Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0503—Inert supplements
  • G03G5/051—Organic non-macromolecular compounds
  • G03G5/0517—Organic non-macromolecular compounds comprising one or more cyclic groups consisting of carbon-atoms only
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
  • C07C17/2635—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving a phosphorus compound, e.g. Wittig synthesis
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
  • C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
• • 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
  • C08K5/02—Halogenated hydrocarbons
  • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
• • 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
  • C08K5/04—Oxygen-containing compounds
• • 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
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/14—Styryl dyes
  • C09B23/141—Bis styryl dyes containing two radicals C6H5-CH=CH-
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
  • G03C1/8155—Organic compounds therefor

Definitions

• R R R or R represent a halogen atom of the group fluorine, chlorine or bromine, whilst another of the symbols R R R or R denotes an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms, or two of the symbols mentioned together represent a methylene dioxy group, and the remaining symbols denote hydrogen.
• the defined compounds are valuable optical brightening agents especially for polyamides polyvinyl chloride and polystyrene.
• the present invention relates to selected distyryl compounds of diphenyl, processes for their manufacture, and their use as optical brighteners for organic materials.
• the new compounds are symmetrically substituted relative to the diphenyl grouping and correspond to the formula wherein either (a) one, two or three of the symbols R R R or R represent halogen atoms of the group fluorine, chlorine or bromine, whilst the remainder of these symbols denote hydrogen, or
• one or two of the symbols R R R or R represent a halogen atom of the group fluorine, chlorine or bromine, whilst another of the symbols R R R or R denotes an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms, or two of the symbols mentioned together represent a methyl- 3,825,534 Patented July 23, 1974 enedioxy group, and the remaining symbols denote hydrogen.
• R R R and R represent halogen atoms of the group fluorine, chlorine or bromine, whilst the remainder of these symbols denote hydrogen, or
• one of the symbols R R R or R represents a halogen atom of the group fluorine, chlorine or bromine whilst another of the symbols R R R or R denotes an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms, or two of the symbols mentioned together represent a methylenedioxy group and the remaining symbols denote hydrogen.
• R R R and R represent a halogen atom from the group fluorine, chlorine or bromine, whilst the remaining symbols denote hydrogen.
• the reaction is in both cases carried out by allowing the components to react in the presence of a strongly basic alkali compound and in the presence of a preferably hydrophilic, strongly polar solvent, and in the case where alkali hydroxides are used as the strongly basic alkali compound, these alkali hydroxides can contain up to 25% of water.
• Toluene, xylene, chlorobenzene or alcohols such as, for example, ethanol, ethylene glycol monomethyl ether, and also N-methylpyrrolidone, diethylformamide, dimethylacetamide and preferably dimethylformamide or dimethylsulphoxide, may, for example, be mentioned as solvents for the process described above for the manufacture of compounds of the formula (1).
• the temperature at which the reaction is carried out can vary within wide limits. It is determined (a) by the stability to the reactants of the solvent used, especially to the strongly basic alkali compounds, (5) by the reactivity of the condensation components and ('y) by the effectiveness of the solvent-base combination as a condensation agent. Preferably the temperature lies approximately in the range of 30 to 60 C., but in many cases satisfactory results are already achievable at room temperature (about 20 C.) on the one hand, or, on the other, at temperatures of C., and even at the boiling point of the solvent, if this is desired for reasons of saving time or employing a less active but cheaper condensation agent. In principle, reaction temperatures in the range of 10 to C. are thus also possible.
• Strongly basic alkali compounds which can be used are above all the hydroxides, amides and alcoholates (preferably those of primary alcohols containing 1 to 4 carbon atoms) of the alkali metals, and for economic reasons those of lithium, sodium and potassium are of predominant interest.
• alkali sulphides and alkali carbonates arylalkali compounds, such as, for example, phenyl-lithium, or strongly basic amines (including ammonium bases, for example trialkylammonium hydroxides).
