CN100362078C - Process for incorporation of UV-luminescent compounds in polymeric materials - Google Patents
Process for incorporation of UV-luminescent compounds in polymeric materials Download PDFInfo
- Publication number
- CN100362078C CN100362078C CNB2003801025415A CN200380102541A CN100362078C CN 100362078 C CN100362078 C CN 100362078C CN B2003801025415 A CNB2003801025415 A CN B2003801025415A CN 200380102541 A CN200380102541 A CN 200380102541A CN 100362078 C CN100362078 C CN 100362078C
- Authority
- CN
- China
- Prior art keywords
- formula
- alkyl
- hydrogen
- compound
- aryl
- 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.)
- Expired - Fee Related
Links
Abstract
The invention relates to a process for the preparation of luminescent textile fibres characterized in that the fibres are treated with a composition comprising (a) one or more luminescent lanthanide chelates containing three organic anionic ligands having at least one UV absorbing group and (b) one or more solvents.
Description
The present invention relates to method for preparing the luminous polymeric material of UV and uses thereof.
Textiles with hidden effect need be provided, and this textiles can be used as safety label, as only just visible special effects material or decoration under UV irradiation.
Therefore, one object of the present invention just provides dyeing composition, comprise naked eyes cannot see in the said composition and be exposed under the UV can strong luminescence material, and said composition can be used in all traditional dyeings application of polymeric material, described polymeric material comprises the textiles such as wool, silk, cellulose materials, natural and synthon, and said composition also can be used for the mass dyeing (mass dyeing) of polymeric material, and the polymeric material that is used for mass dyeing comprises the material that those use in textiles and plastic applications.
The present invention relates to prepare the method for luminous polymer fiber, it is characterized in that, with this fiber of compositions-treated, said composition comprises
(a) one or more luminous lanthanide chelates, this inner complex contain three or four have at least one UV absorb group the organic anion part and
(b) one or more solvents.
Preferably, component (a) is the compound of formula I
L
m-Ln
3+(Ch
-)
n (1)，
Wherein Ln represents lanthanon,
Ch
-For containing the electronegative part that at least one UV absorbs two keys,
N represents 3 or 4, and m represents the number of 0-4,
If n is 3, then m represents the number of 0-4, and L is neutral unidentate ligand or the polydentate ligand that contains N, O or S, and perhaps n is 4 o'clock, and m represents 1, and L is unicharged positively charged ion.
More preferably, component (a) is the compound of formula II, III or IV
L
m-Ln
3+[R
1-O]
n (IV)，
Wherein Ln represents lanthanon,
N represents 3 or 4, and m represents the number of 0-4
If n is 3, then m represents the number of 0-4, and L is the polydentate ligand of neutral unidentate ligand or nitrogenous, oxygen or sulphur, or if n is 4, then m represents 1, and L is unicharged positively charged ion,
R
2Be hydrogen or C
1-C
6Alkyl and
R
1And R
3Independent separately each other is hydrogen, C
1-C
6Alkyl, CF
3, C
5-C
24Aryl or C
4-C
24Heteroaryl.
Formula I, II, the compound of III or IV can mainly contain neutral arbitrarily unidentate ligand or nitrogenous, the polydentate ligand of oxygen or sulphur, for example, the pyridine that does not replace or replace, pyrazine, piperidines, quinoline, aniline, two pyridines, phenanthroline, three pyridines, imidazoles, benzoglyoxaline, bisglyoxaline, biphenyl and imidazoles, pyrimidine, two pyrimidines, naphthyridines, alkylamine, dialkylamine, trialkylamine, the alkylene polyamine, dioxane, methyl-sulphoxide, dimethyl formamide, phosphine-oxide derivative (trialkyl or triaryl), triazine, two triazines, the azoles, two azoles, azoles quinoline oh, two oh azoles quinoline and substitutive derivatives thereof, and all relevant (many) N-oxide derivatives of above-mentioned part.
