WO2004076456A1 - Solvent-free process for the preparation of diketopyrrolopyrrole derivatives - Google Patents
Solvent-free process for the preparation of diketopyrrolopyrrole derivatives Download PDFInfo
- Publication number
- WO2004076456A1 WO2004076456A1 PCT/IB2003/002710 IB0302710W WO2004076456A1 WO 2004076456 A1 WO2004076456 A1 WO 2004076456A1 IB 0302710 W IB0302710 W IB 0302710W WO 2004076456 A1 WO2004076456 A1 WO 2004076456A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- compound
- alkali metal
- pigment
- mixture
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/46—Iso-indoles; Hydrogenated iso-indoles with an oxygen atom in position 1
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0077—Preparations with possibly reduced vat, sulfur or indigo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
Definitions
- the present invention relates to certain organic compounds, processes for their manufacture, and their use.
- the invention particularly relates to an essentially solvent-free process for the preparation of the alkali-metal salts of diketopyrrolopyrrole compounds, their use as latent pigments and their use for the preparation of the corresponding diketopyrrolopyrrole pigments in their suitable pigmentary form.
- Latent pigments are described in EP-A 654 711, as are chemical, thermal or photolytic methods by means of which it is possible to generate finely divided pigment particles in situ in substrates (see also U.S. Pat. Nos. 6071989, 6211347 and 6365720). It is also known that latent pigments can be used advantageously for the preparation of pigment dispersions, and their use in colouring high molecular mass materials ( U.S. Pat. No. 6211347).
- pigments are reacted inter alia with dicarbonates in a solvent, optionally in the presence of a catalyst.
- solvents including also aromatic solvents such as benzene, toluene, xylene, anisole, chlorobenzene and pyridine.
- aromatic solvents such as benzene, toluene, xylene, anisole, chlorobenzene and pyridine.
- Preference is given to the highly polar solvents N,N-dimethylformamide, N-methyl- pyrrolidone or tetrahydrofuran. In the Examples, only N,N-dimethylformamide, N,N- dimethyl-acetamide or tetrahydrofuran are used.
- alkali metal salts of certain pigments which are easy to produce and readily hydrolyse or are induced to hydrolyse in situ to generate the corresponding pigment, are better suited as latent pigments particularly for liquid systems such as paints, printing inks and wood stains. They are particularly suitable for the preparation of pigment dispersions, and their use for pigmenting high molecular mass material.
- the incorporation of such latent pigments does not require any elaborate equipment. Moreover, no potentially hazardous organic volatile materials are liberated thereby.
- the pigments thus generated in situ are auto-dispersed and do not need further dispersion equipment and/or process.
- A is the radical or a mixture of radicals of a chromophore of the diketopyrrolopyrrole quinacridone, anthraquinone, perylene, indigo, quinophthalone, indanthrone, isoindolinone, isoindoline, dioxazine, azo, phthalocyanine or perinone series, which radical is bonded via one or more nitrogen atoms to x groups D and via one or more oxygen atoms to y groups E, the nitrogen atoms and oxygen atoms forming part of the radical A, each group D or E independently of any other(s) is an alkali metal.
- the invention also relates to a method for preparing a compound of the formula A(D)x (E)y (I) by reaction of a compound of the formula II
- suitable solvents are primary, secondary or tertiary alcohols containing 1 to 10 carbon atoms, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert- butanol, n-pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2- methyl-2-hexanol, 3-ethyl-3-pentanol, 2,4,4-trimethyl-2-pentanol, or glycols such as ethylene glycol or diethylene glycol; and also ethers such as tetrahydrofuran or dioxan, or glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; as well as dipolar aprotic solvents such as
- a mixture of solvents may also be used. It is convenient to use 5 to 20 parts by weight of solvent per 1 part by weight of reactants.
- Suitable strong bases include alkali metal hydroxides, alkali metals such as lithium, sodium and potassium, an alkali metal amide, an alkali metal hydride; and alkali metal or alkaline earth metal alkoxides derived in particular from primary, secondary or tertiary aliphatic alcohols having 1 to 10 carbon atoms. It is also possible to use a mixture of the above mentioned alkali metal alkoxides. Preference is given to using alkali metal alkoxides and hydroxides with alkali metal being especially sodium or potassium, and the alkoxide is preferably derived from a primary, secondary or tertiary alcohol.
- Particularly preferred strong bases are for example potassium hydroxide, sodium methylate, sodium isopropylate, sodium tert-butylate and sodium tert-amylate.
- These alkali metal alkoxides can also be prepared in situ by reacting the corresponding alcohol with alkali metal.
- an alcoholate may also be used as a solution or a suspension in the same alcohol or in an inert solvent.
- the alcohol and/or the solvent thus used and formed during the reaction may continuously be distilled off during the reaction thereby providing solvent-free reaction conditions.
- A is preferably the radical of a chromophore of the diketopyrrolopyrrole, quinacridone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, dioxazine, azo or the perinone series.
- derivatives having at least one immediately adjacent or conjugated carbonyl group at each nitrogen atom bonded to x groups D. It is also possible, however, for a plurality, or even all, of the groups D and/or E to be bonded to such nitrogen or oxygen atoms.