• the new compounds defined above possess a more or less pronounced fluorescence in the dissolved or finely divided state. They can be used for the optical brightening of the most diverse synthetic, semi-synthetic or natural organic materials or substances which contain such organic materials.
• Polymerisation products such as are, for example, obtainable by ring opening, for example, polyamides of the polycaprolactam type, and also polymers which are obtainable both via polyaddition and via polycondensati on, such as polyethers or polyacetals,
• Polyaddition products such as polyurethanes (crosslinked and non-crosslinked) and epoxide resins.
• Natural organic materials of animal or vegetable origin for example based on cellulose or proteins, such as cotton, wool, linen, silk, natural lacquer resins, starch and casein.
• the organic materials to be optically brightened can be in the most diverse states of processing (raw materials, semi-finished goods or finished goods). On the other hand, they can be in the form of structures of the most diverse shapes, say for example predominantly three-dimensional bodies such as sheets, profiles, injection mouldings, various machined articles, chips, granules or foams, and also as predominantly two-dimensional bodies such as films, foils, lacquers, coatings, impregnations and coatings, or as predominantly one-dimensional bodies such as filaments, fibres, flocks and wires.
• the said materials can, on the other hand, also be in an unshaped state, in the most diverse homogeneous or inhomogeneous forms of division, such as, for example, in the form of powders, solutions, emulsions, dispersions, latices, pastes or waxes and the like.
• Fibre materials can, for example, be in the form of endless filaments (stretched or unstretched), staple fibres, flocks, hanks, textile filaments, yarns, threads, fibre fleeces, felts, waddings, flock structures or woven textile fabrics, textile laminates, knitted fabrics and papers, cardboards or paper compositions, and the like.
• the compounds to be used according to the invention are of importance, inter alia, for the treatment of organic textile materials, especially woven textile fabrics.
• fibres which can be in the form of staple fibres or endless filaments or in the form of hanks, woven fabrics, knitted fabrics, fleeces, flock substrates or laminates, are to be optically brightened according to the invention, this is advantageously effected in an aqueous medium, wherein the compounds in question are present in a finely divided form, suspensions or possibly solutions.
• dispersing agents, stabilisers, wetting agents and further auxiliaries can be added during the treatment.
• the treatment is usually carried out at temperatures of about 20 to 140 C., for example at the boiling point of the bath or near it (about 90 C.).
• Solutions or emulsions in organic solvents can also be used for the finishing, according to the invention, of textile substrates, as is practised in the dyeing trade in so-called solvent dyeing (pad-thermofix application, or exhaustion dyeing processes in dyeing machines).
• the new optical brighteners according to the present invention can further be added to, or incorporated in, the materials before or during their shaping.
• they can for example be added to the compression moulding composition or injection moulding composition duringthe manufacture of films, foils or mouldings.
• theoptical brighteners can be applied in 'acc'ordance'with the following processes: 7 Addition to the starting substances (for example monomers) or intermediates (for example precondensatesor prepolymers), that is to say before or during the polymerisation, polycondensation or polyaddition,
• the new optical brighteners according to the present invention can, for example, also be employed in the following use forms:
• crosslinking agents or finishes for example starch or synthetic finishes
• synthetic resin finishes for example creaseproof finishes such as wash-and-wear, permanent-press or no-iron
• flameproof finishes soft handle finishes or antistatic finishes, or antimicrobial finishes.
• the combined treatment can in many cases advantageously be carried out with the aid of appropriate stable preparations, which contain the optically brightening compounds in such concentration that the desired brightening effect is achieved.
• the brighteners are made fully effective by an after-treatment.
• This can, for example, represent a chemical treatment (for example acid treatment), a thermal treatment (for example heat) or a combined chemical/ thermal treatment.
• the appropriate procedure to follow in optically brightening a series of fibre substrates with the brighteners according to the invention is to impregnate these fibres with the aqueous dispersions or solutions of the brighteners at temperatures below 75 (3., for example at room temperature, and to subject them to a dry heat treatment at temperatures above 100 C.,.it beingfgenerally advisable.additionally to dry the fibre material beforehand at a moderately 'elevated temperature, for, example at not less than 60.?" C. and-pp to about130 C.
