[go: up one dir, main page]

CH406126A - Process for protecting textiles against ultraviolet rays - Google Patents

Process for protecting textiles against ultraviolet rays

Info

Publication number
CH406126A
CH406126A CH808162A CH808162A CH406126A CH 406126 A CH406126 A CH 406126A CH 808162 A CH808162 A CH 808162A CH 808162 A CH808162 A CH 808162A CH 406126 A CH406126 A CH 406126A
Authority
CH
Switzerland
Prior art keywords
radical
compound
compounds
formula
ultraviolet rays
Prior art date
Application number
CH808162A
Other languages
German (de)
Other versions
CH808162A4 (en
Inventor
Frederick Strobel Albert
Charles Catino Sigmund
Original Assignee
Gen Aniline & Film Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US138574A external-priority patent/US3215724A/en
Priority claimed from US149525A external-priority patent/US3215725A/en
Priority claimed from US191459A external-priority patent/US3272810A/en
Application filed by Gen Aniline & Film Corp filed Critical Gen Aniline & Film Corp
Publication of CH808162A4 publication Critical patent/CH808162A4/xx
Publication of CH406126A publication Critical patent/CH406126A/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62Oxygen or sulfur atoms
    • C07D213/69Two or more oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/315Compounds containing carbon-to-nitrogen triple bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/20Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192Polycarboxylic acids; Anhydrides, halides or salts thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224Esters of carboxylic acids; Esters of carbonic acid
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/345Nitriles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Description

  

  



  Verfahren zum Schützen von Textilien gegen Ultraviolettstrahlen
Die vorliegende Erfindung bezieht sich auf ein Verfahren zum Schützen von Textilmaterialien gegen Ultraviolettstrahlen durch Verwendung von a-Cyan  , B, ss-diphenylacrylsäurederivaten    als Absorptionsmittel für ultraviolettes Licht.



   Verschiedene organische Verbindungen   vermö-    gen elektromagnetische Strahlungen innerhalb des Bandes von 2900 bis 3700   A    zu absorbieren, so dass Textilien durch deren Einverleibung gegen Ultra  violettstrahlen    geschützt werden können.



   Es sind unzählige organische Verbindungen als Absorptionsmittel für den oben beschriebenen Strahlungsbereich in Vorschlag gebracht worden, der als ultravioletter Bereich bezeichnet wird. Bei den ultravioletten Strahlungen handelt es sich am häufigsten um Strahlungen, welche von der Sonne herrühren.



  Die meisten dieser Strahlungen besitzen eine Wellenlänge von 250-400   Millimikron.    Die Wirkung solcher Strahlen auf die menschliche Haut unter Erzeugung von Sonnenbrand und Sonnenbräune sind bestens bekannt. Andere Wirkungen von grosser wirtschaftlicher Wichtigkeit beziehen sich auf den durch Ultraviolettlicht verursachten, photo-chemischen Abbau.



  Manche im Handel'erhältlichen Textilien sind unter dem Einfluss solcher Strahlen unbeständig, oder sie werden in einem solchen Ausmasse beeinträchtigt, dass sie nicht mehr verkäuflich sind. Es ist ferner bekannt, dass gefärbte Textilien bei der Einwirkung von Sonnenlicht und insbesondere bei Einwirkung von Ultraviolettem Licht verblassen.



   In der belgischen Patentschrift Nr.   601 113    wird die Verwendung von Nitrogruppen freien Verbindungen der Formel
EMI1.1     
 worin (Ar) und (Ar) 2 aromatische carbocyclische Kerne, die frei von am Kern gebundenen Aminogruppen sind, Z OY oder
EMI1.2     
 und Y, Yl und Y2 Wasserstoff oder organische Reste bedeuten, zum Schutz von beispielsweise Textilien gegen ultraviolette Strahlen beschrieben.



   Diese Verbindungen haben auf Textilmaterialien eine schlechtere   Sublimierechtheit    als die   erfindungs-    gemäss verwendeten Verbindungen, wie das Beispiel zeigt.



   Es wurde nun festgestellt, dass die   a-Cyan-,/-di-      phenylacrylsäurederivate,    obgleich sie   ausserordent-    lich gute   Absorptionseigenschaften    in der Nähe des sichtbaren Bereiches des elektromagnetischen Feldes zeigen, farblose Verbindungen sind und sich mit Sicherheit so verwenden lassen, dass durch ihre Anwesenheit normalerweise farblose Textilien nicht verfärbt oder gefärbte Textilien hinsichtlich ihrer Farbe nicht beeinflusst werden. Manche der im erfindungsgemässen Verfahren verwendeten Verbindungen absorbieren überdies etwas sichtbares Licht am Violettende des Spektrums, wodurch sie für den  Schutz mancher Textilien, welche sich durch sichtbares Licht leicht abbauen lassen, wertvoll werden.