- Particularly preferred compounds of formula I are the diketopyrrolopyrrole compounds of formula III
- Rt and R 2 independently of the other is an isocyclic or heterocyclic aromatic radical.
- the radicals P and R may be different or identical, but are preferably identical.
- R t and R 2 as isocyclic aromatic radicals are preferably monocyclic to tetracyclic radicals, most preferably monocyclic or bicyclic radicals, i.e. phenyl, biphenyl or naphthyl.
- Heterocyclic aromatic radicals R ⁇ and R 2 are preferably monocyclic to tricyclic radicals.
- These radicals may be entirely heterocyclic or may contain a heterocyclic ring and one or more fused benzene rings, and the cyano group can be linked both to the heterocyclic and to the isocyclic moiety respectively.
- heterocyclic aromatic radicals are: pyridyl, pyrimidyl, pyrazinyl, triazinyl, furyl, pyrrolyl, tliiophenyl, quinolyl, benzimidazolyl, quinazolyl, quinoxalyl, phthalazinyl, phthalazindionyl, phthal- amidyl, isoquinolinyl, isothiazolyl, acridinyl, acridonyl, quinazolindionyl, quinoxalindionyl, benzoxazindionyl, benzoxazinonyl and naphthalimidyl.
- Both the isocyclic and the heterocyclic aromatic radicals may contain the customary non- watersolubilising substituents such as: (1) Halogen atoms, e.g. chlorine, bromine or fluorine atoms.
- alkyl groups containing preferably 1 to 18, especially 1 to 12, more particularly 1 to 8 and, most preferably, 1 to 4 carbon atoms.
- alkyl groups may contain non-watersolubilising substituents, e.g.
- R 5 and Re are alkyl, aryl such as napthyl, or benzyl or benzyl substituted by halogen, alkyl or alkoxy, or a heterocyclic radical
- R and R 8 are hydrogen, alkyl or alkyl substituted by cyano or hydroxy, or C - C 8 cycloalkyl, aryl or heteroaryl, especially phenyl or phenyl substituted by halogen, alkyl or alkoxy, or R and Rs together with the nitrogen atom form a 5- or 6-membered heterocyclic ring, e.g.
- substituents at the alkyl groups are mono- or dialkylated amino groups, aryl radicals such as naphthyl or preferably phenyl or phenyl substituted by halogen, alkyl or alkoxy, or also heterocyclic aromatic radicals such as 2-thienyl, 2-benzoxazolyl, 2- benzthiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridyl, or 2-, 4- or 6- quinolyl radicals.
- unsubstituted or substituted alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, hydroxymethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl.
- Rt and R 2 are phenyl or phenyl substituted by one or two fluorine, chlorine or bromine atoms or mixtures thereof, by one, two or three methoxy or methyl groups or mixtures thereof with chlorine atoms, by cyano, by dimethylamino, by trifluoromethyl, by alkoxycarbonyl of 2 to 3 carbon atoms, by tert-butyl, by cyanophenyl, by acetyl or by alkylbenzoyloxy of 11-14 carbon atoms; biphenyl; naphthyl or naphthyl substituted by methoxy; anthryl; phenanthryl; pyridyl or pyridyl substituted by methyl or by amyloxy; quinolyl; furyl or thienyl.
- the compounds of Formula III can also be prepared directly by essentially solvent free in situ synthesis, which process comprises reacting 1 mole of a disuccinate of formula
- each R 3 and R 4 independently of the other is an alkyl or a cycloalkyl or an aryl radical, with at the most 2 moles of a nitrile of the formula
- the starting materials employed are nitriles of the formula VIII wherein each of R , R 10 and R ⁇ independently of one another is hydrogen, fluorine, chlorine, bromine, cyano, trifluoromethyl, CrC 12 alkyl, C] .
- the starting materials employed are nitriles of the formula IX wherein one of R 12 and R 13 is chlorine, bromine, C 1 -C4 alkyl, cyano, C ⁇ -C 4 alkoxy, or phenoxy, carbamoyl or C 2 -C5 alkylcarbamoyl, each unsubstituted or substituted by chlorine or methyl, or phenylcarbamoyl which is unsubstituted or substituted by chlorine, methyl or methoxy, and the other is hydrogen.
- the disuccinates V to be used in the process of this invention may be dialkyl, dicycloalkyl or diaryl.
- the dialkyl, dicycloalkyl and diaryl succinates may also be unsymmetrical. However, it is preferred to use symmetrical disuccinates, most preferably symmetrical dialkyl succinates.
- disuccinates are dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, dihexyl succinate, diheptyl succinate, dioctyl succinate, diisopropyl succinate, di-sec-butyl succinate, di-tert-butyl succinate, di-tert-amyl succinate, di-[l,l-dimethylbutyi] succinate, di-[l,l,3,3-tetramethylbutyl] succinate, di-[l,l- dimethylpentyl] succinate, di-[l -methyl- 1-ethylbutyl] succinate, di-[l,l-diethylpropy ⁇ ] succinate, diphenyl succinate, di[4-methylphenyl] succinate, di-[2-methylphenyl] succinate, di-[4-chlorophenyl] succinate, monoethyl-monopheny
- the disuccinates V and the nitriles of the formula VI or VII are known compounds and may be prepared by known methods,
- This particular process of the invention is carried out in the absence of any solvent in the temperature range from 70° C to 200° C, with the preferred range being from 80° to 140° C.
