
  • linear and branched unsubstituted alkyi groups having 1 to 22 carbon atoms, preferably 2 to 22 carbon atoms
  • alkyl-substituted cycloalkyl groups having 4 to 22 carbon atoms, and optionally one or more further monomers having polymerizable double bonds which are not (meth)acrylate monomers
  • CHR CH-(CO)-OR 2 wherein the constituents (B), (C), (D) and (E) are dissolved or dispersed in said liquid phase (A).
  • Said polymers (E) are also referred to as (meth)acrylate polymers.
  • the term (meth)acrylates in each case includes acrylates and methacrylates.
  • R 2 is selected from the group consisting of 2-hydroxyethyl, 2-hydroxy propyl, ethyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, cyclohexyl, bornyl, isobornyl, fenchyl, dihydroterpinyl, 4-tertbutylcyclohexyl, 2-tertbutylcyclohexyl, 4-methylcyclohexyl and 4-ethylcyclohexyl.
  • Each generic alkyi group and hydroxy alkyi group listed herein is meant to include all possible isomers (straight-chain and branched).
  • Preferred are polymers (E) having a weight average molecular weight in the range of from 10000 g/mol to 2000000 g/mol as determined by gel permeation chromatography.
  • a second (meth)acrylate monomer selected from the group consisting of ethylmethacrylate and n-dodecylmethacrylate
  • first (meth)acrylate monomer / second (meth)acrylate monomer is preferably in the range of from 1 : 1 to 1 : 15, preferably 1 : 1 to 3:7.
  • Preferably one of these three different (meth)acrylate monomers CHR CH-(CO)-OR 2 is a hydroxy(meth)acrylate monomer.
  • a first (meth)acrylate monomer selected from the group consisting of 2-hydroxyethylmethacrylate and 2-hydroxyethylacrylate
  • a third (meth)acrylate monomer selected from the group consisting of 4-tertbutylcyclohexylmethacrylate, cyclohexylmethacrylate and n-docecylmethacrylate
  • the mole ratio first (meth)acrylate monomer / ethylmethacrylate / third (meth)acrylate monomer is in the range of from 9:9:2 to 1 : 1 : 18, preferably 9:9:2 : 3: 1 :6.
  • Suitable polymers (E) are commercially available or can be obtained from commercially available monomers by preparation processes known to the skilled person.
  • Preferred polymers (E) are those wherein two or more of the above-defined preferred features are combined.
  • composition according to the present invention further comprises
  • Crosslinking of said polymers (B) and/or -if present- said polymers (E) imparts increased chemical and mechanical stability to said polymers (B) and/or said polymers (E).
  • Suitable crosslinking agents are known in the art.
  • said crosslinking agents exhibit significant cross-linking activity only after a certain temperature is reached (thermally activated crosslinking agents).
  • the crosslinking agents (F) are chemically different from the above-defined polymers (B) and (E).
  • composition may optionally contain compounds that serve to enhance the switching speed of the electrochromic system (charge compensator, charge transfer agent). Examples of these are known in the art and include e.g. viologens.
  • composition according to the present invention comprises
  • (A-1 ) a total amount of from 40 wt.-% to 90 wt.-%, preferably 60 wt.-% to 75 wt.-%, of liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more
  • (B) a total amount of from 0.5 wt.-% to 10 wt.-%, preferably 2 wt.-% to 5 wt.-% of polyurethane polymers as defined above
  • (C) a total amount of from 5 wt.-% to 25 wt.-%, preferably 10 wt.-% to 20 wt.-%, of compounds having electrochromic and photochromic properties
  • composition according to the present invention comprises
  • (A-1 ) a total amount of from 40 wt.-% to 90 wt.-%, preferably 60 wt.-% to 75 wt.-%, of liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more
  • (B) a total amount of from 0.5 wt.-% to 10 wt.-%, preferably 2 wt.-% to 5 wt.-% of polyurethane polymers as defined above
  • (C) a total amount of from 5 wt.-% to 25 wt.-%, preferably 10 wt.-% to 20 wt.-%, of compounds having electrochromic and photochromic properties
  • (A-2) a total amount of liquids having a boiling point of 120 °C or less in a range of from 0 wt.-% to 500 wt.-%, preferably 10 wt.-% to 250 wt.-% based on the total weight of constituents (A-1 ), (B), (C) and (D).