  Dies trifft beispielsweise zu für Polyester, Polypropylen, Cellulosenitrat, Polyvinylchlorid und   Polyäthy-    len, deren Stabilisierung unter Verwendung der hier in Betracht gezogenen Verbindungen besonders er  folgreich    ist.   Uberdies    werden Polypropylen und hochpolymere Verbindungen des Formaldehyds (Polyoxymethylen) in unerwartetem und hervorragendstem Masse durch die genannten Verbindungen stabilisiert.



   Die genannten neuen Verbindungen haben ferner den Vorteil, dass sie zur Erzielung der   Lichtbestän-    digkeit keiner phenolischen Hydroxylgruppe bedürfen. Demgegenüber müssen die bis jetzt verwendeten   Hydroxybenzophenon-Absorptionsmittel    eine solche Gruppierung enthalten. Die Anwesenheit einer Hy  droxylgruppe,    welche Salzbildung einzugehen vermag, macht aber solcher Absorptionsmittel für die Verwendung in alkalischen Medien ungeeignet. Allerdings bringt die Anwesenheit solcher Gruppen keinen Nachteil mit sich, sofern eine alkalische Empfind  lichkeit    kein Problem darstellt.



   Das erfindungsgemässe Verfahren ist dadurch gekennzeichnet, dass man Verbindungen der Formel
EMI2.1     
 worin   (Ar) i und    (Ar) 2 aromatische carbocyclische Reste, welche keine Nitrogruppen und keine ringgebundenen Aminogruppen enthalten, bedeuten, X Sauerstoff oder
EMI2.2     
 ist, Y einen gegebenenenfalls substituierten Kohlenwasserstoffrest oder einen heterocyclischen Rest darstellt und   Ri    Wasserstoff oder einen organischen Rest bedeutet, verwendet.



   Die verschiedenen Verbindungen können durch die folgende Gruppe von Formeln dargestellt werden :
EMI2.3     
 worin Y eine Brücke der oben definierten Art darstellt, und
EMI2.4     
 worin Y eine Brücke der oben definierten Art darstellt, wobei   R1    die obige Bedeutung hat.



   Für die Reste   Ri    kommen die folgenden, spezifischen Substituenten innerhalb der oben angegebenen Definition in Frage : Alkyl mit   1    bis etwa 50 Kohlenstoffatomen, z. B.



   Methyl, Äthyl, n-Propyl, Isopropyl, n-Butyl, n-Amyl, n-Hexyl, primäres n-Nonyl,
4-Athyl-heptyl-4, 2, 2, 4-Trimethyl-pentyl-4,    2-Athyl-hexyl-1,    primäres n-Decyl,    Undecyl-1, Tridecyl-1, Tetradecyl-1,   
Hexadecyl,   Eicosyl-1,    Tricosyl-12,
Myrisyl (30 Kohlenstoffatome) usw. ; Alkenyl :
Allyl   (CH2=CHCH2-),   
Methallyl [CH2=C   (CH3)      CH2-],   
Crotyl   (CH3CH=CHCH2-),       Butenyl-1 (CH2=CH-CHCH3),       Pentenyl-1,    y-Isopropyl-allyl,    ss-Äthyl-y-propyl-allyl,    2-Methyl-octenyl-6,
Decenyl-1, Decenyl-2, Undecenyl,
Dodecenyl-2, Octadecenyl, Docosenyl,    Pentamethyl-eicosenyl    ; Cyanalkyl (Alkyl mit 1-50 Kohlenstoffatomen), z.

   B.



     Cyanäthyl,    Cyan-n-propyl,    Cyan-n-octyl,    Cyanstearyl usw. ; Hydroxyalkyl (Alkyl mit 1-50 Kohlenstoffatomen), z. B.



   Hydroxyäthyl, Hydroxy-isobutyl,
Hydroxy-stearyl usw. ;  Carbalkoxyalkyl (jeder Alkylrest mit 1-50 Kohlenstoffatomen), z. B.



