Polyamide-polyester fluorescent pigments

Abstract: The invention provides improved fluorescent pigment compositions comprising a fluorescent dye combined in a polyamide-polyester thermoplastic resin. The resins are prepared from aromatic polycarboxlic acids and lower aliphatic amino alcohols.

Description: The present invention relates to fluorescent compositions including a fluorescent dye and a resin carrier, and, more particularly, to novel fluorescent compositions including an organic fluorescent dye and a polyamide-polyester resin which are useful as colorants or pigments. U.S. Patents 2,938,873; 3,198,741; 3,412,036; 3,812,054; 3,922,232; and 3,915,884 disclose various fluorescent compositions made from thermoplastic resinous materials which incorporate dyes for use as coating compositions and pigments. It would be an advance in the art to have organic fluorescent compositions which resist fading or color due to exposure to light (lightfastness). The preferred organic fluorescent compositions of the present invention nave improved lightfastness. In accordance with the invention, there is provided a fluorescent pigment composition comprising at least one fluorescent dye and a polyamide-polyester thermoplastic resin which is a condensation product of isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid or trimesic acid (or mixtures thereof) with at least one aliphatic primary amino alcohol which contains from 2 to 4 carbon atoms. In a preferred embodiment the condensation reaction of the polycarboxylic acid with the primary amino alcohol is conducted in the presence of from 0.1 to 1 mol of a polyhydric alcohol. The thermoplastic fluorescent dye containing resins preferably contain at least one free carboxylic acid group, but may contain for example from 2 to 5 carboxylic acid groups. As indicated above, the starting dicarboxylic acids or their esters or acid chlorides may be selected from such acids as isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, trimesic acid and mixtures thereof. Of these acids isophthalic acid is preferred. In the preparation of the polyamide-polyester resins in accordance with the invention, a stoichiometric excess of the acid component is preferably used in the condensation reaction. About 1.0 to about 1.5 moles of COOH functional groups are reacted per each mol of NH₂ and/or OH functional groups, and, more preferably, 1.0 to 1.25 moles of COOH functional groups are reacted per mole of NH₂ and/or OH functional groups. The alcohols contain from 2 to 4 atoms, are aliphatic and have a fair degree of solubility in water. Illustrative of such amino alcohols are propanolamine, isopropanolamine, ethanolamine, butanolamine and isobutanolamine. Isopropanolamine and ethanolamine are preferred. The alcohols, in a preferred embodiment of the invention, are dihydric alcohols and are either cycloaliphatic or aliphatic. They preferably contain not more than 12 carbon atoms. Illustrative of these alcohols are ethylene glycol, propylene glycol, glycerin, pentaerythritol, cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane. Of the above cyclohexanedimethanol and ethylene glycol are preferred. The amount of polyhydric alcohol present in the reaction mixture ranges from about 0.1 to about 1 moles. In a preferred embodiment there is incorporated in to the polymer mixture prior to polymerization from about 0.1 to about 0.5 moles of the alcohol. The fluorescent dyes employed in the compositions include fluorescent organics which are brilliantly fluorescent when in solution. These daylight fluorescent-type dyes are well known in the art and belong to the dye families known as rhodamines, fluoresceins, coumarins, naphthalimides, benzoxanthenes and acridines. Typical dyes include Basic Red 1, Basic Violet 10, Basic Violet 11, Basic Violet 16, Basic Yellow 40, Solvent Yellow 44, Solvent Yellow 131 and Solvent Yellow 135. The fluorescent dyes comprise from about 0.1 to about 15% of the total weight of the pigment. The pigment is usually formed by incorporating the fluorescent dye in the condensation resin during its formation and thereafter grinding the cooled resin to the proper particle size. This particle size may range from about .1 to about 200 microns. Alternatively, the fluorescent dye can be added to the resin in a separate step after the resin is formed. The resin has been found to be friable and easily ground. This grinding is done in a conventional manner. In addition to the foregoing components, the fluorescent compositions of the present invention may be modified by inclusion of other ingredients which may react with the acid, amine and/or alcohol components. Typically, modifiers are included to increase the molecular weight by chain extension, alter the softening or melting point, provide enhanced compatibility, provide functional groups of special affinity for particular fluorescent dyes, impart thermal stability to fluorescent dyes or otherwise complement or enhance the suitability of the resin carrier composition for a particular application. Preferred modifiers include bi- and monofunctional acids, monofunctional amines, monofunctional alcohols, epoxies, metal oxides, metal carbonates and metal acetates. Examples of such modifiers include the following compounds. Illustrative bifunctional acids include p-aminobenzoic acid, p-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid and salicylic acid. Illustrative monofunctional acids include stearic acid, lauric acid, pelargonic acid, palmitic acid, and cyclohexanecarboxylic acid. Illustrative monofunctional amines include n-nonylamine, isononylamine, stearylamine, cyclohexylamine and benzylamine. Illustrative monofunctional alcohols include stearyl alcohol, cetyl alcohol, n-nonyl alcohol, benzyl alcohol, monofunctional aliphatic alcohols have a weight-average molecular weight in the range of from 400 to 700, n-decyl alcohol, tridecyl alcohol, cyclohexanol, 2-ethylhexanol and cyclododecanol. Illustrative epoxies include bisphenol A epoxies and aliphatic epoxies. Illustrative metal oxides, metal carbonates and metal acetates include zinc oxide, zinc carbonate, antimony triacetate, antimony pentoxide, antimony trioxide, calcium oxide, calcium carbonate, calcium hydroxide, magnesium oxide and magnesium carbonate. The amount of modifier used should not adversely affect the basic novel properties of the fluorescent compositions. Usually, the amount of the reactive modifier will range from about 0.1 to about 10% based on the total weight of the composition. Conventional additives such as opacifiers, antioxidants and processing aids may also be added to the fluorescent pigments. These materials may be added prior to, during, or after the condensation reaction is completed. In addition, the reaction can be catalyzed by use of catalysts such as are described in U.S. Patent 3,922,232 . MOLECULAR WEIGHT AND GENERAL METHOD OF PREPARING THE POLYMERS The compositions are prepared by condensation polymerization reactions illustrated by the following Examples. The compositions are prepared by heating a mixture of the reactants to effect polymerization thereof. Polymerization is typically completed with heating to a maximum temperature of from about 230 o to about 270 o C. The polymerized condensate is then cooled to about 220 o C and the fluorescent dye is added with stirring. EXAMPLE 1 To a heated resin flask, equipped with a mechanical stirrer, is added 46.3 grams of cyclohexanedimethanol (90%), 86.8 grams of monoisopropanolamine and 246.2 grams of isophthalic acid. Mixture is stirred and heated to 240 o C, cooled to 220 o C at which time fluorescent dyes are added to the composition. Composition is stirred at 220 o C for 5 minutes and the finished composition is cooled rapidly to room temperature. At this time the material is ground to a fine powder and tested. EXAMPLE 2 To a heated resin flask, equipped with a mechanical stirrer, is added 48.6 grams of cyclohexanedimethanol (90%), 74.13 grams of monoethanolamine and 277.4 grams of isophthalic acid. Mixture is stirred and heated to 240 o C, cooled to 220 o C at which time fluorescent dyes are added to the composition. Composition is stirred at 220 o C for 5 minutes and the finished composition is cooled rapidly to room temperature. At this time the material is ground to a fine powder and tested. In addition to improved lightfastness, advantages achieved by using this invention are: 1) Environmentally safer raw materials 2) Useful in a wide range of applications 3) Less effluent from reactor 4) Readily available raw materials

