CN1524112A - Thermoplastic fluorescent pigment - Google Patents
Thermoplastic fluorescent pigment Download PDFInfo
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- CN1524112A CN1524112A CNA028136292A CN02813629A CN1524112A CN 1524112 A CN1524112 A CN 1524112A CN A028136292 A CNA028136292 A CN A028136292A CN 02813629 A CN02813629 A CN 02813629A CN 1524112 A CN1524112 A CN 1524112A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/14—Monomers containing three or more carbon atoms
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
Abstract
The invention relates to a thermoplastic fluorescent pigment obtained by the condensation of a diisocyanate prepolymer and an aliphatic diamine, a cycloaliphatic diamine or a mixture of a diamine and a polyol in the presence of a fluorescent dye, wherein the prepolymer is obtained by the reaction of an aromatic sulfonamide with an excess of aliphatic, cycloaliphatic and/or or aromatic diisocyanate, and wherein the molar excess of diisocyanate in the prepolymer equals the molar amount of the aliphatic diamine, the cycloaliphatic diamine or the mixture of a diamine and polyol present in the condensation suspension.
Description
The invention provides the thermoplasticity high-visibility pigment with improved solvent resistance, this pigment is suitable for to various materials painted, comprises plastics, especially polyolefine, and paint, ink and textiles.
Background of invention
Past, the known method for preparing thermoplasticity pigment was with dicarboxylic acid and difunctional alcohol, diamines and/or alkanolamine reaction.US 3,922, and 232 (Schein) disclose some the resinous precondensate as fluorescence dye matrix, and this precondensate is derived from polyfunctional acid's component and polyol.Yet because the softening temperature of resulting thermoplasticity high-visibility pigment is no more than 150 ℃, this method has many shortcomings.In addition, they are dissolvable in water in many organic solvents, and are therefore very limited in application facet.
In addition, US 6,103, and 006 (DiPietro) discloses the thermoplasticity high-visibility pigment, wherein, reacted fluorogenic dye is introduced, and with covalent bonding on polymer backbone.Described polymer backbone is preferably polymeric amide or polyesteramide.
The softening temperature of many raising thermoplasticity high-visibility pigments and the method for solvent resistance thereof are disclosed.At US 3,741, disclosed method is to make vulcabond and sulphonamide and polyvalent alcohol generation polymerization addition reaction among 907 (Beyerlin).The softening temperature of resulting thermoplasticity high-visibility pigment is 155-270 ℃, and is insoluble to or actual being insoluble in organic coating composition and the ink solvent commonly used.The polymerization addition reaction is carried out at 100-250 ℃ of batch, preferred 150-200 ℃.The shortcoming of present method is that the polymerization addition reaction is thermopositive reaction, and the spontaneous rising of temperature meeting of reaction mixture is easy to surpass the thermal destruction level that is dispersed in the fluorescence dye in the polyblend before resin formation.
US 5,795, and 379 (Schwent etc.) disclose in the presence of dyestuff, make the polyisocyanic acid ester oligomer form thermoplasticity pigment with the mixture reaction of the polyfunctional compound with reactive hydrogen.The formation of this resin is to carry out in batches, for example, under reactive extrusion, carries out when temperature is higher than 200 ℃.Preferred polyisocyanic acid ester oligomer is the trimerization isophorone diisocyanate.Preferred polyfunctional compound is amine, acid amides or alcohol or carboxylic acid, sulfonic acid or phosphoric acid.The shortcoming of this batch reaction method is that the polymerization addition reaction is thermopositive reaction, and the spontaneous rising of temperature meeting of reaction mixture is easy to surpass the thermal destruction level that is dispersed in the fluorescence dye in the polyblend before resin formation.
Improve the softening temperature of thermoplasticity high-visibility pigment and another method of solvent resistance thereof and comprise a kind of two-step approach,, describe among 090 (Waters etc.) as at US 5,714.The first step by with excessive diamines or polyvalent alcohol and di-isocyanate reaction with the prepolymer in the formation water dispersion.The second step usefulness acid anhydrides such as Tetra hydro Phthalic anhydride and metal oxide such as magnesium oxide solidify dispersion.The degraded point of this thermosetting fluorescent pigment is lower than 250 ℃.The shortcoming of present method is that the solubleness of fluorescence dye in polyureas and urethane is limited, thereby the pigment that forms has shallow relatively color.