Particularly preferably be the compound of formula I, II, III or IV, wherein n represents 3, and L is nitrogenous part.
Because L can be many chelating ligands, similar as 4,4 '-bipyridyl, so the compound of formula I, II, III or IV comprises many metallo-chelates, and for example, the compound of formula XIII and XIV, it contains two M that link to each other by the bidentate ligand of following formula
III-(diketone)
3Or M
III-(carboxylate)
3The unit:
When n represents 4, can be any metallic cation basically (as, Li as the cationic L of single electric charge
+, K
+, Na
+), the ammonium that do not replace or replace is (as, NH
4 +, many alkylammoniums), or above-mentioned any protonated or alkylating unidentate ligand or polydentate ligand.
Preferred positive charge part is piperidines , ammonium, alkylammonium, dialkyl ammonium, and trialkyl ammonium especially.
Preferred especially triethyl ammonium.
Particularly preferably be the compound of formula I, II, III or IV, wherein L is the compound of formula V-XII
Or formula H-N
+(R
7)
3Positively charged ion,
R wherein
4, R
5And R
6Independent separately each other is hydrogen, halogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl, C
1-C
6Alkoxyl group, amino, dialkyl amido or cyclic amino group, and R
7Be hydrogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl or vinyl.
As R
1-R
7Substituent alkyl group can be the straight or branched group.The example that can mention is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, n-hexyl and isohexyl.
As R
4-R
6Substituent alkoxyl group can be, for example, and methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy or tert.-butoxy.
C
5-C
24The example of aromatic yl group is phenyl, tolyl, mesityl, isityl, phenylbenzene, naphthyl and anthryl.Preferred phenyl.
Heteroaryl preferably contains 4 or 5 C atoms and one or two is selected from the heteroatoms of O, S and N.Example is pyrryl, furyl, thiophenyl, azoles base, thiazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indyl, purine radicals or chinolyl.
As R
4-R
7Substituent aralkyl can be, for example, and benzyl, 2-phenylethyl, tolyl methyl, mesityl methyl and 4-Chlorophenylmethyl.
Suitable dialkyl amido is, for example, and diethylin, diisopropylaminoethyl, di amino, N-methyl-N-ethylamino, and specifically dimethylamino or pyrrolidyl.
Suitable cyclic amino is pyrrolidyl and piperidino-(1-position only).
As R
4-R
6Substituent halogen atom is preferably fluorine, chlorine or bromine, but especially preferred chlorine.
The preferred present composition contains the formula II compound as component (a), and wherein L is the compound of formula V, VI, VII, VIII, IX, X, XI or XII, wherein R
4, R
5And R
6Be hydrogen, methyl, amino, pyrrolidyl or dimethylamino, or L is formula H-N
+(R
7)
3Positively charged ion, R wherein
7Be C
1-C
6Alkyl.
Preferred ingredients (a) is the compound of formula I, II, III or IV, and wherein Ln is Eu, Tb, Dy, Sm or Nd.
In addition, the compound of formula II and III is preferred, wherein R
1And R
3Be methyl, the tertiary butyl, n-pentyl or phenyl.
R among the formula II
2Be preferably hydrogen.
Especially preferably the compound as component (a) is the compound of formula XIII-CVI:
Derive and the II that comes and some preferred derivatives of III type structure are organized in the following form by above-mentioned I type preferred structure:
The DMAP:4-dimethyl aminopyridine
More suitably lanthanide chelate can contain
Pyridine, aminopyridine, pyrrolidyl pyridine, picoline, methoxypyridine, pyridine-N-oxide, two pyridines, phenanthroline, imidazoles or the list of other deutero-or similarly nitrogenous, oxygen or sulphur-or polydentate ligand arbitrarily are in order to replace DMAP
Piperidines , ammonium, alkylammonium, dialkyl ammonium, trialkyl ammonium, pyridine or any other similarly contain the protonated material of N, in order to replace Et
3NH
+
Use the recommendable combination that is to use different lanthanon, for example combination of Eu and Tb for some.This mixture can improve hidden painted level of safety, improve the accuracy of security level, and codifiability is increased.