Claims: A fluorescent pigment composition comprising at least one fluorescent dye and a polyamide-polyester thermoplastic resin which is a condensation product of isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid or trimesic acid (or a mixture thereof) with at least one aliphatic primary amino alcohol which contains from 2 to 4 carbon atoms. A pigment composition according to claim 1 wherein the condensation product is additionally of 0.1 to 1 mol per cent polyhydric alcohol. A pigment composition according to claim 2 wherein the polyhydric alcohol is cyclohexane dimethanol. A pigment composition according to claim 1, claim 2 or claim 3 wherein the resin contains at least one free carboxylic acid group. A pigment composition according to any one of the preceding claims wherein the aliphatic amino alcohol is isopropanol amine. A pigment composition according to any one of claims 1 to 4 wherein the aliphatic amino alcohol is ethanol amine. A pigment composition according to any one of the preceding claims wherein the resin has a weight average molecular weight in the range of from about 500 to about 10,000. A pigment composition according to any one of the preceding claims which includes from about 0.1 to about 15% by weight of fluorescent dye based on the total weight of the pigment. A pigment composition according to any one of the preceding claims which is particulate and ranges in particle size from about .1 to about 200 microns. A method of making a pigment composition which includes condensing isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid or trimesic acid, or a mixture thereof, with at least one C₂-C₄ aliphatic primary amino alcohol and optionally 0.1 to 1 mol per cent of a polyhydric alcohol and admixing at least one fluorescent dye with the product. A method according to claim 10 wherein in the condensation between 1.0 to 1.5 moles of COOH functional groups are reacted per mole of NH₂ and/or OH functional groups.

Inventors: RUETER GEORGE F, STREITEL STEVEN G, RUETER, GEORGE F., STREITEL, STEVEN G.
Applicants: DAY GLO COLOR CORP, DAY-GLO COLOR CORP.
Application year: 1990
Main classification: C09K11
IPC codes: C09K11, C09B67, C08G69, C08K5