     Carbomethoxyäthyl,    Carbomethoxybutyl,
CarbÏthoxyÏthyl,   Carbäthoxybutyl,       Carbobutoxyäthyl,    Halogenalkyl (Alkyl mit 1-50 Kohlenstoffatomen)
Chloräthyl, Chlorlauryl, BromÏthyl,
Brompropyl (n-Propyl, Isopropyl) ; Alkoxyalkyl (jeder Alkylrest mit 1-50 Kohlenstoffatomen)
MethoxyÏthyl, Mehtoxydecyl,
Athoxybutyl, Athoxylauryl ;   Hydroxyalkoxyalkyl    (jeder Alkylrest mit 1-50 Kohlenstoffatomen)
HydroxyÏthoxyÏthyl, HydroxypropoxyÏthyl,
Hydroxypropoxyamyl, Hydroxybutoxypropyl,
Hydroxybutoxyamyl ;

   Aryl    Phenyl, Tolyl, Xylyl,    Cumyl,    a-Naphthyl, ss-Naphthyl,    a-Anthrachinonyl,   -Anthrachinonyl,       ,-Anthrachinonyl, Phenanthranyl,    Diphenyl und die   alkylsubstituierten    Derivate davon substituierte Aryle, z. B.



   Anisol,   PenetoT,    p-DiÏthoxyphenyl,   l-Methoxy-phenanthryl,       a-Naphthylmethyläther, ss-Naphthylmethyläther,  α-NaphthylÏthylÏther, ss-Naphthyläthyläther,   
HydroxyÏthyl-phenyl, Hydroxypropyl-phenyl,
Chlorphenyl, Bromphenyl,    1,    2-Dichlorphenyl, 1, 3-Dichlorphenyl,
1, 3, 5-Trichlorphenyl,   1,    2-Dibromphenyl,    α-Chlortotyl,      m-Chlortolyl,    m-Bromtolyl,
Brom-o-xylyl,   a, ss-Mchlornaphthyl,   
4-Bromacenaphthyl, Carboxyphenyl,
Carboxytolyle, Carboxyxylyle ; Carbalkoxyphenyle, z. B.



   Carbomethoxyphenyl, CarbÏthoxyphenyl ;   Carbalkoxytolyle,    z. B.



     Carbomethoxytolyle,    Acetophenyl,    Propiophenyl,    Butyrophenyl,    Lauroylphenyl, Stearoylphenyl,       p-Acetotolyl,    o-Acetotolyl,    a-Benzoylnaphthyl, A-Benzoylnaphthyl,   
Acetaminophenyl, Aceto-methylaminophenyl, o-Acetaminotolyl,   p-Acetaminotolyl,    a-Acetaminonaphthyl,   -Acetaminonaphthyl,   
Propioaminophenyl, Butyroaminophenyl, o-Propioaminotolyl,   p-Propioaminotolyl,    o-Butyroaminotolyl,   p-Butyroaminotolyl,       o-Lauroylaminotolyl,    p-Lauroylaminotolyl, o-Stearoylaminotolyl, p-Stearoylaminotolyl,
Sulfamylphenyl, Sulfamylnaphthyl ; Alkaryle, z. B.



   Benzyl, Phenethyl,    Phenyl-n-propyl,    Phenyl-isopropyl,
Phenyl-isobutyl, 2, 4-Dimethylbenzyl,
2-Methylbenzyl, 4-Methylbenzyl usw. ;   beterocyclische    Reste
Furyl, Tetrahydrofurfuryl,   Benzofuryl,   
Thienyl, Pyrryl, Pyrrolidyl,
2-Pyrrolidonyl, Indolyl, Carbazolyl, Oxazolyl,
Thiazolyl, Pyrazolyl, Pyridyl, Pyrimidyl,   Chinolyl,    mit den verschiedenen, folgenden. Substituenten Alkyl, Alkoxy, Halogen, Carboxy, Carboxalkoxy, Acyl und Acylamino.



   Die aromatischen carbocyclischen Kerne (Ar)1 und (Ar) 2 sind vorzugsweise Phenylreste oder   substi-    tuierte Phenylreste, können aber auch Naphthylreste und dergleichen sein. Unter den in den Resten   (Ar) i    und (Ar)   2    eventuell vorhandenen Substituenten kommen irgendwelche der obigen sowie die nachstehenden in Frage : Halogen, z. B.



   Chlor, Brom, Hydroxy, Alkoxy,   Carboxy,   
Carbonamid, Sulfonamid, Cyan, Acyloxy, Y kann einer der folgenden Reste sein :  -CH2CH2-,     -CH2CH2CH2-,  -CHgH2CHg2,  -CH2CH2CH2CH2CH2-,   
EMI3.1     
 
EMI4.1     

Selbstverständlich können andere, nicht chromophore Substituenten in den obigen Resten vorhanden sein, wie z. B.   