  • composition according to the present invention comprises
  • (A-1 ) a total amount of from 40 wt.-% to 90 wt.-%, preferably 60 wt.-% to 75 wt.-%, of liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more
  • (B) a total amount of from 0.5 wt.-% to 10 wt.-%, preferably 2 wt.-% to 5 wt.-% of polyurethane polymers as defined above
  • (C) a total amount of from 5 wt.-% to 25 wt.-%, preferably 10 wt.-% to 20 wt.-%, of compounds having electrochromic and photochromic properties
  • composition according to the present invention comprises
  • (A-1 ) a total amount of from 40 wt.-% to 90 wt.-%, preferably 60 wt.-% to 75 wt.-%, of liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more
  • (B) a total amount of from 0.5 wt.-% to 10 wt.-%, preferably 2 wt.-% to 5 wt.-% of polyurethane polymers as defined above
  • (C) a total amount of from 5 wt.-% to 25 wt.-%, preferably 10 wt.-% to 20 wt.-%, of compounds having electrochromic and photochromic properties
  • (E) a total amount of from 4 wt.-% to 25 wt.-%, preferably 6 wt.-% to 16 wt.-% of polymers which are copolymerization products as defined above
  • (A-2) a total amount of liquids having a boiling point of 120 °C or less in a range of from 0 wt.-% to 500 wt.-%, preferably 10 wt.-% to 250 wt.-% based on the total weight of constituents (A-1 ), (B), (C), (D), (E) and (F).
  • composition according to the present invention comprises
  • (A-1 ) a total amount of from 40 wt.-% to 90 wt.-%, preferably 60 wt.-% to 75 wt.-%, of liquids having a melting point of -20 °C or less and a boiling point of 150 °C or more
  • (B) a total amount of from 0.5 wt.-% to 10 wt.-%, preferably 2 wt.-% to 5 wt.-% of polyurethane polymers as defined above
  • (C) a total amount of from 5 wt.-% to 25 wt.-%, preferably 10 wt.-% to 20 wt.-%, of compounds having electrochromic and photochromic properties
  • a composition according to the present invention preferably comprises
  • (G) polymers selected from the group consisting of polyvinylacetals in an amount of less than 25 wt.-%, preferably less than 10 wt.-%, further preferably less than 5 wt.-%, particularly preferably less than 1 wt.-%, in each case based on the total weight of polymers (B) and (E), and preferably does not comprise polyvinylacetals.
  • compositions according to the present invention are those wherein two or more of the above-defined preferred features are combined. Particularly preferred are compositions wherein each of constituents (A-1 ), (B), (C), (D) and - if present - (A-2), (E) and (F) is selected from the above-defined preferred alternatives and is present in the above defined concentration ranges, preferably in a concentration falling in the above- defined preferred ranges.
  • a process for producing a layer assembly comprising a colored or electrochromic layer. Said process comprises the steps of
  • Said composition is applied to a surface of a first substrate and allowed to form said colored or electrochromic layer on said surface.
  • said composition is applied to said surface of said substrate by means of a printing or coating technique, especially by a technique selected from the group consisting of screen printing and stencil printing.
  • said first substrate has at least one surface which is not covered by the colored or electrochromic layer.
  • said first substrate has a first surface on which said colored or electrochromic layer is arranged and a second surface opposite to said first surface, wherein on said second surface none such colored or electrochromic layer is arranged. This second surface of the first substrate is also referred to as the surface of the first substrate facing away from said colored or electrochromic layer.
  • the colored or electrochromic layer has a surface in contact with said first surface of said first substrate, and a second surface opposite to said first surface.
  • This second surface of the colored or electrochromic layer is also referred to as the surface of the colored or electrochromic layer facing away from said first substrate.
  • composition applied to said surface further comprises any liquids (A-2) having a boiling point of 120 °C or less as defined above, which merely act as a vehicle for applying the composition to a surface of a substrate
  • forming said colored or electrochromic layer comprises removing said liquids (A-2) having a boiling point of 120 °C or less from said composition applied to said surface of said substrate.
  • the process according to the present invention further comprises the step of crosslinking said polymers (B) and - if present - (E) by means of crosslinking agents (F) as defined above.
  • Certain preferred processes according to the present invention further comprise the step of attaching a second substrate on said surface of said electrochromic layer facing away from said first substrate.