Summary of the invention
The invention provides and have the novel thermoplastic high-visibility pigment that softening temperature is higher than 180 ℃ and excellent solvent-resistance.Pigment of the present invention is by a two-step approach preparation.The first step comprises and forms the painted oligopolymer (prepolymer) of a kind of liquid state, by will excessive vulcabond and sulfuryl amine reaction and prepolymer dyeed make.In second step; painted prepolymer dispersion that will be in the protectiveness glue solution is with the diamines of equimolar amount or the mixture solidified of diamines and polyvalent alcohol; obtain having the polycondensate of polyureas or copolymerization (urea) ammonia ester structure; or without any diamines or polyvalent alcohol; in the later case; the prepolymer water cure obtains polyureas by a kind of unsettled carboxylamine intermediate, and this carboxylamine is decomposed into amine and carbonic acid gas.Resulting thermoplasticity high-visibility pigment is insoluble to or actually is insoluble to most of organic solvents, and softening temperature is higher than 180 ℃.They or by having extensive grain size distributes and erose aspherical particle is formed (if not using tensio-active agent), or form (if using one or more tensio-active agents) substantially by the spherical particle of unifying to be of a size of the 1-5 micron.
The present invention also provides the method for preparing such pigment, comprises
A) in the presence of catalyzer, make the compound and the aromatic sulfuryl amine reaction that are selected from aliphatics, alicyclic and aromatic diisocyanate and composition thereof;
B) with the prepolymer dyeing of the composition of a kind of fluorescence dye or fluorescence dye with A;
C) prepolymer after the dyeing of B is introduced in the protection glue solution, this aqueous solution is optional can to comprise tensio-active agent;
D) in the presence of catalyzer, suspension C) and compound that is selected from down group or water reaction, this group compound comprises aliphatics or alicyclic diamine, or the mixture of aliphatics or alicyclic diamine and polyvalent alcohol;
E) from suspension, isolate the hardened resin, the dry hardened resin of subsequent drying and depolymerization.
Detailed Description Of The Invention
Solvent resistance pigment of the present invention can obtain by the following method:
In the presence of catalyzer, make the compound and the aromatic sulfuryl amine reaction that are selected from aliphatics, alicyclic and aromatic diisocyanate and composition thereof, temperature of reaction is 40-90 ℃, preferred 50-60 ℃.The preferred catalyst of steps A is a triethylamine, measures to be 1-5 weight %, most preferably 2-4 weight %.The mixture of aliphatics and/or alicyclic diisocyanate and aromatic diisocyanate preferably comprises the aromatic diisocyanate of 10-50 weight %.To every mole of vulcabond, in reaction mixture, there is the 0.1-0.4 mole, the aromatic sulfuryl amine of preferred 0.2-0.3 mole.The representative of aliphatics and alicyclic diisocyanate comprises, as 1,4-fourth vulcabond, 1, hexamethylene-diisocyanate, trimethylammonium hexamethylene diisocyanate, 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (isophorone diisocyanate) and 4,4 '-two isocyanato-dicyclohexyl methyl hydrides.The representative of aromatic diisocyanate comprises, as penylene-1,4-vulcabond, 2,4-and 2,6-tolylene diisocyanate and their process mixture, naphthylene-1,5-vulcabond, 3,3 '-dimethylbenzene-4,4 '-vulcabond, ditane-4,4 '-vulcabond, 3,3 '-dimethyl diphenyl methane-4,4 '-vulcabond, a phenylene diisocyanate, 2,4-benzyl support vulcabond dipolymer and dianisidine vulcabond.
The representative of aromatic sulfuryl amine comprises, as benzsulfamide, contraposition and ortho position toluol sulfonamide and their process mixture, and naphthylene-1-sulphonamide, naphthylene-2-sulphonamide, m-nitro sulphonamide and p-chloro benzenesulfonamide.
Fluorescence dye is selected from a) water-soluble fluorescent dye, b) oil soluble (water-insoluble) fluorescence dye, c) medium fluorescent polymer solvability dyestuff and d) a) and/or b) and mixture c), ratio be 10-90 weight % a) and/or b) with the c of 90-10 weight %).
Typical case's representative of water-soluble fluorescent dye is a rhodamine, and fluorescein and some tonka bean camphors contain ionic group, as basic yellow 40 in their structure.Typical case's representative of oil soluble (water-insoluble) fluorescence dye is a tonka bean camphor, but as Bo Lun wind SOL, solvent yellow 135 or naphthalimide.Medium fluorescent polymer solvability dyestuff arrives the heterogeneous ring compound of (V) for (I) as the structure that has reactive amino or hydroxyl.
