DE2104716A1 - Daylight fluorescent pigments - on a cross-linked polyester support - Google Patents

Daylight fluorescent pigments - on a cross-linked polyester support

Info

Publication number
DE2104716A1
DE2104716A1 DE19712104716 DE2104716A DE2104716A1 DE 2104716 A1 DE2104716 A1 DE 2104716A1 DE 19712104716 DE19712104716 DE 19712104716 DE 2104716 A DE2104716 A DE 2104716A DE 2104716 A1 DE2104716 A1 DE 2104716A1
Authority
DE
Germany
Prior art keywords
alcohol
cross
acid
fluorescent pigments
parts
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
DE19712104716
Other languages
German (de)
Inventor
Siegfried Dipl.-Chem. Dr. 6500 Mainz Noetzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to DE19712104716 priority Critical patent/DE2104716A1/en
Priority to NL7115272A priority patent/NL7115272A/xx
Priority to US00197154A priority patent/US3769229A/en
Priority to IT3088171A priority patent/IT942552B/en
Priority to AT963571A priority patent/AT310897B/en
Priority to AU35569/71A priority patent/AU457507B2/en
Priority to CA127,327A priority patent/CA967350A/en
Priority to BE775194A priority patent/BE775194A/en
Priority to GB5242371A priority patent/GB1368482A/en
Priority to FR7140556A priority patent/FR2114612A5/fr
Publication of DE2104716A1 publication Critical patent/DE2104716A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C09B67/006—Preparation of organic pigments
    • C09B67/0061—Preparation of organic pigments by grinding a dyed resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Pigments comprise an organic dye and a support constituted by a polyester produced from a dicarboxylic acid and a di- and/or a poly-functional alcohol or a di-alcohol and a di- and/or poly-functional acid, that is cross-linked by a UF or MF resin, non-plasticised and alcohol-modified. The pigments may be used in paints, pastes for serigraphy, heliography and typography, and inks for offset lithography. They have good heat-resistance and may be used in plastics to be heated to 200-300 degrees C and enamels to be used over 150 degrees C.

Description

Polykondensatharze und deren Verwendung in Tagesleuchtpigmenten Zusatz zur Patentanmeldung P 20 55 448.7 Gegenstand der Patentanmeldung P 20 55 448.7 ist ein Verfahren zur Herstellung von Kondensatharzen, das dadurch gekennzeichnet ist, daß man ein vernetzbares, reaktive Gruppen enthaltendes Polykondensat aus einer Dicarbonsäure und einem bi- und/oder polyfunktionellen Alkohol oder einem bifunktionellen Alkohol und einer di- und/oder polyfunktionellen Carbonsäure mit einem unplastifizierten alkoholmodifizierten Harnstoff- oder Aminotriazin-Formaldehydharz in einem Lösungsmittel oder Lösungsmittelgemisch reagieren läßt sowie die Verwendung dieser Kondensatharze als Trägerharze in Tagesleuchtpigmenten.Polycondensate resins and their use in daytime luminous pigments additive for patent application P 20 55 448.7 is the subject of patent application P 20 55 448.7 a process for the production of condensate resins, which is characterized in that that a crosslinkable, reactive group-containing polycondensate from a Dicarboxylic acid and a bifunctional and / or polyfunctional alcohol or a bifunctional Alcohol and a di- and / or polyfunctional carboxylic acid with an unplasticized one alcohol-modified urea or aminotriazine-formaldehyde resin in a solvent or solvent mixture reacts and the use of these condensate resins as carrier resins in daytime luminescent pigments.

In weiterer Ausgestaltung dieses Erfindungsgedankens wurde nun gefunden, daß man die nach dem Verfahren des Hauptpatents erhältlichen Polykondensatharze auch erhält, wenn man die Vernetzung der reaktive Gruppen enthaltenden Polyester mit den harnstoff-oder Ami.notriazin-Forma ldehydharzen in Gegenwart saurer Katalysatoren durchführt.In a further embodiment of this inventive concept it has now been found that the polycondensate resins obtainable by the process of the main patent also obtained when the crosslinking of the polyester containing reactive groups with the urea or ami.notriazine formaldehyde resins in the presence of acidic catalysts performs.