  • the colored or electrochromic layer obtainable by the process of the present invention comprises at least the following constituents:
  • a layer assembly comprising an electrochromic layer is produced.
  • the composition provided and applied to a surface of a first substrate is selected from the above-defined preferred compositions.
  • Preparing a preferred composition according to the present invention comprises the following steps:
  • crosslinking agents (F) for the polymers (B) and optionally (E) are added to the premixture resp. the composition when it has been cooled to a temperature at which the crosslinking agents exhibit no crosslinking activity, in order to preserve the activity of the crosslinking agents (F) for later processing steps (see below).
  • said first substrate and said second substrate each have a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides,
  • compositions comprising constituents (A-1 ), (B), (C) and (D) and optionally constituents (E), (F) and (A-2) as defined above wherein said composition comprises a colorant (C) selected from the group consisting of compounds having electrochromic and photochromic properties, is applied to said surface of the first substrate comprising said at least one electronically conductive material, said composition applied to said surface is allowed to form an electrochromic layer on said surface
  • said surface of the second substrate comprising said at least one electronically conductive material is attached to the surface of said electrochromic layer facing away from said first substrate.
  • a particularly preferred process according to the present invention for producing a layer assembly comprising an electrochromic layer comprises the steps of
  • composition comprising constituents (A-1 ), (B), (C) and (D) and optionally constituents (E), (F) and (A-2) as defined above, wherein said composition comprises a colorant (C) selected from the group consisting of compounds having electrochromic and photochromic properties
  • compositions applied to a surface of a first substrate, said surface of said first substrate comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides
  • a surface of a second substrate on a surface of said electrochromic layer facing away from said first substrate wherein said surface of said second substrate comprises at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides.
  • a further preferred process according to the present invention comprises the steps of providing a first substrate, wherein said first substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides,
  • composition comprising constituents (A-1 ), (B), (C) and (D) and optionally constituents (E), (F) and (A-2) as defined above, wherein said composition comprises a colorant (C) selected from the group consisting of compounds having electrochromic and photochromic properties, and applying said composition to said surface of said first substrate
  • said composition applied to said surface to form an electrochromic layer on said surface of said first substrate optionally providing a second substrate, wherein said second substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides, and attaching said surface of said second substrate on a surface of said electrochromic layer facing away from said first substrate.
  • An especially preferred process according to the present invention for producing a layer assembly comprising an electrochromic layer comprises the steps of
  • composition comprising constituents (A-1 ) (B), (C) and (D) and optionally constituents (E), (F) and (A-2) as defined above, wherein said composition comprises a colorant (C) selected from the group consisting of compounds having electrochromic and photochromic properties
  • compositions applied to a surface of a first substrate, said surface of said first substrate comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides
  • a further especially preferred process according to the present invention comprises the steps of
  • first substrate wherein said first substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides,
  • composition comprising constituents (A-1 ) (B), (C) and (D) and optionally constituents (E), (F) and (A-2) as defined above, wherein said composition comprises a colorant (C) selected from the group consisting of compounds having electrochromic and photochromic properties, and applying said composition to said surface of said first substrate
  • said composition applied to said surface to form an electrochromic layer on said surface of said first substrate providing a second substrate, wherein said second substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides, and attaching said surface of said second substrate on a surface of said electrochromic layer facing away from said first substrate.
  • the first substrate and the second substrate each have a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides
  • a composition according to the present invention comprising a colorant (C) selected from the group consisting of compounds having electrochromic and photochromic properties is applied to said surface of the first substrate comprising said at least one electronically conductive material, said composition applied to said surface is allowed to form an electrochromic layer on said surface and the surface of the second substrate comprising said at least one electronically conductive material is attached to the surface of said electrochromic layer facing away from said first substrate.
  • C colorant
  • the process according to the present invention further comprises the step of crosslinking said polymers (B) and/or (E) by means of crosslinking agents (F) as defined above after attaching said surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides of said second substrate on said surface of said electrochromic layer facing away from said first substrate.
  • the materials of the substrates are preferably selected such that at least one of said first and second substrate has a light transmission of 70 % or more, preferably 90 % or more, measured according to ASTM D1003 (Procedure A) as published in November 2013.
  • both of said substrates have a light transmission of 70 % or more, preferably 90 % or more, measured according to ASTM D1003 (Procedure A) as published in November 2013.