Wherein,
X is oxygen or NR
2', R
2' be defined as R independently
2
R
1Be hydrogen, halogen ,-NR
2R
3, R
3-O-or R
3-S-,
R
2Be hydrogen, C
1-6Alkyl, C
6-10Aryl, (C
6-10) aryl-(C
1-6) alkyl or (C
1-6) alkyl-(C
6-10) aryl, alkyl and/or aromatic yl group be by hydroxyl, C
1-6Alkoxyl group, C
6-10Aryloxy or halogen replace; With
R
3Be C
1-6Alkyl, C
6-10Aryl, (C
6-10) aryl-(C
1-6) alkyl or (C
1-6) alkyl-(C
6-10) aryl, alkyl and/or aromatic yl group be by hydroxyl, C
1-6Alkoxyl group, C
6-10Aryloxy or halogen replace;
R
4And R
5Be defined as R independently
2
Y is a sulphur, oxygen or-NR
2", R
2" be defined as R independently
2And n, m and p are 0-12.
Preferred dyestuff is a basic yellow 40, solvent yellow 16 0, and Basonyl red 485 and Basonyl are red 560, and formula (I) and the dye composition (III) represented, and wherein, X is oxygen or NR
2', R
2' be hydrogen or methyl.R
1Be hydrogen, Y is sulphur and n, and m and p are 2-6, are preferably 2 or 3.
The amount that fluorescence dye adds is 1-5 weight %, and preferred 2-4 weight % is most preferably about 3 weight %.
For the protection glue solution of preparation process C and D, with 1-5 weight %, preferred 2-4 weight %, most preferably the water-soluble polymers of (based on the weight of painted prepolymer B) and water mix to form protection glue about 3 weight %.The optional tensio-active agent that adds 1-3 weight %, itself or nonionic surface active agent, or the mixture of ionic and nonionic surface active agent.
The typical water soluble polymers that forms protection glue is a Natvosol, sodium carboxymethyl-cellulose, methylcellulose gum, ethyl cellulose, the water-soluble polymers of polyvinyl alcohol and vinylformic acid and methacrylic acid and multipolymer.
Suitable nonionogenic tenside has Solsperse 41090 (from the phosphorylation alkoxylate polymkeric substance of ZENECASpecialties), and Surfinol CT-111 is (from Air Product ﹠amp; 2,4,7 of Chemicals company, 9-methyl-5-decine-4,7-glycol) and Triton CF-10 (from the alkyl aryl polyether of Union Carbide).The example of non-ionic type and ionogenic surfactant mixture is above-mentioned nonionic surface active agent of mentioning and Potassium tripolyphosphate, and sodium lauryl sulphate or Surfinol CT-131 are (from Air Product﹠amp; Chemicals company) mixture, the ratio of nonionic surface active agent and ionogenic surfactant are 1: 1 to 3: 1.
In addition,, add the aliphatie diamine of 0.6-0.9 mole to every mole vulcabond, alicyclic diamine, perhaps, the mixture of aliphatie diamine or alicyclic diamine and polyvalent alcohol.The molar weight of the diamines that adds in the prepolymer of steps A (or diamines and polyvalent alcohol) adds that the molar weight of sulphonamide must equal to add the molar weight of the vulcabond in the prepolymer of steps A.When not having diamines and polyvalent alcohol, the vulcabond group in the prepolymer will react with excessive water, forms polyureas through a kind of unstable carboxylamine intermediate that is decomposed into amine and carbonic acid gas.
The representative of aliphatics and alicyclic diamine comprises, for example, and 1,1,4-butanediamine, 1,6-hexanediamine, trimethylammonium hexanediamine, 1,4-diamino-cyclohexane, different phorone diamines, hydrogenant 4,4 '-diaminodiphenyl-methane.
The mixture of diamines and polyvalent alcohol comprises the diamines of 90-10 weight % and the polyvalent alcohol of 10-90 weight %.
The representative of polyvalent alcohol comprises, for example, and ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,4-hydroxymethyl-cyclohexane, dihydroxyphenyl propane, TriMethylolPropane(TMP), glycerine, tetramethylolmethane and Dipentaerythritol.
Painted prepolymer B is added in the protection glue solution for preparing, and comprises catalyzer and aliphatie diamine in this aqueous solution, alicyclic diamine, perhaps, the mixture of aliphatie diamine or alicyclic diamine and polyvalent alcohol.This solution is 40-90 ℃ of reaction, preferred 70-80 ℃.The preferred catalyst of step D is a triethylamine, and the amount of existence is 1-5 weight %, most preferably 2-4 weight %.
Preferably under high-shear is stirred (as, with the homogeneous agitator of 6000-7000rpm) slowly add painted prepolymer has high softening temperature with acquisition insoluble pigment.Continuing under the stirring (for example, using the homogeneous agitator), reaction mixture was being kept 0.5-2 hour in preferred temperature.If being solidificated in of this prepolymer carried out in the short period of time that is less than 0.5 hour or not stirring, will observe granules of pigments and partly or entirely assemble.
By for example filtering, the hardened resin is separated from suspension, and dry, preferably at 100-200 ℃ of dry 2-10 hour, carries out depolymerization then, as the hardened resin being ground to the granularity of expectation with pin mill or jet mill.Preferred pigment granularity is less than 10 microns, most preferably is the 1-5 micron.