Als saure Katalysatoren kommen beispielsweise in Frage Oxalsäure, Adipinsäure, p-Toluolsulfonsäure, d,l-Camphersulfonsäure, Atilchsaure, Chloressigsäureamid, Phosphorsäure, Phosphorsäureester, Glyceri.ndichlorhydrin, Natriumsalze von Halogencarbonsäuren und ,Ammoniumchlorid. ~ Diese sauren Katalysatoren werden zu den die Polyesterkondensate und die Vernetzerharze enthaltenden Lösungen gegeben und zwar in einer Menge von 0,5 bis 20, vorzugsweise 2 bis 10 Gewichts-%.Suitable acidic catalysts are, for example, oxalic acid, Adipic acid, p-toluenesulfonic acid, d, l-camphorsulfonic acid, lactic acid, chloroacetic acid amide, Phosphoric acid, phosphoric acid esters, glyceryl dichlorohydrin, sodium salts of halocarboxylic acids and, ammonium chloride. ~ These acidic catalysts become the the polyester condensates and the crosslinking resin-containing solutions are given and although in an amount of 0.5 to 20, preferably 2 to 10% by weight.

Im übrigen gestalten sich die Vcrfahrensbedingullgen und die verwendeten Ausgangskomponenten in der gleichen Art wie in der Hauptanme ldung angegeben.In addition, the procedural conditions and the used Starting components in the same way as specified in the main application.

Die durch den Zusatz der sauren Katalysatoren erhaltenen Polykondensate zeichnen sich gegenüber den nach dem Verfahren der Hauptanineldung erhältlichen Produkten durch eine größere Sprödig keit bei sonst gleichen Eigenschaften aus. Sie sind daher ebenfalls als Trägerharze für Tagesleuchtpigmente geeignet.The polycondensates obtained by adding the acidic catalysts stand out compared to those obtainable by the procedure of the main application Products due to their greater brittleness with otherwise identical properties. They are therefore also suitable as carrier resins for daytime luminous pigments.

Beispiel 194 Teile Dimethylterephthalat, 201 Teile 1,1,1-Trimethylolpropan und 0,058 Teile Mangan-(II)-acetat werden unter Stickstoff innerhalb einer halben Stunde im Ölbad auf eine Ölbadtemperatur von 1500C erhitzt. Die Masse ist dann geschmolzen. Unter Rühren wird dann die Ölbadtemperatur auf 2500C gesteigert, und zwar so, daß jeweils eine Stunde eine Ölbadtemperatur von 175°, 20()O, 2250 und 250°C eingehalten wird. Während dieser Reaktionszeit destillieren 47 Teile Methanol entsprechend 73 % der theoretischen Menge ab. Das entstanderle heiße, viskose Polyesterharz wird ausgegossen. Es erstarrt beim Erkalten zu einem transparenten, schwach klebrigen Produkt, das in der Hitze in Xylol/Butanol (50/50 Vol.Teile) löslich ist und eine OH-Zahl von 377-380 hat.Example 194 parts of dimethyl terephthalate, 201 parts of 1,1,1-trimethylolpropane and 0.058 parts of manganese (II) acetate are under nitrogen within half a Heated in an oil bath to an oil bath temperature of 1500C for an hour. The mass is then melted. The oil bath temperature is then increased to 2500C with stirring in such a way that An oil bath temperature of 175 °, 20 () O, 2250 and 250 ° C is maintained for one hour each will. During this reaction time, 47 parts of methanol distill corresponding to 73 % of the theoretical amount. The resulting hot, viscous polyester resin is poured out. When it cools, it solidifies to a transparent, slightly sticky appearance Product that is soluble in xylene / butanol (50/50 parts by volume) and a Has an OH number of 377-380.

Zur Herstellung der Vernetzerharzlösungen werden 126 Teile Melamin und 180 Teile Paraformaldehyd in 306 Teilen n-Butanol 3 Stunden lang auf 110 - 1200C erhitzt. Die erhaltene Lösung hat einen Feststoffgehalt von 50 <M4> %, bastiz L alls; Einbrennrückstand bei 1500C während 5 Stunden.126 parts of melamine are used to produce the crosslinking resin solutions and 180 parts of paraformaldehyde in 306 parts of n-butanol for 3 hours at 110-1200C heated. The solution obtained has a solids content of 50 <M4>%, basically L alls; Burn-in residue at 1500C for 5 hours.

60 Teile des obigen Polyesterharzes werden als ziege Lösung in Xylol/Butanol (50/50 Vol.-Teile) mit 40 Gew.-Teilen eines Melamin-Formaldehyd-Harzes, das als 50%ige Lösung in Butanol vorliegt und 2 Gew.-% 10-Methoxybenzoxanthen-3,4-dicarbonsäurehydrazid enthält, bei Raumtemperatur vermischt und nach Zusatz von 4 Gew.-Teilen Adipinsäure bei 1500C im Vakuum (300 mm Hg-Säule) in 15 Stunden gehärtet. Das feste Härtungsprodukt fluoresziert intensiv grüngelb und ist außerordentlich spröde.60 parts of the above polyester resin are used as a goat solution in xylene / butanol (50/50 parts by volume) with 40 parts by weight of a melamine-formaldehyde resin, which as 50% solution in butanol is present and 2% by weight 10-methoxybenzoxanthene-3,4-dicarboxylic acid hydrazide contains, mixed at room temperature and after adding 4 parts by weight of adipic acid cured at 1500C in a vacuum (300 mm Hg column) in 15 hours. The solid hardening product fluoresces intensely green-yellow and is extremely brittle.