- the present invention provides a process for the preparation of 1,4- diketopyrrolo[3,4-c]pyrroles of the formula III essentially in the absence of any organic solvent and in the presence of a strong base at elevated temperature, thereby alleviating the said disadvantages of the state-of-the-art solvent based process.
- the present invention also provides a process of preparation of the corresponding l,4-diketopyrrolo[3,4-c]pyrrole pigments of the formula IV in their finely divided suitable pigmentary form.
- a further preferred embodiment of the process consists in using the nitrile to be reacted with the disuccinate in no more than the stoichiometric proportions. It has been found that the yield of final product can usually be further improved by using an excess of disuccinate over the nitrile, in which case the optimum amount must be determined according to the respective reactants and may be up to 50 per cent in excess over the stoichiometric amount required with respect to the nitrile.
- D ls D 2 , D 3 and D 4 are fluorine, chlorine or bromine atoms or mixtures thereof, methoxy, methyl groups or mixtures thereof, cyano, dimemylamino, trifluoromethyl, tert-butyl or acetyl groups; the isoindolinone compounds of formula
- M is an alkali metal, preferably sodium or potassium, Zj. halogen or hydrogen, and Yi is an aromatic residue of the formula
- XVIII wherein Ei through E 4 represent CN, CONH-alkyl or CONH-aryl.
- E] . /E 2 and E 3 /E 4 can also be members of a mono- and poly-heterocyclic ring systems or combinations thereof. Examples of such compounds are the derivatives of: C.I. Pigment Yellow 139, C.I. Pigment Yellow 185, C.I. Pigment Orange 66, Pigment Orange 69, Pigment Red 260, Pigment Brown 38.
- Further compounds of the formula A(H) x (H) y (II) suitable for the formation of the compounds of formula A(D) x (E) y (I) are for example a) the azo pigments: CL Pigment Yellow 154, CL Pigment Yellow 180, CL Pigment Yellow 181, CL Pigment Yellow 182, CL Pigment Orange 36, CL Pigment Orange 62, CL Pigment Orange 64, CL Pigment Red 176, CL Pigment Red 185, CL Pigment Brown 23; b) the perylene pigments: CL Pigment Red 224, CL Pigment Violet 23; c) the perinone pigment: CL Pigment Orange 43; d) the anthraquinone pigments: CL Pigment Red 177, CL Pigment Blue 60; e) the pyrazoloquinazolone pigments: CL Pigment Orange 67, CL Pigment Red 251; f) the phthalocyanine pigment: CL Pigment Blue 16; g) the heterocyclic pigments: thiazine (THI) pigments such
- the present invention is also related to a process of making a finely divided particulate compound of formula A(H) x (H) y (II) from the corresponding initial crude compound of the same formula.
- organic pigments which are particulate organic solids
- the first stage involves the synthesis of the corresponding chemical moiety in which the product is usually formed in a large crystalline form not suitable for pigment applications.
- the primary particles are sub-divided and then tailored to meet the requirements of their application.
- Such processes of finishing or conditioning of pigments are, however, usually very energy consuming (such as wet and dry milling) or highly polluting (such as acid pasting or acid swelling). Finishing of organic pigments such as isoindolinone pigments via their alkali metal salts in situ is also described. However, the use of large quantities of an organic solvent is imperative.
- the process also requires the use of very special inert organic solvents. Besides being inert, the solvents need to be substantially anhydrous. Furthermore, the solvents need to " be regenerated for reuse in a separate process after their use in the process. Regeneration of solvents, particularly the most preferred alcoholic solvents, in substantially anhydrous form makes the process further cumbersome. Moreover, the use of large quantities of solvent also reduces the productivity and requires higher energy consumption thereby making the process less economical.
- the present process has the advantage that the use of solvent is not imperative in the finishing stage. Moreover, if the most preferred alcoholic solvents are used in place of and/or in combination with water, they need not be anhydrous, thereby making their regeneration very facile and economical..
- the final pigment composition is obtained with a fine particle size and the desired application properties such as excellent dispersability, high color strength, high weatherability, and high saturation of color.
- water or a mixture of water and a primary or a secondary is used as medium of hydrolysis.
- pigments with a particle size below 2 microns are obtained.
- the conditioned pigment is isolated by filtration, the press cake being washed with water and/or an organic solvent, preferably methanol, followed by water and dried. Good results can be obtained by performing the filtration in acidic conditions.
- an organic solvent preferably methanol
- a further objective of the present invention is to provide pigment dispersions, which possess high stability and good transparency, and a process for preparing them.
- Recent pigment applications such as color filters and ink jet applications are placing stringent requirements on the coloristic and processing properties of pigments.
- the pigments are required to possess clean, strong and bright shades to allow the opening-up of a large color area. Furthermore, they should be able to be used not only as an individual pigment but also as an element for combination in, say, trichromatic pigmentations.