The thermoplasticity high-visibility pigment that obtains with method of the present invention shows extraordinary dispersity, thermotolerance and solvent resistance.Therefore, the vividness of used dyestuff and tinting strength can display effectively.
Thermoplasticity high-visibility pigment of the present invention is suitable for the mass pigmentation of substrate, and described substrate comprises synthetic polymer, and synthetic resins and regenerated fibre are chosen wantonly in the presence of solvent and carried out.These substrates comprise oil type more specifically, water type and solvent type topcoating, polyester spinning melt, polyethylene, polystyrene and polyvinyl chloride melt, polymethacrylate and polymethylmethacrylate melt, urethane melt, rubber and synthetic leather.In addition, this pigment can be used for making printing-ink, is used for filming and printing of the mass pigmentation of paper and textiles.
Thermoplasticity high-visibility pigment of the present invention also is suitable in the toning agent and developer of electrofax, as list or two-pack powder toner (being also referred to as list or two-pack developer), magnetic color tuner, liquid toner, polymerization toner and special-purpose toning agent.
Typical toning agent binding is an addition polymerization, polymerization addition and condensation resin, as the vinylbenzene that is used alone or in combination, cinnamic acrylic ester, styrene butadiene, acrylate, polyester and phenol-Resins, epoxy, polysulfones, urethane also has polyethylene and polypropylene, they also may comprise other component, as charge control agent, wax or glidant, or carry out modification with these additives subsequently.
In addition, thermoplasticity high-visibility pigment of the present invention also is suitable as the tinting material of powder or powder coating material, especially static or the moving electricity powder coating that can spray, these coating are used for the surface coated by the article of making as metal, timber, plastics, glass, pottery, textile materials, paper or rubber.
Normally used powder coating resin is a Resins, epoxy, contains the vibrin of carboxyl and hydroxyl, and urethane resin and acrylic resin use with stiffening agent commonly used.Also use the composition of these resins.For example, Resins, epoxy often is used in combination with the vibrin that contains carboxyl and hydroxyl.Typically hardener component (playing the function of resin system) is, for example, acid anhydrides, imidazoles also has Dyhard RU 100 and derivative thereof, blocked isocyanate, di-acetyl carbamate, phenol and melamine resin, three-glycidyl based isocyanate, oxazoline and dicarboxylic acid.
In addition, thermoplasticity high-visibility pigment of the present invention also is suitable as the tinting material of jetted ink.
Following examples will be used for more fully setting forth the present invention.Unless otherwise specified, the per-cent that uses among the embodiment all is based on weight by weight.
Embodiment 1
To being equipped with an agitator, add 200 parts different phorone vulcabond in the four-hole boiling flask of a reflux exchanger and a thermopair, the triethylamine of 38.5 parts para toluene sulfonamide and 10 parts.When stirring the mixture, its temperature is risen to 70 ℃, reaction was carried out 1.5 hours, obtained liquid prepolymer.The prepolymer that obtains like this when being 50-60 ℃, temperature is mixed with 7.2 parts of fluorescence dye solvent yellow 16s 0.
Dividually, prepared a kind of protection glue solution, its preparation method is for being dissolved in acrylamide/sodium acrylate copolymer of 6.0 parts (CYANAMER370 that is produced by Cytec industrial) in 2000 parts of water.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, add 120 parts of different phorone diamines, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain jonquilleous suspension.Then, this suspension was 80 ℃ of vigorous stirring 1 hour.
The product that obtains is separated from suspension by filtering, and filter cake is 120 ℃ of heating 3 hours in temperature 100 ℃ of dryings subsequently, obtains 330 parts of pigment aggregates, and this aggregate grinds disaggregation with pin.
Character:
Measure products therefrom with scanning electron microscope.Find this product discrete by the size-grade distribution of suitable wide region, granulometric composition in irregular shape.Measuring the particulate mean particle size with Beckman-Coulter LS230 particle-size analyzer is 4.3 microns.The yellow fluorescence powder shows fabulous dispersiveness, high softening-point (195-198 ℃), good thermotolerance and solvent resistance.