The compound of formula I, II, III and IV is known, and for example from people's such as WO 96/20942 and C.R.Hurt Nature 212,179-180 learns in (1966), perhaps can be prepared by methods known in the art.For example; under proper condition; can make such as the part of Acetyl Acetone, benzoyl acetone, phenyl phenacyl ketone, dipivaloylmethane(DPVM), Whitfield's ointment, valeric acid or caproic acid and rare earth metal halide and react, with the preparation rare-earth chelates such as the lanthanon trichloride.Again with the polydentate ligand L reaction of unidentate ligand or nitrogenous, oxygen or sulphur, thereby make the rare earth metal chelate compound of formula I, II, III and IV.
This luminous lanthanide chelate can be used as powder, solution or dispersion and uses.
Therefore, component (b) can be the mixture of water, organic solvent, two or more organic solvents or the mixture of water and one or more organic solvents.
Preferably, component (b) be water, one or more can with the miscible organic solvent of water or water and one or more can with the mixture of the miscible organic solvent of water.
Suitable organic solvent comprises alcohol, glycol, ether alcohol, sulfoxide, acid amides, amine, heterocyclic solvents, ketone, ether, ester, nitrile and aliphatics, alicyclic and aromatic hydrocarbons.
Suitable representative examples of organic is a methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, glycerine, ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, polyoxyethylene glycol, polypropylene glycol, ethylene glycol monoethyl ether, Polyethylene glycol dimethyl ether, the oxyethyl group butanols, butoxy ethanol, methyl-sulphoxide (DMSO), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone (NMP), acetone, 2-butanone, diethyl ether, di ether, tetrahydrofuran (THF) (THF), ethyl acetate, ethyl propionate, acetonitrile, pyridine, Skellysolve A, normal hexane, hexanaphthene, benzene and toluene.
Can be preferably fatty alcohol, ether alcohol, glycol, aliphatic ketone, carboxylicesters, carboxylic acid amide, aliphatic nitrile, aliphatic polyether or aliphatics sulfoxide with the miscible organic solvent of water.
Particularly preferred can be ethanol, butoxy ethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofuran (THF) (THF), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone (NMP), acetonitrile, Polyethylene glycol dimethyl ether and methyl-sulphoxide (DMSO) with the miscible organic solvent of water.
Composition according to the present invention except that comprise component (a) and (b) also can comprise one or more tinting materials.
The appropriate colouring agent is known pigment and dyestuff, also comprises the mixture of different pigment and dyestuff.
In composition according to the present invention, component (a) and (b) and the amount of suitable (c) and/or other composition (d) can in very wide scope, change.
For the mass dyeing process, composition according to the present invention comprises component (a).Randomly, also can be and/or (d) add with (a) with other composition (c) so that polymeric material UV-is luminiferous also to have other additional character simultaneously having.
For dyeing course, in the total amount of component (a)+(b), preferred composition contains 0.01-20.0%, the more preferably heavy component (a) of 0.05-10%, especially 0.1-5.0%, and 80.0-99.99%, the component (b) that more preferably 90.0-99.95%, especially 95.0-99.9% are heavy.
The amount of component (c) depends on matrix type and concrete pigment or dyestuff.In the weight of fiber, it is heavy that favourable painted dosage is generally 0.01%-15%, and especially 0.1%-10% is heavy.
The other composition (d) that can contain in composition of the present invention is, for example, and optional brightening agent, biocide, sterilant, mycocide, sterilant and spices.
The composition that contains at least a lanthanide chelate can prepare according to the known any proper method of those of ordinary skills.For example, the component of composition can merge or mix in suitable mixing tank or blender.
Composition according to the present invention is applicable to that the dip-dye synthetical is natural, artificial, particularly hydrophobic synthetic material, particularly textile material.