- it proves advantageous to apply the pigment as dispersion since it is then possible to avoid laborious mixing and milling operations, which represent an additional hygiene burden.
- the dispersions make the pigmentation process more reproducible, since there is a more homogeneous distribution of the pigment particles than in the powder form.
- Alkali metal salts of pigments of the present invention used as latent pigments are particularly suitable for preparation of all such pigment dispersions, typically known for example from U.S. Pat. No. 6,302,953; U.S. Pat. No. 6,462,125, 4; U.S. Pat. No. 4,986,851; WO 99/01511; WO 03/008510.
- alkali metal salt pigments get auto-dispersed upon incorporation and by in situ hydrolysis, no special dispersing equipment such as bead-mills or kneaders are required for their dispersion, unlike any state-of -the-art processes for the preparation of pigment dispersions.
- Smaller particles tend to form aggregates, which in the course of the dispersion process are broken up by known techniques, by means of high-energy input in the form, for example, of ultrasound.
- One consequence of the propensity of smaller particles to aggregate is their flocculation tendency, and. so these dispersions are inherently unstable.
- the present invention accordingly, provides a process for preparing pigment dispersions composed of a pigment, a polymer and/or a dispersant, a liquid medium and optionally an alkali metal salt of an organic acid which comprises
- Organic acids suitable for this process are aliphatic, or aromatic poly-carboxylic or poly- sulphonic acids or poly-phosphonic acids containing up to 4 acid groups acids for the each aliphatic or the aromatic rest.
- Preferred organic acids acid are the ones that, besides interacting with the alkali metal salt of the pigment, can act both as a dispersing as well as an anti-microbial agent.
- Typical acids are up to C18 aliphatic acids, aromatic acid such as benzoic acids, phthalic acids terephthalic acids, isophthalic acids trimesic acids and pyromelitic acids; benzene, aikylbenzene, naphthalene and alkylnaphthalene sulphonic or phosphonic acids.
- Typical state-of-the art liquids are water organic solvents are aliphatic C] . -C alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ketones such as acetone methyl ethyl ketone, methyl isobutyl ketone or diacetone alcohol, and also polyols, cellosolves and carbitols, such as ethylene glycol, diethylene glycol, triethylene glycol, glycerol, propylene glycol, ethylene glycol monomethyl or monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, diethylene glycol monomethyl or monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol mono
- the process is particularly suitable for the preparation of aqueous pigment dispersions.
- the fine pigment dispersions prepared by the process of the invention preferably possess an average particle size distribution of 0.02-0.6 micrometers, with particular preference 0.03-0.5 micrometers and, with very particular preference, 0.06-0.4 micrometers.
- the particle size distribution was determined by the Joyce-Loebl disk centrifuging method.
- the dispersants can be ionic or non-ionic in character, preferably which possess a preferred spatial orientation in solvents of different density.
- the aqueous dispersions for example, comprise large molecules consisting of a hydrophilic head and a hydrophobic tail for example Fluorad FC-170, a non-ionic fluorine-containing surfactant from 3M Inc. (or such as OLOA.TM.
- the resulting dispersions preferably contain 20% by weight, with particular preference 10% by weight and, with very particular preference, 5% by weight of additives and may if desired include further co-solvents, examples being cyclohexanone, cyclopentanone, N,N'-dimethylformamide and dimethyl sulfoxide.
- Polymers for aqueous pigment dispersions are preferably polymers consisting of a hydrophilic and hydrophobic part.
- the former can be ionisable, and form salts, or non-ionisable.
- the polymers are preferably random, block or graft polymers.
- the hydrophilic part of the polymers is formed, for example, from monomers which in addition to functional groups such as alcohol, carboxyl, carboxamido, carboxylato or sulfo groups comprise sulfato, cyanato or carboxylic anhydride groups, or ether groups such as ethylene or propylene oxide groups, and in addition a polymerizable vinyl or vinylene radical, such as an acrylic or methylacrylic, crptyl, sulfoethylmethylacrylic, sulfopropylmethylacrylic, vinylnaphthyl, vinylphenyl or vinyltolyl radical, itaconyl radical, for example itaconyl monoesters, maleic acid or maleinyl radical, for example maleic monoesters, fumaryl radical, for example fumaryl monoesters, and especially vinylbenzoic acid.
- the monoesters are for example monoesters of itaconic, maleic or fumaric acid.
- Monomers which form the hydrophobic part of the polymers are preferably for example selected from the group of the apolar monomers consisting of styrene, styrene derivatives, such as Ci -C 4 alkyl-substituted styrene, and vinyl chloride, vinylnaphthalene, vinylnaphthalene derivatives, such as C 1 -C 4 . alkyl-substituted vinylnaphthalene, vinyltoluene, alpha. -, m-, p- or m/p-vinyltoluene and aliphatic C 12 -C 18 alkenes.
- Preferred hydrophobic apolar monomers are for example styrene, vinyltoluene and octadecene.
- the copolymers chosen preferably have a narrow molar mass distribution of 1-2 Mw/Mn (where Mw is the mass average and Mn the number average).