Products therefrom further test in following bleeding test:
25 parts of vinyl composition CPI Freedom Plus A-1-B-02 Ultra Soft Base and 25 parts of Diisononil phtalate from Exxon are carefully mixed with 5.6 parts of pigment.Said composition is placed on the aluminium dish, and heats 5 minutes in baking oven in 150 ℃.After being cooled to room temperature, coloured plasticising ethene sample contacts with a slice white plasticising ethene, heats 24 hours in baking oven in 43 ℃.Viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 2
To being equipped with an agitator, add 200 parts different phorone vulcabond in the four-hole boiling flask of a reflux exchanger and a thermopair, the triethylamine of 38.5 parts para toluene sulfonamide and 10 parts.When stirring the mixture, its temperature is risen to 70 ℃, reaction was carried out 1.5 hours, obtained liquid prepolymer.Reaction soln with 5.0 parts oxalic acid treatment with the excessive triethylamine that neutralizes.The prepolymer that obtains like this when being 50-60 ℃, temperature is mixed with 7.2 parts of fluorescence dye basic yellows 40.
Dividually, prepared a kind of protection glue solution, its preparation method is for being dissolved in acrylamide/sodium acrylate copolymer of 6.0 parts (CYANAMERP-21 that is produced by Cytec industrial) in 2000 parts of water.After this aqueous solution is warming up to 70 ℃, mixture is stirred at 7000rpm with high speed agitator.When this protection glue solution is stirred, add the HCl solution of 120 parts of different phorone diamines and 204 part 36%.In 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain jonquilleous suspension.Then, this suspension was 80 ℃ of vigorous stirring 2.5 hours.
The product that obtains is separated from suspension by filtering, and filter cake is 120 ℃ of heating 3 hours in temperature 100 ℃ of dryings subsequently, obtains 340 parts of pigment aggregates.
Character:
Median size is 3.9 microns, and softening temperature is 197-201 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 3
To being equipped with an agitator, add 150 parts different phorone vulcabond in the four-hole boiling flask of a reflux exchanger and a thermopair, 50 parts 2,4 toluene diisocyanate, the triethylamine of 38.5 parts para toluene sulfonamide and 10 parts.When stirring the mixture, its temperature is risen to 70 ℃, reaction was carried out 1.5 hours, obtained liquid prepolymer.The prepolymer that obtains like this when being 50-60 ℃, temperature is mixed with 0.80 part of red 485 and 4.3 parts of Basonyl red 560 of Basonyl.
Dividually, with the protection glue solution in 2000 parts of water of operation preparation of embodiment 1.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, add the mixture of 52.8 parts of different phorone diamines and 85.6 parts of tetramethylolmethanes, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain the suspension of bright pink colour.Then, this suspension was 80 ℃ of vigorous stirring 2.5 hours.
The product that obtains is separated from suspension by filtering, and filter cake is 120 ℃ of heating 3 hours in temperature 100 ℃ of dryings subsequently, obtains 310 parts of pigment aggregates.
Character:
Median size is 4.6 microns, and softening temperature is 203-206 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 4
According to 238.5 parts of prepolymers of the preparation of the operation in embodiment 1, and 40-50 ℃ and red 560 mixing of the red 485 and 4.30 parts of Basonyl of 0,3.70 part of Basonyl of 4.70 parts of fluorescence dye solvent yellow 16s.
Dividually, prepared a kind of protection glue solution, its preparation method is the CYANAMER A-370 with 8.0 parts, 8.0 Solsperse41090 (from the phosphorylation alkoxylate polymkeric substance of ZENECASpecialties) of part and 4.0 parts SURFINOLCT-131 are (from Air Product ﹠amp; Chemicals company) is dissolved in 2000 parts of water.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, add 120 parts of different phorone diamines, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain the suspension of shiny red.Then, this suspension was 80 ℃ of vigorous stirring 1.5 hours.
From steady suspension, isolate most of curing granules of pigments of spheric fine separation that are by filtering No. 4 filter paper of filtration Whatman.
Character:
Measure products therefrom with scanning electron microscope.Find this product by what disperse, majority is the spheric granulometric composition.Measuring the particulate mean particle size with Beckman-Coulter LS230 particle-size analyzer is 4.0 microns.Softening temperature is 205-208 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 5
According to 238.5 parts of prepolymers of the preparation of the operation in embodiment 1, and, mixed with the medium fluorescence dye of 7.2 parts of structures for (I) with 3 hours at 85-90 ℃.
Dividually, prepared a kind of protection glue solution, its preparation method is the CYANAMER A-370 with 6.0 parts, and the SURFINOL CT-121 of 8.0 parts Solsperse and 4.0 parts is (from Air Product ﹠amp; Chemicals company) is dissolved in 2000 parts of water.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When stirring this protection glue solution, add 120 parts of different phorone diamines, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain jonquilleous suspension.Then, this suspension was 80 ℃ of vigorous stirring 1 hour.
Character:
Median size is 3.5 microns, and softening temperature is 185-190 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 6
According to 238.5 parts of prepolymers of the preparation of the operation in embodiment 1, and, mixed with the medium fluorescence dye of 7.2 parts of structures for (I) with 3 hours at 85-90 ℃.