• the heat treatment. in the dr'y state is then advantageously carried out at temperatures between 120 and 200 C., for example by heating in a drying chamber, by ironing within the specified temperature range or by treatment with dry, superheated steam.
• the drying and dry heat treatment can also be carried out in immediate succession or be combined in a single process stage.
• the amount of the new optical brighteners to be used according to the invention, relative to the material to be optically brightened, can vary within wide limits. A distinct and durable effect is already achievable with very small amounts, in certain cases, for example, amounts of 0.0001 percent by weight. However, amounts of up to about 0.8 percent by weight and above can also be employed. For most practical purposes, amounts between 0.0005 and 0.5 percent by weight are of preferred interest.
• 4,4-bis-(dimethoxyphosphonomethyl)-diphenyl and 2- chlorobenzaldehyde can also be initially introduced as a solution in dimethylformamide, and the sodium methylate introduced at the reaction temperature, either as asolid or as a suspension in dimethylformamide.
• omomornom 1 h I EXAMPLE 2 18 g.. of sodium methylate are dissolved in 75 ml. of
• a polyester fabric for example Dracron
• Dracron is padded at room temperature (about 20 C.) with an aqueous dispersion which per litre contains 031 to 1 g. of one of the compounds of the formula (1'1), 13), (I14), (15), (16), (17), (18), (20), (21) or (22) and 1 g. of an addition product of about 35 mols of ethylene oxide to 1 mol of octadecyl alcohol, and dried at about 100 C.
• the dry material is subsequently subjected to a heat treatment at about 220 C. for seconds.
• the polyester fabric treated in this way shows a strong optical brightening effect.
• EXAMPLE 4 10,000 g. of a polyamide, manufactured in a known manner from hexamethylenediamine adipate, in chip form are mixed with 30 g. of titanium dioxide (rutile modification) and 5 g. of one of the compounds of the formula (11), (13), 14) or ('15) in a tumbler vessel for 12 hours.
• the chips treated in this way are fused in a kettle, heated by oil or diphenyl vapour to 300'310 C., after having displaced the atmospheric oxygen by steam, and the melt is stirred for half an hour. It is then extruded through a spinneret under a nitrogen pressure of 5 atmospheres gauge, and the filament spun in this way is cooled and wound on a spinning bobbin.
• the filaments produced show an excellent brightening effect of good fastness to washing and to light.
• EXAMPLE 6 An intimate mixture of parts of polyvinyl chloride, 3 parts of st'abiliser (Advastat ED 100; Ba/Cd complex), 2 parts of titanium dioxide, 59 parts of dioctyl phthalate and 0.01 to 0.2 part of one of the compounds of the formula (I11), (15) or (16) is rolled to give a film on a calender at to C.
• the opaque polyvinyl chloride film thus obtained has a substantially higher white content than a film which does not contain the optical brightener.
• EXAMPLE 7 100 parts of polystyrene and 0.1 part of one of the compounds of the formula (11), (14) or (1 8) are fused for 20 minutes at 210 C. in a tube of 1 cm. diameter, with exclusion of air. After cooling, an optically brightened polystyrene composition of good fastness to light is obtained.
• a new styryl compound according to claim 1, which corresponds to the formula I R1 R2 wherein one, two or three of the symbols R R R and R represent halogen atoms of the group fluorine, ch10- rine or bromine, whilst the remainder of these symbols -11 denote hydrogen, characterised in that a compound of the formula is reacted in a solvent and in the presence of a strongly basic alkali compound, in a molecular ratio of 1:2, with a compound of the formula wherein, in these formulae, R R R and R have the above-mentioned meaning and one of the symbols Z and Z denotes a O CH- group and the other denotes one of the groupings of the formulae References Cited in which the in which the UNITED STATES PATENTS 3,177,153 4/1965 Pommer a a1.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Artificial Filaments (AREA)

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Cited By (8)

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• 1970
  • 1970-07-23 CH CH1817372A patent/CH540958A/de not_active IP Right Cessation
  • 1970-07-23 CH CH1117170A patent/CH547243A/de not_active IP Right Cessation
• 1971
  • 1971-07-14 DE DE2135139A patent/DE2135139C3/de not_active Expired
  • 1971-07-19 CS CS5293A patent/CS160147B2/cs unknown
  • 1971-07-19 US US00164051A patent/US3825534A/en not_active Expired - Lifetime
  • 1971-07-19 CA CA118,513A patent/CA945552A/en not_active Expired
  • 1971-07-20 FR FR7126450A patent/FR2099330A5/fr not_active Expired
  • 1971-07-20 GB GB3393671A patent/GB1360279A/en not_active Expired
  • 1971-07-21 IT IT5178971A patent/IT939329B/it active
  • 1971-07-22 NL NL7110128A patent/NL7110128A/xx not_active Application Discontinuation
  • 1971-07-22 BE BE770324A patent/BE770324A/xx unknown
  • 1971-07-23 JP JP7154709A patent/JPS5414137B1/ja active Pending

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