- polyvinyl butyrate for ethanolic dispersions and of methyl methacrylate for dispersions with methyl ethyl ketone as solvent, or to copolymers of methyl methacrylate and butyl acrylate for pigment dispersions with chloroform as solvent.
- Preferred polymers for aqueous pigment dispersion are composed for example of carboxyl- containing polymers, for example styrene, vinyltoluene and vinylbenzoic acid, or vinylbenzoic acid and apolar monomers, and of styrene and maleic anhydride or of copolymers of long-chain alkenes (C 12 -C 18 ) with maleic anhydride, for example styrene- maleic anhydride, styrene-vinyltoluene- vinylbenzoic acid or octadecene-maleic anhydride.
- carboxyl- containing polymers for example styrene, vinyltoluene and vinylbenzoic acid, or vinylbenzoic acid and apolar monomers
- styrene and maleic anhydride or of copolymers of long-chain alkenes (C 12 -C 18 ) with maleic anhydride for example styrene
- a preferred embodiment of the process of the invention relates to the preparation of aqueous basic pigment dispersions from a latent pigment with a solution of a copolymer comprising vinylbenzoic acid and a non-polar monomer or with a solution comprising a carboxyl- containing polymer.
- the reaction mass becomes crumbly and finally largely disintegrates into an almost semi-powdery material.
- the reaction mixture is heated to 120° C in 30 minutes and kept at 120° C for 30 minutes.
- the mixture is cooled to 50° C
- the material is emptied into a polyethylene sack, tightly fitted to the outlet of the reactor; affording 3248 g (90 % of theory, based on p-chlorobenzonitrile) of pigment of the formula XIX.
- Approximately 200 g (5.54 % of theory, based on p- chlorobenzonitrile) of the product are still contained in the reactor to be used in the next batch.
- the total yield thus corresponds to approximately 3448 g (approximately 95.54 % of theory, based on p-chlorobenzonitrile).
- This product produces an intense red colour when dispersed with stirring into a state-of-the- art waterborne paint system.
- the mixture is cooled to 50° C
- the material is emptied into a polyethylene sack, tightly fitted to the outlet of the reactor; the yield is 3490 g (approximately 87% of theory, based on p-chlorobenzonitrile) of the compound of formula XIX.
- the crude pigment is then finished by treating with seven volume parts of dimethyl formamide at 130° C for three hours.
- the suspension is filtered at 100° C, washed with the same volume of dimethyl formamide heated to 100°. C followed by water at 70° C
- the press cake is dried at 100° C yielding a bright red prod ⁇ ct.
- the inside temperature first drops to 75° C and thereafter rises again to 85° C as soon as the mixture of alcohols is completely distilled off.
- the reaction mass becomes crumbly and finally largely disintegrates into an almost semi- powdery material.
- the reaction mixture is stirred for another 30 minutes at 87° C under vacuum of 50 mbar.
- the mixture is cooled to 60° C and the material is emptied into a steel container.
- the yield is 2950 g of the crude compound of formula XIX of example 21 of 81.4% purity (approximately 95% of theory, based on p- chlorobenzonitrile).
- a 500 ml glass reactor is charged with 150 ml of anhydrous ter-amyl alcohol under nitrogen. 4.6 g (0.2 moles) of sodium are added thereto, and the mixture is heated to and maintained at 100- 105° C for 12 hours. To the resulting solution are then added at 80° C, 20.6 g (0.15 moles) of 4- chlorobenzonitrile. Subsequently 20.1 g (O.OLmoles) of diisopropyl succinate are metered in at 96° C. over 3 hours. The isopropanol formed during the reaction along with some tert-amyl alcohol is allowed to distil off simultaneously during the addition.
- reaction mixture is stirred for another 4 hours after the addition of diisopropyl succinate is complete. Thereafter the reaction mixture is transferred to a 500 ml round bottomed flask and the residual tert-amyl alcohol is distilled off on a rotavap (Buechi) under vacuum to yield the compound of Formula XIX as a dark red powder.
- a vacuum of 800 mbar is applied at the outlet of the condenser which is then gradually further reduced to 50 mbar, thereby allowing the tert-butyl alcohol to distil off.
- the inside temperature first drops to 75° C and thereafter rises again to 85° C as soon as the alcohol is completely distilled off.
- the reaction mass becomes crumbly and finally largely disintegrates into an almost semi -powdery material.
- the mixture is stirred for another 30 minutes at 85° C under vacuum of 50 mbar.
- the reaction mixture is cooled to 60° C.
- the material is emptied into a steel drum affording 1890 g of the product of the formula XXX.
- the resulting dispersion is homogeneous and transparent. It has a viscosity of 2.16 mPas at 25.degree. C. After several days, no tendency to precipitate is observed.
- a sample is diluted 50-fold with water and the transmission spectrum is measured in a 1 mm cell. At the maximum (520 nm) the absorption is 1.42, while at 660 nm it is only 0.1, which points to fine particles with good transparency.
- electron micrographs show that all particle dimensions are below 0.5 micrometers.
- Example 54 10 g of the pigment dispersion of Example 54 are mixed with 0.8 g of a 2% (percent by weight) solution of a surface-active substance (Fluorad FC-171 from 3M Inc.) and diethylene glycol and with 1.2 g of diethylene glycol, 0.5 g of 2-propanpl, 0.2 g of morpholine and 0.2 g of butyl sulfoxide.