   -CHCICHCI-,  -CHBrCHoCHBr-,   
EMI4.2     

Die im erfindungsgemässen Verfahren verwendeten Verbindungen können auch polyoxyalkyliert sein. Zur Herstellung solcher   polyoxyalkylierter    Verbindungen kann man eine beliebige Verbindung der obigen Formel   I,    welche mindestens ein reak  tionsfähiges    Wasserstoffatom enthält, mit einem Alkylenoxyd oder einer als Oxyd wirkenden Verbindung, wie z. B.



   Athylenoxyd, Propylenoxyd, Butylenoxyd,
Butylendioxyd, Cyclohexenoxyd,
2,   3-Epoxy-l-propanol,    Epichlorhydrin,
Butadiendioxyd, Isobutylenoxyd, Styroloxyd und Mischungen davon und dergleichen, umsetzen, um das entsprechende polyoxyalkylierte Produkt zu erhalten. Man kann 1 bis etwa 200 Oxyalkylgruppen in das Molekül einführen.



   Sofern dabei etwa vorhandene phenolische Hy  droxylgruppen    nicht oxyalkyliert werden sollen, können sie, beispielsweise mit Benzolsulfonylchlorid, verestert und später regeneriert werden. Anderseits kann man phenolische Hydroxylgruppen unter Ausschluss der Amidgruppierung   oxyalkylieren,    da die letztere wesentlich langsamer reagiert. 



   Die nicht oxyalkylierten Verbindungen der Formel I sind in Wasser unlöslich. Jene Verbindungen, welche eine kleinere Menge an   Oxyalkylgruppen    enthalten, das heisst solche Verbindungen, welche bis zu etwa 4 bis 6 solcher Gruppen pro Molekül aufweisen, sind im allgemeinen in den nichtpolaren Lösungsmitteln weniger löslich, jedoch in Wasser leicht dispergierbar. Die grössere Mengen   Alkylen-    oxyd enthaltenden Verbindungen, das heisst solche mit mehr als etwa 6 Mol davon pro Mol Grundverbindung, sind wasserlöslich, wobei die Wasserlöslichkeit mit zunehmender Anzahl an Oxyalkylengruppen zunimmt.



   Die im erfindungsgemässen Verfahren zu verwendende Menge an Verbindungen der Formel I ist nicht von Bedeutung, wobei allerdings hervorzuheben ist, dass sie in ausreichender Menge zugegen sein sollten, um einen angemessenen   Stabilisierungsgrad    zu erzielen, wobei man an für sich nicht mehr davon verwenden sollte, als zur Erreichung des gewünschten Ziels erforderlich ist. Im allgemeinen können zwischen etwa 0, 1 Gew. % und 10 Gew. %, bezogen auf das Gewicht an zu stabilisierenden Textilien, verwendet werden.



   Beispiel
Das Kondensationsprodukt von Athyl-a-cyanacetat mit Benzophenon gemäss der belgischen Patentschrift Nr. 601 113 (Verbindung A) und die Verbindung der Formel
EMI5.1     
 wurden, verglichen. Je eine     Dacron 64  -Probe    wurde mit einer 2   %    igen Lösung der Verbindung A bzw. B in einem Gemisch von Benzol und Aceton (50 : 50) geklotzt, um   1      %    ige Färbungen herzustellen, und dann bei   191  C    eine Minute   l'ang    heiss fixiert. Die resultierenden Proben wurden dann in einem   W-    Reflektometer verglichen.

   Eine unbehandelte Probe reflektierte   83%    des   UV-Lichtes,    die mit Verbindung A behandelte Probe reflektierte   82      des W-    Lichtes, und die mit Verbindung B behandelte Probe reflektierte   72%    des   W-Lichtes.    Diese Werte zeigen, dass die erfindungsgemässe Behandlung einen erheblichen Schutz der Textilie ergibt, wie die wesentlich stärkere Absorption des UV-Lichtes gegenüber der Blindprobe und der mit Verbindung A behandelten Probe zeigt. Die Verbindung A sublimierte offenbar während der   Heissfixierbehandlung    ab. Die erfindungsgemäss behandelte Probe ist auch viel weniger gefärbt als die mit Verbindung A behandelte Probe.



  



  Process for protecting textiles against ultraviolet rays
The present invention relates to a method for protecting textile materials against ultraviolet rays by using α-cyano, B, ß-diphenylacrylic acid derivatives as ultraviolet light absorbers.



   Various organic compounds are able to absorb electromagnetic radiation within the band from 2900 to 3700 A, so that textiles can be protected against ultra violet rays by incorporating them.



   A myriad of organic compounds have been proposed as absorbents for the region of radiation described above, which is referred to as the ultraviolet region. The ultraviolet radiation is most often radiation that comes from the sun.