Similarly, the textile material of being made up of the mixed goods that comprises this synthetical natural polymer or hydrophobic synthetic filamentary material can be contaminated with prescription of the present invention.
Useful artificial natural polymer textile material is wool, cotton, silk, rhodia and cellulose triacetate especially.
The hydrophobic textile material of synthetic is the straight chain aromatic polyester especially, for example, by terephthalic acid and glycol, the polyester that forms of ethylene glycol especially, or terephthalic acid and 1, the condensation product of 4-two (methylol) hexanaphthene; Polycarbonate, for example, by α, alpha-alpha-dimethyl-4, those materials that 4 '-dioxydiphenyl methane photoreactive gas forms; Or based on the fiber of polyvinyl chloride or polymeric amide.
According to known dyeing course preparation of the present invention is used for textile material.For example, at 80-140 ℃, under preferred 120-135 ℃ the temperature, in the presence of negatively charged ion commonly used that has or do not have common carrier or non-ionic dispersing agent, from aqueous dispersion, dye (exhaust dye) trevira to the greatest extent.Cellulose acetate preferably dyes under 60-85 ℃, and cellulosetri-acetate dyes under up to 115 ℃.
Used prescription according to the present invention is applicable to and adopts thermosol, dyes with continuation method and dye to the greatest extent, and is applicable to printing process.Preferably dye process to the greatest extent.Liquid fraction depends on device, matrix and layout form.But liquid fraction can be selected in very wide scope, for example 4: 1-100: 1, but be preferably 6: 1-25: 1.
Mentioned textiles can exist by different form processings, for example is fiber, yarn or reticulation, or is fabric or one-tenth ring knitted fibers.
Luminous lanthanide chelate of the present invention is equally applicable to the mass dyeing of plastics.
Therefore, the invention still further relates to a kind of method for preparing luminescent plastics, it is characterized in that,, in the presence of 0.01-10.0% heavy formula I, II, III or IV compound, extrude this plastic material in the amount of plastic material.
The plastics that are applicable to mass dyeing comprise, for example, high molecular weight organic materials (polymkeric substance), especially polyester, polycarbonate (PC), polystyrene (PS), polypropylene (PP), polymethylmethacrylate (PMMA), polymeric amide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or the acrylonitrile/butadiene/styrene (ABS) of stainable, specific inductivity 〉=2.5.Preferred polyester and polymeric amide.Especially preferred is can be by terephthalic acid and glycol, especially the straight chain aromatic polyester that obtains of the polycondensation of ethylene glycol, or terephthalic acid and 1, the condensation product of 4-two (methylol) hexanaphthene, for example, polyethylene terephthalate (PET) or polybutylene terephthalate (PBTP); Polycarbonate, for example by α, alpha-alpha-dimethyl-4, the polycarbonate that 4 '-dioxydiphenyl methane photoreactive gas forms; Based on the polymkeric substance of polyvinyl chloride or polymeric amide, for example, nylon 6 or nylon 6.6, polystyrene (PS) or polypropylene (PP).
More specifically preferably based on the plastics of straight chain aromatic polyester, for example those are by terephthalic acid and glycol, especially the plastics that form of ethylene glycol, or terephthalic acid and 1, the condensation product of 4-two (methylol) hexanaphthene, polymethylmethacrylate (PMMA), polypropylene (PP) or polystyrene (PS).
Can plastics be dyeed according to the mode of following example: for example, use roller crusher or mixing or milling device to sneak in these plastics substrates, thereby make lanthanide chelate dissolving or fine dispersion in plastics according to the luminous lanthanide chelate of component (a).Then in a conventional manner, for example, compacting, punching press, extrude, brushing, spin coating, casting or jet molding process the plastics that this has mixing colouring agent, thereby make painted material obtain its net shape.The mixing of component also can directly be carried out before actual procedure of processing; for example; by continuously with solid; as the powdered lanthanide chelate; with particle or Powdered plastics; the optional in addition additional substances while such as additive kind directly is metered into the entry zone of forcing machine, and mixes in this zone in first being processed.But, preferably lanthanide chelate is pre-mixed in the plastics usually, because can obtain more uniform dip-dye matrix like this.