Es wird in einer Kugel- oder Schwingmühle gemahlen. Das gemahlene Produkt hat einen beträchtlich geringeren Grobkornanteil als das nach Beispiel 1 der Hauptanmeldung hergestellte Produkt.It is ground in a ball or vibration mill. The ground The product has a considerably lower proportion of coarse grain than that of Example 1 the product manufactured in the main application.

Anstelle von Adipinsäure kann die gleiche Menge an d,l-Campher sulfonsSure als Härtungskatalysator verwendet werden.Instead of adipic acid, the same amount of d, l-camphor sulfonic acid can be used as a curing catalyst.

Claims (2)

PATENTANSPRÜCHEPATENT CLAIMS 1. Weitere Ausgestaltung des Verfahrens zur Herstellung von Kondensatharzen durch Vernetzung eines Vernetzbaren, reaktive Gruppen enthaltenden Polykondensats aus einer Dicarbonsäure und einem bi- und/oder polyfunktionellen Alkohol oder einem bifunktionellen Alkohol und einer di- und/oder polyfunktionellen Carbonsäure mit einem unplastifizierten, alkoholmodifizierten Harnstoff- oder Aminotriazin-Formaldehydharz in einem Lösungsmittel oder Lösungsmittelgemisch gemäß Patent (Patentanmeldung P 20 55 448.7), dadurch gekennzeichnet, daß man hier die Vernetzung in Gegenwart saurer Katalysatoren durchführt.1. Further development of the process for the production of condensate resins by crosslinking a crosslinkable polycondensate containing reactive groups from a dicarboxylic acid and a bi- and / or polyfunctional alcohol or a bifunctional alcohol and a di- and / or polyfunctional carboxylic acid with an unplasticized, alcohol-modified urea or aminotriazine-formaldehyde resin in a solvent or solvent mixture according to patent (patent application P. 20 55 448.7), characterized in that the crosslinking in the presence of acidic Performs catalysts. 2. Verfahren zur Herstellung von Tagesleuchtpigmenten, dadurch gekennzeichnet, daß man ein Kondensatharz nach Anspruch 1 als Trägermaterial verwendet.2. A process for the production of daytime luminescent pigments, characterized in that that a condensate resin according to claim 1 is used as the carrier material.
DE19712104716 1970-11-11 1971-02-02 Daylight fluorescent pigments - on a cross-linked polyester support Pending DE2104716A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DE19712104716 DE2104716A1 (en) 1971-02-02 1971-02-02 Daylight fluorescent pigments - on a cross-linked polyester support
NL7115272A NL7115272A (en) 1970-11-11 1971-11-05
US00197154A US3769229A (en) 1970-11-11 1971-11-09 Daylight fluorescent pigments and process for preparing them
IT3088171A IT942552B (en) 1970-11-11 1971-11-09 LUMINESCENT PIGMENT IN DAYLIGHT AND PROCEDURE FOR THEIR PREPARATION
AT963571A AT310897B (en) 1970-11-11 1971-11-09 Process for the production of new daytime luminous pigments
AU35569/71A AU457507B2 (en) 1970-11-11 1971-11-10 New daylight fluorescent pigments and process for preparing them
CA127,327A CA967350A (en) 1970-11-11 1971-11-10 Daylight fluorescent pigments and process for preparing them
BE775194A BE775194A (en) 1970-11-11 1971-11-10 NEW FLUORESCENT PIGMENTS AND THEIR PREPARATION
GB5242371A GB1368482A (en) 1970-11-11 1971-11-11 Daylight fluorescent pigments and process for their preparation
FR7140556A FR2114612A5 (en) 1970-11-11 1971-11-12

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712104716 DE2104716A1 (en) 1971-02-02 1971-02-02 Daylight fluorescent pigments - on a cross-linked polyester support

Publications (1)

Publication Number Publication Date
DE2104716A1 true DE2104716A1 (en) 1972-08-17

Family

ID=5797574

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19712104716 Pending DE2104716A1 (en) 1970-11-11 1971-02-02 Daylight fluorescent pigments - on a cross-linked polyester support

Country Status (1)

Country Link
DE (1) DE2104716A1 (en)

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