  Most of these radiations have a wavelength of 250-400 millimicrons. The effect of such rays on human skin to produce sunburn and tan is well known. Other effects of great economic importance relate to the photochemical degradation caused by ultraviolet light.



  Some commercially available textiles are unstable under the influence of such radiation, or they are deteriorated to such an extent that they are no longer salable. It is also known that dyed textiles fade when exposed to sunlight and especially when exposed to ultraviolet light.



   In the Belgian patent specification No. 601 113 the use of nitro group-free compounds of the formula
EMI1.1
 wherein (Ar) and (Ar) 2 aromatic carbocyclic nuclei which are free from amino groups bonded to the nucleus, Z OY or
EMI1.2
 and Y, Yl and Y2 denote hydrogen or organic radicals, described for the protection of, for example, textiles against ultraviolet rays.



   These compounds have a poorer sublimation fastness on textile materials than the compounds used according to the invention, as the example shows.



   It has now been found that the a-cyano -, / - diphenylacrylic acid derivatives, although they show extraordinarily good absorption properties in the vicinity of the visible range of the electromagnetic field, are colorless compounds and can be used with certainty that their The presence of normally colorless textiles is not discolored or the color of colored textiles is not influenced. Some of the compounds used in the process of the invention also absorb some visible light at the violet end of the spectrum, making them valuable for protecting some textiles which are easily degraded by visible light.



  This applies, for example, to polyester, polypropylene, cellulose nitrate, polyvinyl chloride and polyethylene, the stabilization of which is particularly successful using the compounds considered here. In addition, polypropylene and high-polymer compounds of formaldehyde (polyoxymethylene) are stabilized to an unexpected and outstanding degree by the compounds mentioned.



   The new compounds mentioned also have the advantage that they do not require a phenolic hydroxyl group to achieve light stability. In contrast, the hydroxybenzophenone absorbents used up to now must contain such a group. The presence of a hydroxyl group, which is capable of forming salt, makes such absorbents unsuitable for use in alkaline media. However, the presence of such groups is not disadvantageous as long as alkaline sensitivity is not a problem.



   The inventive method is characterized in that compounds of the formula
EMI2.1
 in which (Ar) i and (Ar) 2 are aromatic carbocyclic radicals which contain no nitro groups and no ring-bound amino groups, X is oxygen or
EMI2.2
 is, Y is an optionally substituted hydrocarbon radical or a heterocyclic radical and Ri is hydrogen or an organic radical, is used.



   The various compounds can be represented by the following group of formulas:
EMI2.3
 wherein Y represents a bridge of the type defined above, and
EMI2.4
 wherein Y represents a bridge of the type defined above, where R1 has the above meaning.



   The following specific substituents within the definition given above are suitable for the radicals Ri: alkyl having 1 to about 50 carbon atoms, e.g. B.



   Methyl, ethyl, n-propyl, isopropyl, n-butyl, n-amyl, n-hexyl, primary n-nonyl,
4-ethyl-heptyl-4, 2, 2, 4-trimethyl-pentyl-4, 2-ethyl-hexyl-1, primary n-decyl, undecyl-1, tridecyl-1, tetradecyl-1,
Hexadecyl, eicosyl-1, tricosyl-12,
Myrisyl (30 carbon atoms), etc.; Alkenyl:
Allyl (CH2 = CHCH2-),
Methallyl [CH2 = C (CH3) CH2-],
Crotyl (CH3CH = CHCH2-), butenyl-1 (CH2 = CH-CHCH3), pentenyl-1, y-isopropyl-allyl, ss-ethyl-y-propyl-allyl, 2-methyl-octenyl-6,
Decenyl-1, decenyl-2, undecenyl,
Dodecenyl-2, octadecenyl, docosenyl, pentamethyl-eicosenyl; Cyanoalkyl (alkyl of 1-50 carbon atoms) e.g.

   B.



     Cyanoethyl, cyano-n-propyl, cyano-n-octyl, cyanostearyl, etc.; Hydroxyalkyl (alkyl of 1-50 carbon atoms), e.g. B.



   Hydroxyethyl, hydroxyisobutyl,
Hydroxy-stearyl, etc.; Carbalkoxyalkyl (any alkyl radical having 1-50 carbon atoms), e.g. B.