The invention still further relates to luminous textile fibres and luminescent plastics by method for preparing.
The present invention can be attached to colourless or procrypsis mark in different colourless, white, the light or dark matrix, and this mark can show under the UV irradiation.
Method required for protection is specially adapted to make safety fibre or the safety line that can be used as trust indenture or other material.
The purpose that safety fibre is joined in trust indenture or other material is in order to ensure discerning, approve, prevent forgery, imitated or fraud.Safety line is the continuous thin film line or belt, and it is identical that it is joined in the trust indenture purpose with fiber safe in utilization.
Wording " trust indenture " is meant such as the file of banknote, check, stock, bill, stamp, official document, identity card, passport, minute book, notes, ticket, receipt, report, accounts basis and credit card, debt card, charge card or multifunction card and the file of the level of safety that similarly needs are very high.
The manufacturing of safety fibre or safety line can be according to for example, United States Patent (USP) 4,655,788,5,759,349 and 6,045,656, the method described among EP-A 185 396 and the EP-A 1 013 824 finishes.
Sneaking into of lanthanide chelate can be carried out according to traditional dyeing or printing process.
The fiber that is fit to that is used for described method can derive from wool or plant paper pulp, cellulose pulp, cotton, flax or synthon.
Preferred unusable paper fiber or synthon.
In particularly preferred embodiments, will be used for preparing anti--pseudo-file, card, check or banknote according to the method for claim 1.
Composition according to the present invention is different with similar compositions in the prior art, and it has excellent luminescent quantum yield, secular luminous and very high luminous intensity.
With the following example the present invention is described.
Ink composite A:
Compounds X VII is 1, the enriched material in the 2-propylene glycol
The 1g compound VIII is dissolved in 99g 1, in the 2-propylene glycol, and under 100 ℃, heated 1 hour.Filter this clarifying yellow solution of back (purification) cooling, so that stable ink composite A to be provided, it demonstrates intensive ruddiness under UV light.Also this enriched material can be used in the tradition or high-tech (ink-jet) printable formulation of solvent-Ji or water-Ji, to be used for paper, textiles, leather, wool, plastics or other matrix that is fit to.
Embodiment 1:
Under 35 ℃, in alternate cycles dyeing apparatus (Callebault de Blicquy) (3 minute cycle), press the flowing fluid ratio of 1-10 and contaminated Mierocrystalline cellulose bobbin (0.75kg cotton thread, 40 spies) 20 minutes.This liquid is meant and contains 4.5% formula XVII compound in butoxy ethanol
After the processing, centrifugal and this bobbin of dry air has been observed intensive orange fluorescence under UV light.
Embodiment 2:
Under 25 ℃, in the liquid identical and under the ratio of identical liquid and textile material, contaminated silk thread (10g) 10-60 minute with embodiment 1.After the processing, centrifugal and this silk thread of dry air, it demonstrates intensive orange fluorescence under UV light.
Embodiment 3:
Under 25 ℃, in the liquid identical and under the ratio of identical liquid and textile material with embodiment 1, contaminate contain some kinds of different synthetic, artificial, natural (plant and animal) fibers pieced together fiber (20g) 10-60 minute.After the processing, this pieces together fiber centrifugal and dry air, and most of fiber demonstrates intensive orange fluorescence under UV light.
Use other group of the lanthanides complex compound that under UV irradiation, demonstrates other emission wavelength (as, terbium, dysprosium, samarium, neodymium), obtained equivalent result according to similar approach.
Embodiment 4:
The high temperature dyeing (HTD) (135 ℃, 60 minutes) of polyester (PES) silk
PES silk (10g) is incorporated in the container of 250mL sealed against leakage, contains 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in the solvent-based sols (5-30mL) of group of the lanthanides complex compound among the NMP, that contain 3-5% formula XVII
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/lUnivadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.PES silk after the processing demonstrates intensive orange fluorescence under the irradiation of 365nm.