Dividually, prepared the protection glue solution in a kind of 2000 parts of water, its preparation method is with the operation of embodiment 5.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, add 120 parts of different phorone diamines, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain jonquilleous suspension.Then, this suspension was 80 ℃ of vigorous stirring 1 hour.
Character:
Median size is 4.5 microns, and softening temperature is 184-188 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 7
According to 238.5 parts of prepolymers of the preparation of the operation in embodiment 1, and, mixed with the medium fluorescence dye of 7.2 parts of structures for (I) with 3 hours at 85-90 ℃.
Dividually, prepared the protection glue solution in a kind of 2000 parts of water, its preparation method is with the operation of embodiment 5.Add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, add 120 parts of different phorone diamines, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain jonquilleous suspension.Then, this suspension was 80 ℃ of vigorous stirring 1 hour.
Character:
Median size is 3.8 microns, and softening temperature is 180-185 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 8
According to 238.5 parts of prepolymers of the preparation of the operation in embodiment 1, and, mixed with the medium fluorescence dye of 7.2 parts of structures for (III) with 3 hours at 85-90 ℃.
Dividually, prepared the protection glue solution in a kind of 2000 parts of water, its preparation method is with the operation of embodiment 5.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, add 120 parts of different phorone diamines, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain bright bisque suspension.Then, this suspension was 80 ℃ of vigorous stirring 1 hour.
Character:
Median size is 3.5 microns, and softening temperature is 192-196 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 9
According to 238.5 parts of prepolymers of the preparation of the operation in embodiment 1, and, mixed with 3.6 parts of structures medium fluorescence dye and 3.6 parts of solvent yellow 16s 0 for (I) with 3 hours at 85-90 ℃.
Dividually, prepared the protection glue solution in a kind of 2000 parts of water, its preparation method is with the operation of embodiment 5.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, add 120 parts of different phorone diamines, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution then, obtain jonquilleous suspension.Then, this suspension was 80 ℃ of vigorous stirring 1 hour.
Character:
Median size is 4.5 microns, and softening temperature is 199-202 ℃.Products therefrom shows good dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Embodiment 10
To being equipped with an agitator, add 200 parts different phorone vulcabond in the four-hole boiling flask of a reflux exchanger and a thermopair, the triethylamine of 38.5 parts para toluene sulfonamide and 10 parts.When stirring the mixture, its temperature is risen to 70 ℃, reaction was carried out 1.5 hours, obtained liquid prepolymer.The prepolymer that obtains like this when being 50-60 ℃, temperature is mixed with 7.2 parts of fluorescence dye solvent yellow 16s 0.
Dividually, prepared a kind of protection glue solution, its preparation method is for being dissolved in 6.0 parts polyvinylpyrrolidone PVP K-30 in 2000 parts of water.After this aqueous solution is warming up to 70 ℃, add 10 parts of triethylamines, mixture stirs at 7000rpm with high speed agitator.When this protection glue solution is stirred, in 0.5 hour, liquid prepolymer is slowly added in the protection sol solution, obtain jonquilleous suspension.Then, this suspension was 80 ℃ of vigorous stirring 1 hour.The product that obtains is separated from suspension by filtering, and filter cake obtains 330 parts of pigment aggregates, this aggregate jet mill disaggregation 150 ℃ of dryings 4 hours.
Character:
Median size is 2.5 microns, and softening temperature is 210-215 ℃.This yellow fluorescent powder shows fabulous dispersiveness, thermotolerance and solvent resistance.Show that with the embodiment 1 identical bleeding test of carrying out with plasticized polyvinyl chloride viewed gamut significantly is less than the gamut with melamine-formaldehyde commonly used-sulphonamide pigment takes place.
Claims (12)
1. thermoplasticity high-visibility pigment, it is by in the presence of fluorescence dye, with vulcabond prepolymer and aliphatie diamine, the mixture of alicyclic diamine or diamines and polyvalent alcohol carries out condensation and gets, wherein, prepolymer is by aromatic sulfuryl amine and excess fat family, alicyclic and/or aromatic diisocyanate reacts and gets, and wherein the molar excess number of vulcabond equals aliphatie diamine in condensation reaction in the prepolymer, the mole number of alicyclic diamine or diamines and polyol blends.