  • Said first and second substrate are both in a form selected from the group consisting of foils, films, webs, panes and plates.
  • said first and said second substrate have the same form and have equal dimensions.
  • Said first and said second substrate may comprise the same or different materials.
  • said substrate has a thickness in the range of from 1 ⁇ to 1000 ⁇ , preferably 10 ⁇ to 500 ⁇ and more preferably from 50 ⁇ to 200 ⁇ .
  • said substrates comprise one or more materials selected from the group consisting of glasses, metals, transparent conducting oxides and organic polymers.
  • the first substrate and the second substrate each comprise an optically transparent material selected from the group of glasses and organic polymers, which is electronically insulating, and have a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides. Said surfaces of the first and said second substrate may comprise the same or different electronically conductive materials.
  • the electronically conductive material forms electrodes capable of interacting with the electrochromic layer, i.e. applying an electrical field across said electrochromic layer.
  • Preferred types of glass are e.g. float glass, low iron float glass, heat strengthened glass and chemically strengthened glass.
  • the glass has a low-emissivity (low-e) coating, sun-protection coating or any other coating on the surface facing away from the above-described electrochromic layer.
  • Preferred organic polymers are selected from the group consisting of polymethylmethacrylate (PMMA, commercially available e.g. as PlexiglasTM), polycarbonate (PC), polyethylene (PE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), low density polypropylene (LDPP), polyethylene therephthalate (PET), glycol modified polyethylene therephthalate, polyethylene napthalate (PEN), cellulose acetate butyrate, polylactide (PL), polystyrene (PS), polyvinyl chloride (PVC), polyimides (PI), polypropyleneoxide (PPO) and mixtures thereof.
  • PET and PEN are particularly preferred.
  • said transparent conducting oxides are selected from the group consisting of ITO (indium doped tin oxide), AZO (aluminum doped zinc oxide), IGZO (indium gallium doped zinc oxide), GZO (gallium doped zinc oxide), FTO (fluorine doped tin oxide), indium oxide, tin oxide and zinc oxide.
  • said metals are present in the form of a structure which is substantially optically transparent, e.g. in the form of fine mesh or nanowires.
  • said metals are selected from the group consisting of Cu, Ag, Au, Pt and Pd.
  • the first substrate and the second substrate each comprise an optically transparent material selected from the group of organic polymers, which is electronically insulating, and have a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides.
  • an electrochromic layer is formed, i.e. a layer comprising a colorant (C) in the form of a compound having electrochromic and photochromic properties as defined above.
  • Said electrochromic layer comprises
  • polyurethane polymers (B) which are polyadducts of
  • (B1 ) diisocyanate monomers is 20 wt.-% to 80 wt.-%
  • (B2-1 )said first diols is 5 wt.-% to 35 wt.-%
  • (B2-2)said second diols is 5 wt.-% to 60 wt.-%
  • said electrochromic layer further comprises one or more polymers (E) which are copolymerization products of
  • R is hydrogen or methyl
  • R 2 is selected from the group consisting of
  • linear and branched unsubstituted alkyl groups having 1 to 22 carbon atoms, preferably 2 to 22 carbon atoms
  • the electrochromic layer comprises
  • the polymer (B) and/or -if present- the polymer (E) are cross-linked.
  • said electrochromic layer comprises no liquids having a boiling point of 120 °C or less.
  • Said electrochromic layer preferably has a thickness in the range of from 1 ⁇ to 250 ⁇ , more preferably of from 5 ⁇ to 50 ⁇ , most preferably of from 20 ⁇ to 40 ⁇ . Thickness may be determined by interferometry, optical 3D microscopy or usual mechanical methods. Without being bound to theory, it is believed that within the electrochromic layer the polymers (B) and (E) (if present) form a contiguous gel-like phase (sometimes also referred to as a semisolid phase) extending throughout the electrochromic layer. Said contiguous gel-like phase is herein referred to as a matrix. Said matrix accommodates the above-defined constituents of the electrochromic layer which are dispersed within said matrix.
  • said liquid phase comprising the liquids (A-1 ) (as defined above) wherein said constituents (C) and (D) as defined above are dissolved, is confined within free spaces extending through the matrix comprising said polymers (B) and (E) (if present), thus providing a network of paths throughout the electrochromic layer extending between a first and a second electrode.