Embodiment 5:
The high temperature dyeing of VELVET PES fiber (HTD) (135 ℃, 60 minutes)
VELVET PES fiber (10g) is incorporated in the container of 250mL sealed against leakage, contains 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in the solvent-based sols (5-30mL) of group of the lanthanides complex compound among the NMP, that contain 3-5% formula XVII
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.PES silk after the processing demonstrates intensive orange fluorescence under the irradiation of 365nm.
Embodiment 6:
The high temperature dyeing of VELVET PES fiber (HTD) (135 ℃, 60 minutes)
White VELVET PES fiber (10g) is incorporated in the container of 250mL sealed against leakage, contains 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in solvent-based sols (5-30mL) of following formula group of the lanthanides complex compound XV among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.VELVET PES fiber after the processing is a white, demonstrates the intensive green fluorescence under the irradiation of 254nm.
Embodiment 7:
The high temperature dyeing of polyamide (PA) tricot (HTD) (135 ℃, 60 minutes)
PA tricot (10g) are incorporated in the container of 250mL sealed against leakage, contain 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in solvent-based sols (5-30mL) of group of the lanthanides complex compound XVII among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.PA tricot after the processing demonstrate intensive orange fluorescence under the irradiation of 365nm.
Embodiment 8:
The high temperature dyeing of PA tricot (HTD) (135 ℃, 60 minutes)
White PA tricot (10g) are incorporated in the container of 250mL sealed against leakage, contain 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in solvent-based sols (5-30mL) of group of the lanthanides complex compound XV among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.PA tricot after the processing are white, demonstrate green fluorescence under the irradiation of 254nm.
Embodiment 9:
The high temperature dyeing (HTD) of the PA silk of clear, colorless (135 ℃, 60 minutes)
The PA silk (10g) of clear, colorless is incorporated in the container of 250mL sealed against leakage, contains 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in solvent-based sols (5-30mL) of group of the lanthanides complex compound XVII among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.Clear PE S silk after the processing demonstrates intensive orange fluorescence under the irradiation of 365nm.
Embodiment 10:
By the mass dyeing process XVII is bonded in the polyamide (PA)
Under 260 ℃, in the presence of 2% group of the lanthanides complex compound XII, extrude Ultramid B3K with 2 fens clock times, it produces orange fluorescence under the 365nm irradiation.
Embodiment 11:
By the mass dyeing process XVII is bonded in the polystyrene (PS)
Under 300 ℃, in the presence of 2% group of the lanthanides complex compound XVII, with 5 fens clock time extruded polystyrene H165, it produced orange fluorescence under the 365nm irradiation.
Embodiment 12:
By the mass dyeing process XVII is bonded in the polypropylene (PP)
The uniform mixture of polypropylene GRANULES (200g) and compounds X VII (2g) is incorporated in the melting chamber (200 ℃) of 3mm cable forcing machine.After the cooling, the rigid cable with gained cuts into particle again, and then is introduced in the melting chamber (230 ℃) of silk forcing machine in water-bath.The transparent multifilament polypropylene filament (8 dtex) of gained demonstrates intensive orange fluorescence through exciting under 365nm.
Embodiment 13:
By the mass dyeing process XVII is bonded in the polypropylene (PP)
Use titanium dioxide and compounds X VII then to obtain similar process and consequent photoluminescent property simultaneously.
Embodiment 14:
By the mass dyeing process with XVII be bonded to poly-(methyl methacrylate) (PMMA) in
Under 260 ℃, in the presence of 2% group of the lanthanides complex compound XVII, extrude Plexiglas 6N with 5 fens clock times, it produces orange fluorescence under the 365nm irradiation.