     Carbomethoxyethyl, carbomethoxybutyl,
CarbÏthoxyÏthyl, carbethoxybutyl, carbobutoxyethyl, haloalkyl (alkyl with 1-50 carbon atoms)
Chloroethyl, chloro-lauryl, bromo-ethyl,
Bromopropyl (n-propyl, isopropyl); Alkoxyalkyl (any alkyl radical with 1-50 carbon atoms)
MethoxyÏthyl, Mehtoxydecyl,
Ethoxybutyl, ethoxylauryl; Hydroxyalkoxyalkyl (any alkyl radical with 1-50 carbon atoms)
HydroxyÏthoxyÏthyl, hydroxypropoxyÏthyl,
Hydroxypropoxyamyl, hydroxybutoxypropyl,
Hydroxybutoxyamyl;

   Aryl phenyl, tolyl, xylyl, cumyl, a-naphthyl, s-naphthyl, a-anthraquinonyl, -anthraquinonyl,, -anthraquinonyl, phenanthranyl, diphenyl and the alkyl substituted derivatives thereof substituted aryls, e.g. B.



   Anisole, PenetoT, p-DiÏthoxyphenyl, l-Methoxyphenanthryl, α-Naphthylmethyläther, s-Naphthylmethyläther, α-NaphthylÏthyläther, s-Naphthyläthylether,
HydroxyÏthyl-phenyl, Hydroxypropyl-phenyl,
Chlorophenyl, bromophenyl, 1, 2-dichlorophenyl, 1, 3-dichlorophenyl,
1, 3, 5-trichlorophenyl, 1, 2-dibromophenyl, α-chlorototyl, m-chlorotolyl, m-bromotolyl,
Bromo-o-xylyl, a, ss-chloronaphthyl,
4-bromoacenaphthyl, carboxyphenyl,
Carboxytolyls, carboxyxylyls; Carbalkoxyphenyls, e.g. B.



   Carbomethoxyphenyl, carbÏthoxyphenyl; Carbalkoxytolyls, e.g. B.



     Carbomethoxytolyle, acetophenyl, propiophenyl, butyrophenyl, lauroylphenyl, stearoylphenyl, p-acetotolyl, o-acetotolyl, a-benzoylnaphthyl, A-benzoylnaphthyl,
Acetaminophenyl, Aceto-methylaminophenyl, o-Acetaminotolyl, p-Acetaminotolyl, a-Acetaminonaphthyl, -Acetaminonaphthyl,
Propioaminophenyl, butyroaminophenyl, o-propioaminotolyl, p-propioaminotolyl, o-butyroaminotolyl, p-butyroaminotolyl, o-lauroylaminotolyl, p-lauroylaminotolyl, o-stearoylaminotolyl, p-stearoylaminotolyl,
Sulfamylphenyl, sulfamylnaphthyl; Alkaryls, e.g. B.



   Benzyl, phenethyl, phenyl-n-propyl, phenyl-isopropyl,
Phenyl-isobutyl, 2,4-dimethylbenzyl,
2-methylbenzyl, 4-methylbenzyl, etc.; beterocyclic residues
Furyl, tetrahydrofurfuryl, benzofuryl,
Thienyl, pyrryl, pyrrolidyl,
2-pyrrolidonyl, indolyl, carbazolyl, oxazolyl,
Thiazolyl, pyrazolyl, pyridyl, pyrimidyl, quinolyl, with the various following. Substituents alkyl, alkoxy, halogen, carboxy, carboxalkoxy, acyl and acylamino.



   The aromatic carbocyclic nuclei (Ar) 1 and (Ar) 2 are preferably phenyl radicals or substituted phenyl radicals, but can also be naphthyl radicals and the like. Possible substituents in the radicals (Ar) i and (Ar) 2 include any of the above and the following: Halogen, e.g. B.



   Chlorine, bromine, hydroxy, alkoxy, carboxy,
Carbonamide, sulfonamide, cyano, acyloxy, Y can be one of the following radicals: -CH2CH2-, -CH2CH2CH2-, -CHgH2CHg2, -CH2CH2CH2CH2CH2-,
EMI3.1
 
EMI4.1

Of course, other, non-chromophoric substituents can be present in the above radicals, e.g. B.



   -CHCICHCI-, -CHBrCHoCHBr-,
EMI4.2

The compounds used in the process according to the invention can also be polyoxyalkylated. To prepare such polyoxyalkylated compounds, any compound of the above formula I which contains at least one reactive hydrogen atom with an alkylene oxide or a compound acting as an oxide, such as. B.



   Ethylene oxide, propylene oxide, butylene oxide,
Butylene dioxide, cyclohexene oxide,
2, 3-epoxy-l-propanol, epichlorohydrin,
Butadiene dioxide, isobutylene oxide, styrene oxide and mixtures thereof and the like, to react to obtain the corresponding polyoxyalkylated product. From 1 to about 200 oxyalkyl groups can be introduced into the molecule.