  • This network of paths allows flow of ions of the electrolytes (D) and molecules of the compounds (C) when an electric voltage is applied.
  • the electrochromic layer preferably comprises
  • a matrix comprising one or more polymers (B) as defined above and optionally one or more polymers (E) as defined above
  • a further aspect of the present invention relates to an article comprising a layer assembly consisting of
  • an electrochromic layer arranged on and in contact with a surface of said first substrate, said electrochromic layer comprising
  • polyurethane polymers (B) which are polyadducts of (B1 ) diisocyanate monomers
  • (B1 ) diisocyanate monomers is 20 wt.-% to 80 wt.-%
  • a second substrate having a surface arranged on and in contact with a surface of said electrochromic layer facing away from said first substrate wherein said surfaces of said substrates which are in contact with said electrochromic layer comprise at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides.
  • said electrochromic layer further comprises one or more polymers (E) which are copolymerization products of
  • R is hydrogen or methyl
  • R 2 is selected from the group consisting of
  • linear and branched unsubstituted alkyl groups having 1 to 22 carbon atoms, preferably 2 to 22 carbon atoms
  • an article according to the present invention consists of a layer assembly consisting of
  • electrochromic layer as defined above, said electrochromic layer being arranged on and in contact with a surface of said substrate,
  • an article according to the present invention consists of a layer assembly consisting of
  • said first substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides
  • said second substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides
  • said electrochromic layer is interposed between and in contact with
  • said surface of the first substrate which comprises at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides and
  • said surface of the second substrate which comprises at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides.
  • an article according to the present invention comprises a layer assembly consisting of
  • said first substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides
  • said second substrate has a surface comprising at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides
  • said electrochromic layer is interposed between and in contact with
  • said surface of the first substrate which comprises at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides and
  • said surface of the second substrate which comprises at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides.
  • the electronically conductive materials at the surface of the first and second substrate form electrodes capable of interacting with the electrochromic layer, i.e. applying an electrical field across said electrochromic layer.
  • the electrochromic layer is arranged on a surface of said substrate in such manner that it partially or completely covers said surface of said substrate.
  • the electrochromic layer forms a pattern on said surface of said substrate.
  • the pattern may be selected from any random and non-random structures, like grids, stripes, waves, dots and circles.
  • a preferred article according to the present invention further comprises a first support layer comprising a material selected from the group consisting of glass and organic polymers, and a second support layer comprising a material selected from the group consisting of glass and organic polymers, wherein said layer assembly is disposed between said first support layer and said second support layer.
  • Said first and second support layer are both in a form selected from the group consisting of foils, films, webs, panes and plates.
  • said first and said second support layer are of the same material, have the same form and have equal dimensions.
  • Preferred types of glass are e.g. float glass, low iron float glass, heat strengthened glass and chemically strengthened glass.
  • the glass has a low-emissivity (low-e) coating, sun-protection coating or any other coating on the surface facing away from the above-described layer assembly.
  • the materials of the support layers are selected such that at least one of said support layers has a light transmission of 70 % or more, preferably 90 % or more, measured according to ASTM D1003 (Procedure A) as published in November 2013.
  • both of said support layers have a light transmission of 70 % or more, preferably 90 % or more, measured according to ASTM D1003 (Procedure A) as published in November 2013.
  • antireflection (AR) coating can be used to enhance the transmittance through optical devices, and a variety of low refractive index, nanoporous, and/or nanostructured coatings can be applied to glass and plastic substrates (see for example: C. G. Granqvist, Transparent conductors as solar energy materials: a panoramic review, Solar Energy Mater. Solar Cells 91 , 1529-1598 (2007)). It has been demonstrated that coating both sides of a glass pane with self-assembled silica nanoparticle films made it possible to obtain a transmittance as large as 99.5% in the middle of the luminous spectrum (cf. P. Nostel, A. Roos, and B.
  • Preferred organic polymers are selected from the group consisting of polymethylmethacrylate (PMMA, commercially available e.g. as PlexiglasTM), polycar- bonate (PC), polyethylene (PE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), low density polypropylene (LDPP), polyethylene therephthalate (PET), glycol modified polyethylene therephthalate, polyethylene napthalate (PEN), cellulose acetate butyrate, polylactide (PL), polystyrene (PS), polyvinyl chloride (PVC), polyimides (PI), polypropyleneoxide (PPO) and mixtures thereof.