2. the thermoplasticity high-visibility pigment of claim 1, wherein fluorescence dye is selected from a) water-soluble fluorescent dye, b) oil soluble fluorescence dye, c) structure is the medium fluorescent polymer solvability dyestuff of molecular formula (I) to (V)
Wherein,
X is oxygen or NR
2', R
2' be defined as R independently
2
R
1Be hydrogen, halogen ,-NR
2R
3, R
3-O-or R
3-S-,
R
2Be hydrogen, C
1-6Alkyl, C
6-10Aryl, (C
6-10) aryl-(C
1-6) alkyl or (C
1-6) alkyl-(C
6-10) aryl, alkyl and/or aromatic yl group be by hydroxyl, C
1-6Alkoxyl group, C
6-10Aryloxy or halogen replace;
R
3Be C
1-6Alkyl, C
6-10Aryl, (C
6-10) aryl-(C
1-6) alkyl or (C
1-6) alkyl-(C
6-10) aryl, alkyl and/or aromatic yl group be by hydroxyl, C
1-6Alkoxyl group, C
6-10Aryloxy or halogen replace;
R
4And R
5Be defined as R independently
2
Y is a sulphur, oxygen or-NR
2", R
2" be defined as R independently
2And n, m and p are 0-12.
3. the thermoplasticity high-visibility pigment of claim 1, wherein fluorescence dye is selected from basic yellow 40, solvent yellow 16 0, Basonyl red 485 and Basonyl are red 560, and the formula (I) and (III) dye composition of expression, and wherein, X is oxygen or NR
2', R
2' be hydrogen or methyl, R
1Be hydrogen, Y is a sulphur, n, and m and p are 2-6, are preferably 2 or 3.
4. the thermoplasticity high-visibility pigment of claim 1, wherein the amount that adds of fluorescence dye is 1-5 weight %, preferred 2-4 weight %.
5. prepare claim 1, the method for 2,3 or 4 color compositions comprises the steps:
A) in the presence of catalyzer, make the compound and the aromatic sulfuryl amine reaction that are selected from aliphatics, alicyclic and aromatic diisocyanate and composition thereof;
B) with the prepolymer dyeing of the composition of a kind of fluorescence dye or fluorescence dye with A;
C) prepolymer after the dyeing of B is introduced in the protection glue solution the optional tensio-active agent that comprises of this aqueous solution;
D) in the presence of catalyzer, the suspension of C and the compound reaction that is selected from down group, this group compound comprises aliphatics or alicyclic diamine, or the mixture of aliphatics or alicyclic diamine and polyvalent alcohol;
E) from suspension, isolate the hardened resin after, dry and depolymerization drying hardened resin.
6. the method for claim 5, wherein the catalyzer of steps A and D is a triethylamine, amount is 1-5 weight %
7. the method for claim 5, wherein steps A and D carry out in 40-90 ℃ of temperature range, and the temperature of steps A is preferably 50-60 ℃, and the temperature of step D is preferably 70-80 ℃.
8. the method for claim 5 wherein protects glue solution to comprise the water-soluble polymers of 1-3 weight %.
9. the method for claim 8 wherein contains the water conservation colloidal suspension and also comprises the nonionogenic tenside of 1-3 weight % or the mixture of nonionic and ionic surface active agent.
10. the method for claim 5, wherein painted prepolymer under agitation adds, and reaction mixture remains on 70-80 ℃ under continuing to stir, preferably continue 0.5-2 hour.
11. the purposes of the thermoplasticity high-visibility pigment of claim 1 comprises the mass pigmentation that is used for synthetic polymer, is used for marking ink, the mass pigmentation that is used for paper, be used for filming or stamp of textiles, be used for the toning agent and the developer of electrofax, be used for powder coating material and ink for inking.
12. comprise a kind of polymeric articles of the thermoplasticity high-visibility pigment of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0116677.6 | 2001-07-09 | ||
| GBGB0116677.6A GB0116677D0 (en) | 2001-07-09 | 2001-07-09 | Thermoplastic fluorescent pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1524112A true CN1524112A (en) | 2004-08-25 |
Family
ID=9918131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028136292A Pending CN1524112A (en) | 2001-07-09 | 2002-07-08 | Thermoplastic fluorescent pigment |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1406973A1 (en) |
| JP (1) | JP2004534142A (en) |
| KR (1) | KR20040018436A (en) |
| CN (1) | CN1524112A (en) |
| GB (1) | GB0116677D0 (en) |
| WO (1) | WO2003006557A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011110089A1 (en) * | 2010-03-10 | 2011-09-15 | Akzo Nobel Powder Coatings (Ningbo) Co. Ltd. | Powder coating having anodized look |