- the resulting ink is tested in a "QuietJet" (Hewlett-Packard) thermal inkjet printer, which is fitted with a plastic device provided to accommodate the ink.
- a clear, sharp print quality is obtained, as is a surface coverage with a maximum optical density of 1.09 (this value is measured with a spectrometer in reflection mode, which is subtracted from the reflection of the paper).
- the ink shows no tendency to bleed or penetrate through customary commercial copier paper.
- Example 57 ⁇ • . . , . - . . ..
- the pigment dispersion shows excellent flow properties and storage stability. It is particularly suitable for ink-jet applications.
- Example 58
- the pigment dispersion shows excellent flow properties and storage stability. It is particularly suitable for tinting of architectural paints.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/545,924 US7728139B2 (en) | 2003-02-27 | 2003-06-24 | Solvent-free process for the preparation of diketopyrrolopyrrole derivatives |
DE60324970T DE60324970D1 (en) | 2003-02-27 | 2003-06-24 | SOLVENT-FREE PROCESS FOR THE PREPARATION OF DIKETOPYRROLOPYRROL DERIVATIVES |
EP03816042A EP1603913B1 (en) | 2003-02-27 | 2003-06-24 | Solvent-free process for the preparation of diketopyrrolopyrrole derivatives |
JP2004568706A JP4555087B2 (en) | 2003-02-27 | 2003-06-24 | Solvent-free production method of diketopyrrolopyrrole derivative. |
AU2003242896A AU2003242896A1 (en) | 2003-02-27 | 2003-06-24 | Solvent-free process for the preparation of diketopyrrolopyrrole derivatives |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IBPCT/IB03/00758 | 2003-02-27 | ||
PCT/IB2003/000758 WO2004076457A1 (en) | 2003-02-27 | 2003-02-27 | Solvent-free process for the preparation of pyrrolo (3,4c) pyrrole compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004076456A1 true WO2004076456A1 (en) | 2004-09-10 |
Family
ID=32922902
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2003/000758 WO2004076457A1 (en) | 2003-02-27 | 2003-02-27 | Solvent-free process for the preparation of pyrrolo (3,4c) pyrrole compounds |
PCT/IB2003/002710 WO2004076456A1 (en) | 2003-02-27 | 2003-06-24 | Solvent-free process for the preparation of diketopyrrolopyrrole derivatives |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2003/000758 WO2004076457A1 (en) | 2003-02-27 | 2003-02-27 | Solvent-free process for the preparation of pyrrolo (3,4c) pyrrole compounds |
Country Status (9)
Country | Link |
---|---|
US (1) | US7728139B2 (en) |
EP (1) | EP1603913B1 (en) |
JP (1) | JP4555087B2 (en) |
KR (1) | KR100985689B1 (en) |
CN (1) | CN100582107C (en) |
AT (1) | ATE415404T1 (en) |
AU (1) | AU2003242896A1 (en) |
DE (1) | DE60324970D1 (en) |
WO (2) | WO2004076457A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007093259A2 (en) * | 2006-02-18 | 2007-08-23 | Clariant International Ltd | High-fastness diketopyrrolopyrrole pigments |
EP1892240A1 (en) | 2006-08-18 | 2008-02-27 | Toyo Ink Mfg. Co., Ltd. | Benzoisoindole derivative, pigment composition comprising the same and colored composition |
EP3733783A4 (en) * | 2017-12-25 | 2021-11-17 | Cinic Chemicals Shanghai Co. Ltd. | Diketopyrrolopyrrole pigment compound having high weather resistance, preparation method therefor and use thereof |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005040284A1 (en) | 2003-10-23 | 2005-05-06 | Ciba Specialty Chemicals Holding Inc. | Heat-stable diketopyrrolopyrrole pigment mixtures |
DE102006007621A1 (en) * | 2006-02-18 | 2007-08-23 | Clariant International Limited | Diketopyrrolopyrrole pigments with increased fastnesses and process for their preparation |
DE102007011068A1 (en) * | 2007-03-07 | 2008-09-11 | Clariant International Ltd. | Process for the direct preparation of finely divided diketopyrrolopyrrole pigments |
WO2009074504A2 (en) * | 2007-12-10 | 2009-06-18 | Basf Se | Synthesis of dyes in mixing units |
CN101918497B (en) * | 2007-12-26 | 2014-05-28 | 东洋油墨制造股份有限公司 | Pigment composition for red color filter, method for producing the same, color composition using the same, and color filter |
JP5659823B2 (en) * | 2011-01-28 | 2015-01-28 | 東洋インキScホールディングス株式会社 | Color filter pigment composition, coloring composition, and color filter |
WO2012102399A1 (en) * | 2011-01-28 | 2012-08-02 | 東洋インキScホールディングス株式会社 | Diketopyrrolopyrrole-type pigment composition for color filters, colored composition for color filters, and color filter |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4579949A (en) * | 1982-05-17 | 1986-04-01 | Ciba-Geigy Corporation | Preparation of pyrrolo[3,4-c]pyrroles |