Embodiment 15:
By the mass dyeing process XVII is bonded in acrylonitrile/butadiene/styrene-multipolymer (ABS)
Under 220 ℃, in the presence of 2% group of the lanthanides complex compound XVII, extrude Terluran 877M with 5 fens clock times, it produces orange fluorescence under the 365nm irradiation.
Embodiment 16:
The high temperature dyeing of coloured PES filament (HTD) (135 ℃, 60 minutes)
Blue-greenish colour PES filament (10g)-before Irgalite Blue GLGP (C.I. blue pigment 15:3), titanium dioxide (C.I. white pigments 6) and carbon black (C.I. mineral black 7) mixture are carried out mass dyeing-be incorporated in the container of 250mL sealed against leakage, contain 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in solvent-based sols (5-30mL) of group of the lanthanides complex compound XV among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.Blue-greenish colour PES filament after handling like this is a blue-greenish colour, and it demonstrates the intensive green fluorescence under the 254nm irradiation, and does not have fluorescence under the 365nm irradiation.
Embodiment 17:
The high temperature dyeing of coloured PES filament (HTD) (135 ℃, 60 minutes)
Black PES filament (10g)-is before carried out mass dyeing-be incorporated in the container of 250mL sealed against leakage with the pigment composition that contains titanium dioxide (C.I. white pigments 6) and carbon black (C.I. mineral black 7), contain 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in solvent-based sols (5-30mL) of group of the lanthanides complex compound XV among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.Black PES filament after handling like this is a black, and it demonstrates the intensive green fluorescence under the 254nm irradiation, and does not have fluorescence under the 365nm irradiation.
Embodiment 18:
The high temperature dyeing of coloured PES filament (HTD) (135 ℃, 60 minutes)
Yellow PES filament (10g)-before Filester Yellow RNB (C.I. yellow ultramarine 147) is carried out mass dyeing-be incorporated in the container of 250mL sealed against leakage, contain 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in solvent-based sols (5-30mL) of group of the lanthanides complex compound XV among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.Yellow PES filament after handling like this is a yellow-green colour, and it demonstrates the intensive yellow-green fluorescence under the 254nm irradiation, and does not have fluorescence under the 365nm irradiation.
Embodiment 19:
The high temperature dyeing of PES silk (HTD) (135 ℃, 60 minutes)
PES silk (10g) is incorporated in the container of 250mL sealed against leakage, contains 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in the solvent-based sols (5-30mL) of following formula group of the lanthanides complex compound among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.PES silk after handling like this demonstrates intensive orange fluorescence under the 365nm irradiation.
Embodiment 20:
The high temperature dyeing of PES silk (HTD) (135 ℃, 60 minutes)
White PES silk (10g) is incorporated in the container of 250mL sealed against leakage, contains 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о contains the NMP suspension (5-30mL) of 2% following formula group of the lanthanides complex compound
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.White PES silk after handling like this is a white, and it demonstrates pink fluorescence under the 254nm irradiation, and does not have fluorescence under the 365nm irradiation.
Embodiment 21:
The high temperature dyeing of PES silk (HTD) (135 ℃, 60 minutes)
White PES silk (10g) is incorporated in the container of 250mL sealed against leakage, contains 200mL dye bath (that is, bath raio is 1-20) in this container.
This dye bath is made the mixture of following two kinds of solution:
о is dissolved in the solvent-based sols (5-30mL) of following formula group of the lanthanides complex compound among the NMP, that contain 3-5%
The aqueous solution of о pH=4.5 (195-170mL), it contains
0.6g/l Univadin DP (Ciba specialty pharmaceutical chemicals)
2.5g/l Cibatex AB 45 (Ciba specialty pharmaceutical chemicals)
0.4g/l sodium bicarbonate
This container is placed the high temperature dyeing autoclave of rotation, and initial bath temperature is 70 ℃.With 30 fens clock times temperature is increased to 135 ℃ then, and keeps again stablizing 1 hour.With 15 fens clock times treatment temp is reduced to 40 ℃ at last, takes out silk thread afterwards from container, with warm water (35 ℃) rinsing 5 minutes, Rotary drying used warm air (90-105 ℃) to carry out drying at last.White PES silk after handling like this is a white, and it demonstrates green fluorescence under the 254nm irradiation, and does not have fluorescence under the 365nm irradiation.