| CN102746710A (en) * | 2012-02-10 | 2012-10-24 | 麾䶮化工（扬州）有限公司 | Preparation method for solvent resistance fluorescence pigment |
| CN110982249A (en) * | 2019-12-20 | 2020-04-10 | 广东省稀有金属研究所 | TPU (thermoplastic polyurethane) noctilucent master batch and preparation method thereof |
| CN113563562A (en) * | 2021-08-23 | 2021-10-29 | 无锡安睿驰科技有限公司 | Disc-type self-repairing safety tire rubber material and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406461C (en) * | 2003-04-30 | 2008-07-30 | 华东理工大学 | Sulphur containing heterocyclic and naphthalimides compound and use thereof |
| US7659342B2 (en) * | 2005-02-03 | 2010-02-09 | Bridgestone Corporation | Polymer nano-particle with polar core and method for manufacturing same |
| US8986842B2 (en) | 2011-05-24 | 2015-03-24 | Ecole Polytechnique Federale De Lausanne (Epfl) | Color conversion films comprising polymer-substituted organic fluorescent dyes |
| US9052624B2 (en) | 2012-05-02 | 2015-06-09 | Eastman Kodak Company | Use of fluorescing toners for imaging |
| WO2019013264A1 (en) * | 2017-07-14 | 2019-01-17 | 富士フイルム株式会社 | Inkjet ink, ink cartridge, inkjet printer, inkjet textile printing method, method for producing colored fabric, and method for producing inkjet ink |
| WO2019013265A1 (en) * | 2017-07-14 | 2019-01-17 | 富士フイルム株式会社 | Inkjet ink, inkjet printing method, and colored fabric |
| WO2022059311A1 (en) * | 2020-09-15 | 2022-03-24 | コニカミノルタ株式会社 | Benzothioxanthene compound, resin particles, and fluorescent immunostaining reagent |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2063948C3 (en) * | 1970-03-20 | 1975-01-02 | G. Siegle & Co Gmbh, 7000 Stuttgart | Use of resins or resin mixtures for the production of fluorescent pigments |
| US3922232A (en) * | 1973-11-23 | 1975-11-25 | Hercules Inc | Fluorescent colorants |
| DE2546118C3 (en) * | 1975-10-15 | 1978-07-13 | Basf Farben + Fasern Ag, 2000 Hamburg | Process for the production of concentrates which contain fluorescent pigments |
| JPS55739A (en) * | 1978-06-20 | 1980-01-07 | Toyo Rubber Chem Ind Co Ltd | Preparation of luminescent urethane foam |
| JPH01164301A (en) * | 1987-12-09 | 1989-06-28 | Asahi Corp | Method for manufacturing shoe sole of foamed polyurethane |
| EP0638613B1 (en) * | 1993-08-13 | 1998-12-23 | Ciba SC Holding AG | Perylene amidine-imide dyes, a process for their production and their use |
| DE19541054B4 (en) * | 1995-11-03 | 2006-09-07 | Giesecke & Devrient Gmbh | Pigments and process for their preparation |
| US5714090A (en) * | 1996-05-14 | 1998-02-03 | Day-Glo Color Corporation | Solvent resistant non-formaldehyde thermoset fluorescent pigment |
| DE19629431A1 (en) * | 1996-07-22 | 1998-01-29 | Clariant Gmbh | Optically lightened polyurethane |
| US6103006A (en) * | 1998-01-28 | 2000-08-15 | Day-Glo Color Corporation | Fluorescent polymeric pigments |
-
2001
- 2001-07-09 GB GBGB0116677.6A patent/GB0116677D0/en not_active Ceased
-
2002
- 2002-07-08 KR KR10-2004-7000261A patent/KR20040018436A/en not_active Application Discontinuation
- 2002-07-08 EP EP02741099A patent/EP1406973A1/en not_active Withdrawn
- 2002-07-08 CN CNA028136292A patent/CN1524112A/en active Pending
- 2002-07-08 JP JP2003512317A patent/JP2004534142A/en not_active Withdrawn
- 2002-07-08 WO PCT/IB2002/002682 patent/WO2003006557A1/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011110089A1 (en) * | 2010-03-10 | 2011-09-15 | Akzo Nobel Powder Coatings (Ningbo) Co. Ltd. | Powder coating having anodized look |
| CN102746710A (en) * | 2012-02-10 | 2012-10-24 | 麾䶮化工（扬州）有限公司 | Preparation method for solvent resistance fluorescence pigment |
| CN110982249A (en) * | 2019-12-20 | 2020-04-10 | 广东省稀有金属研究所 | TPU (thermoplastic polyurethane) noctilucent master batch and preparation method thereof |
| CN113563562A (en) * | 2021-08-23 | 2021-10-29 | 无锡安睿驰科技有限公司 | Disc-type self-repairing safety tire rubber material and preparation method thereof |
| CN113563562B (en) * | 2021-08-23 | 2022-05-13 | 无锡安睿驰科技有限公司 | Disc-type self-repairing safety tire rubber material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1406973A1 (en) | 2004-04-14 |
| WO2003006557A1 (en) | 2003-01-23 |
| KR20040018436A (en) | 2004-03-03 |
| GB0116677D0 (en) | 2001-08-29 |
| JP2004534142A (en) | 2004-11-11 |
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