   If any phenolic hydroxyl groups present are not to be oxyalkylated, they can be esterified, for example with benzenesulfonyl chloride, and later regenerated. On the other hand, phenolic hydroxyl groups can be oxyalkylated to the exclusion of the amide group, since the latter reacts much more slowly.



   The non-oxyalkylated compounds of the formula I are insoluble in water. Those compounds which contain a smaller amount of oxyalkyl groups, that is to say those compounds which have up to about 4 to 6 such groups per molecule, are generally less soluble in the non-polar solvents, but easily dispersible in water. The compounds containing larger amounts of alkylene oxide, that is to say those with more than about 6 moles thereof per mole of basic compound, are water-soluble, the water solubility increasing with an increasing number of oxyalkylene groups.



   The amount of compounds of the formula I to be used in the process according to the invention is not important, although it should be emphasized that they should be present in sufficient amounts in order to achieve an adequate degree of stabilization, whereby one should not use more than is necessary to achieve the desired goal. In general, between about 0.1% by weight and 10% by weight, based on the weight of the textiles to be stabilized, can be used.



   example
The condensation product of ethyl-a-cyanoacetate with benzophenone according to Belgian patent specification No. 601 113 (compound A) and the compound of the formula
EMI5.1
 were compared. One Dacron 64 sample was padded with a 2% solution of compound A or B in a mixture of benzene and acetone (50:50) in order to produce 1% coloration, and then at 191 ° C. for one minute hot fixed. The resulting samples were then compared in a UV reflectometer.

   An untreated sample reflected 83% of the UV light, the sample treated with compound A reflected 82% of the UV light, and the sample treated with compound B reflected 72% of the UV light. These values show that the treatment according to the invention results in a considerable protection of the textile, as the significantly stronger absorption of UV light compared to the blank sample and the sample treated with compound A shows. Compound A apparently sublimed off during the heat-setting treatment. The sample treated according to the invention is also much less colored than the sample treated with compound A.

 

Claims (1)

PATENTANSPRUCH Verfahren zum Schützen von Textilien gegen Ultraviolettstrahlen, dadurch gekennzeichnet, dal3 man Verbindungen der Formel EMI5.2 worin (Ar) und (Ar) 2 aromatische carbocyclische Reste, welche keine Nitrogruppen und keine ringgebundenen Aminogruppen enthalten, bedeuten, X Sauerstoff oder EMI5.3 ist, Y einen gegebenenenfalls substituierten Kohlenwasserstoffrest oder einen heterocyclischen Rest darstellt und Ri Wasserstoff oder einen organischen Rest bedeutet, verwendet. PATENT CLAIM Process for protecting textiles against ultraviolet rays, characterized in that compounds of the formula EMI5.2 where (Ar) and (Ar) 2 are aromatic carbocyclic radicals which contain no nitro groups and no ring-bound amino groups, X is oxygen or EMI5.3 is, Y is an optionally substituted hydrocarbon radical or a heterocyclic radical and Ri is hydrogen or an organic radical, is used. UNTERANSPRUCHE 1. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass man eine Verbindung der Formel EMI5.4 worin (Ar), (Ar) 2 und Y die obigen Bedeutungen haben, verwendet. SUBClaims 1. The method according to claim, characterized in that a compound of the formula EMI5.4 wherein (Ar), (Ar) 2 and Y have the above meanings, is used. 2. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass man eine Verbindung der Formel EMI5.5 worin (Ar) i, (Ar) 2 und Y die obigen Bedeutungen haben, verwendet. 2. The method according to claim, characterized in that a compound of the formula EMI5.5 wherein (Ar) i, (Ar) 2 and Y have the above meanings, is used. 3. Verfahren nach Patentanspruch und Unteranspruch 1, dadurch gekennzeichnet, dass man eine Verbindung verwendet, in welcher die Reste (Ar) 3 und (Ar) a Benzolringe und der Rest Y einen Alkylenrest, z. B. den Rest-CH2CH2-, bedeuten. 3. The method according to claim and dependent claim 1, characterized in that a compound is used in which the radicals (Ar) 3 and (Ar) a benzene rings and the radical Y is an alkylene radical, e.g. B. the radical -CH2CH2- mean. General Aniline & Film Corporation Vertreter : A. Braun, Basel 60 65 70 75 80 85 90 95 100 105 110 General Aniline & Film Corporation Representative: A. Braun, Basel 60 65 70 75 80 85 90 95 100 105 110
CH808162A 1961-07-05 1962-07-05 Process for protecting textiles against ultraviolet rays CH406126A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US12182061A 1961-07-05 1961-07-05
US138574A US3215724A (en) 1961-09-18 1961-09-18 alpha-cyano-beta, beta-diphenyl acrylic acid esters
US149525A US3215725A (en) 1961-11-02 1961-11-02 Bis-alpha-cyano-beta, beta-diphenylacrylic acid derivatives
US15087861A 1961-11-08 1961-11-08
US191459A US3272810A (en) 1962-05-01 1962-05-01 Alpha-cyano-beta, beta-diphenylacrylamide compounds