US4931566A (en) * | 1987-07-31 | 1990-06-05 | Ciba-Geigy Corporation | Process for the preparation of pyrrolo[3,4-c]pyrroles |
EP0962499A2 (en) * | 1998-06-02 | 1999-12-08 | Ciba SC Holding AG | Direct preparation of pigmentary pyrrolo-(3,4-C)pyrroles |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4911248B1 (en) * | 1970-05-25 | 1974-03-15 | ||
JPS54132626A (en) * | 1978-04-05 | 1979-10-15 | Toyo Soda Mfg Co Ltd | Purification of isoindorinon pigment |
JPS5650965A (en) * | 1979-10-03 | 1981-05-08 | Dainippon Ink & Chem Inc | Preparation of isoindolinone pigment |
DE3115532A1 (en) * | 1980-04-17 | 1982-01-28 | Canon K.K., Tokyo | INK-JET RECORDING METHOD AND RECORDING INK FOR RECORDING ON AN IMAGE RECEIVER |
JPS57149341A (en) * | 1981-03-13 | 1982-09-14 | Dainippon Ink & Chem Inc | Colorant for polyolefin |
DE3535276A1 (en) * | 1985-10-03 | 1987-04-09 | Basf Ag | METHOD FOR PRODUCING TETRACHLOR-3-IMINO-ISOINDOLIN-1-ON |
US4791204A (en) * | 1985-11-26 | 1988-12-13 | Ciba-Geigy Corporation | 1,4-diketopyrrolo[3,4-c]pyrrole pigments |
DE3627023A1 (en) * | 1986-08-09 | 1988-02-11 | Hoechst Ag | PIGMENT DISPERSIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
US5030669A (en) * | 1988-05-27 | 1991-07-09 | Minnesota Mining And Manufacturing Company | Pigment dispersions |
US5106533A (en) * | 1988-05-27 | 1992-04-21 | Minnesota Mining And Manufacturing Company | Pigment dispersions |
JP2764606B2 (en) * | 1989-04-14 | 1998-06-11 | 日本カーリット株式会社 | Toner for developing electrostatic images |
US5085698A (en) * | 1990-04-11 | 1992-02-04 | E. I. Du Pont De Nemours And Company | Aqueous pigmented inks for ink jet printers |
JP3141959B2 (en) * | 1992-02-12 | 2001-03-07 | 株式会社リコー | Aqueous ink composition and recording method using the same |
DE59409750D1 (en) * | 1993-07-29 | 2001-06-21 | Ciba Sc Holding Ag | New finely divided cyano-substituted diketopyrrolopyrrole pigments and production thereof |
EP0648817B1 (en) | 1993-10-13 | 1999-11-10 | Ciba SC Holding AG | Novel fluorescent dyes |
EP0648815B1 (en) * | 1993-10-15 | 1998-07-29 | DyStar Textilfarben GmbH & Co. Deutschland KG | Water soluble metal-free phthalocyanine dyes, process for their manufacture and use thereof |
EP0654711B1 (en) | 1993-11-22 | 1999-06-02 | Ciba SC Holding AG | Compositions for making structured color images and application thereof |
JP3640969B2 (en) | 1994-11-14 | 2005-04-20 | ミネソタ・マイニング・アンド・マニュファクチュアリング・カンパニー | Method for producing a dispersion of hard particles in a solvent |
KR100500572B1 (en) | 1997-01-27 | 2005-07-20 | 시바 스페셜티 케미칼스 홀딩 인크. | Soluble chromophore compounds, products comprising the compounds and the process for the preparation of mixed crystals using the compounds |
JP2002514263A (en) * | 1997-06-30 | 2002-05-14 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Method for producing fine pigment dispersion |
JP3625143B2 (en) * | 1998-12-28 | 2005-03-02 | 大日精化工業株式会社 | Pigment dispersant, pigment dispersion and color filter |
AU1980800A (en) * | 1998-12-29 | 2000-07-31 | Ciba Specialty Chemicals Holding Inc. | Improved method for producing thermally cleavable, soluble pigment derivatives |
JP2001139576A (en) * | 1999-11-11 | 2001-05-22 | Futaba Corp | Organic material, organic el element using the same and color conversion film |
US6462125B1 (en) * | 1999-12-16 | 2002-10-08 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants prepared by controlled radical polymerization having hydrophilic and hydrophobic segments |
JP2001279238A (en) * | 2000-03-30 | 2001-10-10 | Futaba Corp | Material for organic el element and organic el element |
JP2001315424A (en) * | 2000-05-08 | 2001-11-13 | Konica Corp | Ink composite and image forming method as well as acid generating method |
DE10028104A1 (en) * | 2000-06-07 | 2001-12-13 | Clariant Gmbh | Process for the preparation of diketopyrrologyrrole pigments |
WO2002085988A1 (en) * | 2001-04-19 | 2002-10-31 | Ciba Specialty Chemicals Holding, Inc. | Water-soluble salt of sulfonamides as colorants for the pigmenting of porous materials and for use in inkjet printing |
-
2003
- 2003-02-27 WO PCT/IB2003/000758 patent/WO2004076457A1/en not_active Application Discontinuation
- 2003-06-24 WO PCT/IB2003/002710 patent/WO2004076456A1/en active Application Filing
- 2003-06-24 US US10/545,924 patent/US7728139B2/en not_active Expired - Fee Related
- 2003-06-24 JP JP2004568706A patent/JP4555087B2/en not_active Expired - Fee Related