  • PMMA polymethylmethacrylate
  • said first support layer is attached to the first substrate by an adhesive and/or said second support layer is attached to said second substrate by an adhesive.
  • said article comprises a first adhesive layer between said first substrate and said first support layer and a second adhesive layer between said second substrate and said second support layer.
  • the adhesives are selected such that the adhesive layer has a light transmission which is not lower than the light transmission of the support layer which is attached to the layer assembly by said adhesive.
  • Suitable adhesives are thermoplastics, e.g. polyvinylbutyral commercially available e.g. under the trade names Butvar, Mowital, Pioloform, BUTACITE, SAFLEX, S-Lec, TROSIFOL, polyvinylalcohol, polyvinylacetate, ethylene-vinylacetate-copolymers, silicones, polyurethanes, ionomer resins (commercially available e.g. under the trade name SentryGlas®) and polymethylmethacrylate (PMMA).
  • thermoplastics e.g. polyvinylbutyral commercially available e.g. under the trade names Butvar, Mowital, Pioloform, BUTACITE, SAFLEX, S-Lec, TROSIFOL, polyvinylalcohol, polyvinylacetate, ethylene-vinylacetate-copolymers, silicones, polyurethanes, ionomer resins (commercially available e.g. under the trade name
  • attaching said support layers to said layer assembly are known in the art and are described e.g. in WO 2013/152425.
  • attaching said support layers to said layer assembly is achieved by application of heat, or heat and pressure (e.g. in an autoclave or a press or by means of heated rolls), or heat with reduced pressure (e.g. in a vacuum bag).
  • An article according to the invention typically comprises further elements, e. g. electrical connections, switches, controlling units, supporting structures and sealants. Such further elements are known in the art.
  • figure 1 is a schematic side elevation of said article not drawn to scale.
  • the article 1 according to figure 1 consists of
  • first support layer 1 1 and a second support layer 12
  • a layer assembly 15 consisting of
  • a first substrate 25 having a surface 251 and a surface 252
  • a second substrate 26 having a surface 261 and a surface 262.
  • Said electrochromic layer 20 comprises
  • Said electrochromic layer 20 is interposed between surface 251 of the first substrate 25 and surface 261 of the second substrate 26.
  • the materials of the substrates 25 and 26 are selected such that at least one of said substrates has a light transmission of 70 % or more, preferably 90 % or more, measured according to ASTM D1003 (Procedure A) as published in November 2013.
  • Surface 251 of said first substrate 25 which is in contact with electrochromic layer 20 comprises at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides, thereby forming a first electrode at surface 251 of said first substrate 25.
  • Electrode 261 of said second substrate 26 which is in contact with electrochromic layer 20 comprises at least one electronically conductive material selected from the group consisting of metals and transparent conducting oxides, thereby forming a second electrode at surface 261 of said second substrate 26.
  • Said electrodes are capable of interacting with the electrochromic layer 20, i.e. applying an electrical field across said electrochromic layer 20.
  • Article 1 further comprises a first adhesive layer 13 between said first substrate 25 and said first support layer 1 1 and a second adhesive layer 14 between said second substrate 26 and said second support layer 12.
  • said first support layer 1 1 is attached by means of first adhesive layer 13 to surface 252 of said first substrate 25 facing away from said electrochromic layer 20
  • said second support layer 12 is attached by means of second adhesive layer 14 to said surface 262 of said second substrate 26 facing away from said electrochromic layer 20.
  • compositions were prepared and the rheological behavior was studied by means of viscosity curves (viscosity as a function of the shear rate).
  • Basic studies of the rheolog- ical behavior were carried out with compositions comprising constituents (A-1 ), (B) and/or (E), but without constituents (C) and (D). In this manner, a combination of polymers (B) and (E) having very promising rheological behavior was identified.
  • constituent (D) was omitted.
  • the constituents of the tested composition are listed in table 1.
  • the data in the columns “amount wt.-%” refer to the weight percentage of the corresponding constituent based on the total weight of all constituents (A-1 ), (B), (E) and (C).
  • H 12MDI means 4,4-methylene dicyclohexyl diisocyanate
  • pTHF1000 means polytetrahydrofurane having a molecular weight in the range of from 975 to 1025 g/mol.
  • the polyurethane polymers used in the examples only the type of the diisocyanate (B1 ) and the second diol (B2-1 ) are indicated in table 1.