Publications (2)

Publication Number Publication Date
CH808162A4 CH808162A4 (en) 1965-10-15
CH406126A true CH406126A (en) 1966-08-15

Family

ID=27537618

Family Applications (2)

Application Number Title Priority Date Filing Date
CH808162A CH406126A (en) 1961-07-05 1962-07-05 Process for protecting textiles against ultraviolet rays
CH722163A CH458342A (en) 1961-07-05 1962-07-05 Use of compounds to protect non-textile organic materials against ultraviolet rays

Family Applications After (1)

Application Number Title Priority Date Filing Date
CH722163A CH458342A (en) 1961-07-05 1962-07-05 Use of compounds to protect non-textile organic materials against ultraviolet rays

Country Status (3)

Country Link
BE (1) BE619809A (en)
CH (2) CH406126A (en)
DE (1) DE1443923C3 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5303579A (en) * 1979-01-26 1980-07-31 Gaf Corporation (2-cyano-3,3-diphenylacryloxy) alkylene compounds
FR2594332B1 (en) * 1986-02-14 1988-12-16 Jung Louis DERIVATIVES OF AMINO-BENZOIC ACIDS, HYDROXY-BENZOIC ACIDS, CINNAMIC ACIDS, UROCANIC ACID AND BENZIMIDAZOLE WITH OR WITHOUT A GROUP OF AMINO ACID ABSORBING UVB AND / OR UVA AND FOR AVOIDING PHOTODERMATOSES, IN MAN, CONSECUTIVE TO THE ADMINISTRATION OF MEDICINES, TO THE USE OF COSMETIC PERFUMES OR PERFUMES

Also Published As

Publication number Publication date
DE1443923A1 (en) 1969-03-06
DE1443923C3 (en) 1975-04-17
DE1443923B2 (en) 1974-08-22
CH808162A4 (en) 1965-10-15
BE619809A (en) 1962-11-05
CH458342A (en) 1968-06-30

Similar Documents

Publication Publication Date Title
DE1215712B (en) Use of new hydroxyphenyl-1, 3, 5-triazines to stabilize organic materials against ultraviolet radiation
DE1291511B (en) Ultraviolet protectants for organic materials
CH318461A (en) Process for making coated paper and apparatus for carrying out this process
CH396831A (en) Process for protecting textiles against ultraviolet damage
CH350461A (en) Use of oxyketones to protect against ultraviolet radiation
DE2118798A1 (en) Organic product and UV absorber protected against the harmful effects of UV light
DE2505309C3 (en) Mixture of triazole and phenolic antioxidants to stabilize polyurethane against UV exposure
EP0674038A1 (en) Use of 4-H-3,1-benzoxazin-4-one compounds for improving the light fastness of textile materials
DE2042652A1 (en) Thiobisphenol Nickel Alkanolamm Complexes
DE1222926B (en) Protect organic substances against UV radiation
CH370874A (en) Use of oxazole derivatives for protection against ultraviolet radiation
CH406126A (en) Process for protecting textiles against ultraviolet rays
DE1190425B (en) Process for wrinkle-free textile finishing
DE2123383A1 (en) Derivatives of alpha cyanoacrylic acid, their production and use as stabilizers for organic materials
DE1914059A1 (en) UV absorber
DE1238030B (en) Protective agent for organic compounds
DE1443944C3 (en) Use of methylenemalonic acid derivatives free from microgroups to protect organic substances against ultraviolet radiation
AT203488B (en) Process for the production of new oxyketones
DE943075C (en) Process for the production of new disazo dyes and their metal complex compounds
DE2139781A1 (en) Process for the preparation of alkylated N, N diphenyl oxamides
AT222810B (en) Protection agent against ultraviolet radiation
WO1993015138A1 (en) Method of improving the heat-insulation properties of polyamide 6.6 filaments, and filaments produced by this method
DE1109172B (en) Protective agent for organic compounds against ultraviolet radiation
AT208821B (en) Protection agent against ultraviolet radiation
AT233526B (en) Protective agent against ultraviolet radiation