- 2003-06-24 AT AT03816042T patent/ATE415404T1/en not_active IP Right Cessation
- 2003-06-24 KR KR1020057015982A patent/KR100985689B1/en not_active IP Right Cessation
- 2003-06-24 EP EP03816042A patent/EP1603913B1/en not_active Expired - Lifetime
- 2003-06-24 CN CN03826053A patent/CN100582107C/en not_active Expired - Fee Related
- 2003-06-24 AU AU2003242896A patent/AU2003242896A1/en not_active Abandoned
- 2003-06-24 DE DE60324970T patent/DE60324970D1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4579949A (en) * | 1982-05-17 | 1986-04-01 | Ciba-Geigy Corporation | Preparation of pyrrolo[3,4-c]pyrroles |
US4931566A (en) * | 1987-07-31 | 1990-06-05 | Ciba-Geigy Corporation | Process for the preparation of pyrrolo[3,4-c]pyrroles |
EP0962499A2 (en) * | 1998-06-02 | 1999-12-08 | Ciba SC Holding AG | Direct preparation of pigmentary pyrrolo-(3,4-C)pyrroles |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007093259A2 (en) * | 2006-02-18 | 2007-08-23 | Clariant International Ltd | High-fastness diketopyrrolopyrrole pigments |
WO2007093259A3 (en) * | 2006-02-18 | 2007-11-01 | Clariant Int Ltd | High-fastness diketopyrrolopyrrole pigments |
EP1892240A1 (en) | 2006-08-18 | 2008-02-27 | Toyo Ink Mfg. Co., Ltd. | Benzoisoindole derivative, pigment composition comprising the same and colored composition |
KR101533665B1 (en) * | 2006-08-18 | 2015-07-03 | 토요잉크Sc홀딩스주식회사 | Benzoisoindole derivatives, and pigment composition and colored composition containing same |
EP3733783A4 (en) * | 2017-12-25 | 2021-11-17 | Cinic Chemicals Shanghai Co. Ltd. | Diketopyrrolopyrrole pigment compound having high weather resistance, preparation method therefor and use thereof |
US11873407B2 (en) | 2017-12-25 | 2024-01-16 | Cinic Chemicals (Shanghai) Co., Ltd. | Diketopyrrolopyrrole pigment compound having high weathering resistance and preparation method therof |
Also Published As
Publication number | Publication date |
---|---|
JP2006519167A (en) | 2006-08-24 |
KR100985689B1 (en) | 2010-10-05 |
ATE415404T1 (en) | 2008-12-15 |
CN1745082A (en) | 2006-03-08 |
DE60324970D1 (en) | 2009-01-08 |
KR20050106460A (en) | 2005-11-09 |
EP1603913A1 (en) | 2005-12-14 |
US7728139B2 (en) | 2010-06-01 |
WO2004076457A1 (en) | 2004-09-10 |
CN100582107C (en) | 2010-01-20 |
US20060246023A1 (en) | 2006-11-02 |
AU2003242896A1 (en) | 2004-09-17 |
JP4555087B2 (en) | 2010-09-29 |
EP1603913B1 (en) | 2008-11-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4720305A (en) | Mixtures of pigments | |
US8883889B2 (en) | Pigment compositions comprising pyrrolo[3,4-c]pyrroles | |
KR960015030B1 (en) | Process for the preparation of pyrrolo (3,4-c) pyrroles | |
TWI383026B (en) | Pigment dispersing agent, pigment composition and pigment dispersion | |
US7728139B2 (en) | Solvent-free process for the preparation of diketopyrrolopyrrole derivatives | |
GB2238550A (en) | New diketopyrrolopyrrole pigment mixtures comprising both sulfonated and unsulfonated components | |
JP4745226B2 (en) | Production of flopirole | |
KR100892229B1 (en) | Pigment compositions, and the preparation method and use of the same | |
US7695558B2 (en) | Diketopyrrolopyrrole pigments having heightened fastnesses and processes for preparing them | |
EP1046680B1 (en) | Pigments, the process of their manufacture and their use | |
US9346963B2 (en) | Surface-modified pigment preparations | |
US5502208A (en) | Finely particulate cyano-substituted diketopyrrolopyrrole pigments and the preparation thereof | |
US7002021B2 (en) | Diketopyrrolopyrrole pigments | |
US7967906B2 (en) | Method for directly producing fine-particle diketopyrrolopyrrol pigments | |
JP2013087260A (en) | Triphenyl methane compound | |
MXPA99005087A (en) | Direct preparation of pirrolo [3,4-c] pirro |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2006246023 Country of ref document: US Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10545924 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2035/CHENP/2005 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004568706 Country of ref document: JP Ref document number: 20038260530 Country of ref document: CN Ref document number: 1020057015982 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003816042 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057015982 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2003816042 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 10545924 Country of ref document: US |