  • the first diol (B2-1 ) was in each case selected from the group consisting of 1 ,3-propanediol, 1 ,4-butanediol and 1 ,6-hexanediol, and the proportions of (B1 ), (B2-1 ) and (B2-2) were within the above- defined ranges. Preparing the compositions was carried out as follows:
  • constituents (C) added to the premixture to obtain a composition comprising the constituents (A-1 ), (C) and (B) and/or (E), keeping the composition for 15 minutes under stirring at said temperature in the range of from 80 °C to 100 °C to dissolve constituent (C)
  • compositions 1-13 are shown in figures 2-14.
  • Compositions 1-3 are comparison examples.
  • the viscosity curves were measured at 25 °C by means of a Rheometer Anton Paar MCR 302.
  • compositions of comparison examples 1 -3 which do not contain any polyurethane polymers (B) exhibit approximately Newtonian behavior, as the viscosity is not significantly influenced by the shear rate over a broad range (from low shear to high shear).
  • the compositions of examples 4-9 exhibit shear thinning (beyond a shoulder at low shear rate, the viscosity declines with increasing shear rate). However, the overall viscosity is rather high, due to gel formation.
  • compositions of examples 10-12 exhibit shear thinning and a significantly reduced gel formation, compared to examples 4-9. Accordingly, the viscosity was lower compared to examples 4-9. For compositions 10-12 the measurement was repeated 8 times. The deviations were within the measurement accuracy.
  • Example 13 shows that the advantageous rheological behavior of the combination of polymers (B) and (E) according to example 10 also occurs in the presence of constituent (C). Obviously the rheological behavior is mainly effected by the polymers (B) and (E) while the influence of dissolved constituents like constituent (C) on the rheological behavior is virtually negligible.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une composition, en particulier pour l'impression ou le revêtement, l'utilisation de certains polymères de polyuréthane en tant que modificateurs rhéologiques dans des compositions pour l'impression ou le revêtement, un procédé de production d'un ensemble couche comprenant une couche électrochromique, et un article comprenant un tel ensemble couche.
PCT/EP2017/070921 2016-08-18 2017-08-18 Composition notamment pour l'impression ou le revêtement comprenant des polymères de polyuréthane WO2018033620A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP16184752.0 2016-08-18
EP16184742.1 2016-08-18
EP16184752.0A EP3284764A1 (fr) 2016-08-18 2016-08-18 Composition, particulièrement d'impression ou de revêtement comprenant des polymères de polyuréthane
EP16184742.1A EP3284799A1 (fr) 2016-08-18 2016-08-18 Composition, particulièrement d'impression ou de revêtement comprenant des polymères (méth)acrylate

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WO2018033620A1 true WO2018033620A1 (fr) 2018-02-22

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WO2010142019A1 (fr) 2009-06-11 2010-12-16 Switch Materials, Inc. Filtre optique à transmittance variable et utilisations correspondantes
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WO2005023529A2 (fr) 2003-09-09 2005-03-17 Vision-Ease Lens, Inc. Stratifie de polyurethanne photochromique
WO2010142019A1 (fr) 2009-06-11 2010-12-16 Switch Materials, Inc. Filtre optique à transmittance variable et utilisations correspondantes
WO2012079160A1 (fr) * 2010-12-15 2012-06-21 Switch Materials, Inc. Filtre optique à facteur de transmission variable avec système d'électrodes sensiblement coplanaires
WO2013044371A1 (fr) 2011-09-30 2013-04-04 Switch Materials, Inc. Dérivés de diarylcyclopentène photochromes et électrochromes comme filtres optiques
US20130258439A1 (en) * 2012-03-30 2013-10-03 Ricoh Company, Ltd. Method for manufacturing an electrochromic display device and an electrochromic display device
WO2013152425A1 (fr) 2012-04-09 2013-10-17 Switch Materials , Inc. Matériaux de commutation, et compositions et procédés pour les fabriquer
WO2013190118A1 (fr) 2012-06-22 2013-12-27 Basf Se Polyuréthane thermoplastique ignifugé à base de polycarbonate-diols
WO2014060342A1 (fr) 2012-10-16 2014-04-24 Basf Se Mélanges transparents transformables thermoplastiquement constitués de polyuréthanes thermoplastiques et de poly(méth)acrylates
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