Embodiment 22:
The high temperature dyeing of PES (HTD) (135 ℃, 60 minutes)
Do not use NMP, adopt and preparation dispersed dye similar methods, and replace these dispersed dye to realize above-mentioned all high temperature dyeings test with used UV fluoresce lanthanide inner complex.
Embodiment 23:
The transfer printing preparation that use contains one or more UV fluorescence lanthanide chelates carries out the transfer printing of UV fluorescence lanthanide chelate.According to the traditional transfer printing preparation similar methods of preparation, use one or more lanthanide chelates to replace dispersed dye, perhaps except that using dispersed dye, also use one or more lanthanide chelates to prepare these preparations.
Embodiment 24:
The preparation of polycomponent security thread
With polymeric blends (as, the polymeric amide Akulon of copolymerization is provided by Akzoplastiks) be dispensed in three forcing machines, and make particles fuse.The melts that is equipped with as the outer component of silk mixes by certain mode with 3% heavy formula (XVII) compound respectively, so that it solves homogeneously in the polyamide melts.After extruding the polycomponent silk, obtained security thread, its peripheral zone sends fluorescence under UV light, and its center band does not show any fluorescence.Lanthanide chelate and one or more dyestuffs or pigment coextrusion are then obtained coloured silk, and it has fluorescence equally under UV light.
Embodiment 25:
The preparation of polycomponent security thread
As described in embodiment 24, polyamide extruded melts is with the preparation security thread, and this melts contains 3% heavy 1: 1 formula (XVII) and formula (XV) mixture.Under the UV of different wave length irradiate light, observed red and/or green fluorescence.
Claims (15)
1. method for preparing luminous polymer fiber, it is characterized in that: with this fiber of compositions-treated, said composition comprises
(a) one or more luminous lanthanide chelates, this inner complex contain three or four and have the organic anion part that at least one UV absorbs group, and this inner complex is selected from
Formula I compound
L
m-Ln
3+(Ch
-)
n (I)，
Wherein, Ch
-For containing the electronegative part that at least one UV absorbs two keys, wherein, Ln represents lanthanon,
N represents 3 or 4, and m represents the number of 0-4,
If n is 3, then m represents the number of 0-4, and L is selected from the compound of formula V-XII
Perhaps,
If n is 4, then m represents 1, and L is formula H-N
+(R
7)
3Positively charged ion,
R
2Be hydrogen or C
1-C
6Alkyl and
R
1And R
3Independently of one another is hydrogen, C
1-C
6Alkyl, CF
3, C
5-C
24Aryl or C
4-C
24Heteroaryl,
R
4, R
5And R
6Independently of one another is hydrogen, halogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl, C
1-C
6Alkoxyl group, amino, dialkyl amido or cyclic amino group, and R
7Be hydrogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl or vinyl,
With
(b) one or more solvents.
2. according to the method for claim 1, it is characterized in that inner complex is selected from formula II compound
Wherein, Ln represents lanthanon,
N represents 3 or 4, and m represents the number of 0-4,
If n is 3, then m represents the number of 0-4, and L is selected from the compound of formula V-XII
Perhaps,
If n is 4, then m represents 1, and L is formula H-N
+(R
7)
3Positively charged ion,
R
2Be hydrogen or C
1-C
6Alkyl and
R
1And R
3Independently of one another is hydrogen, C
1-C
6Alkyl, CF
3, C
5-C
24Aryl or C
4-C
24Heteroaryl,
R
4, R
5And R
6Independently of one another is hydrogen, halogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl, C
1-C
6Alkoxyl group, amino, dialkyl amido or cyclic amino group, and R
7Be hydrogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl or vinyl.
3. according to the method for claim 1, it is characterized in that inner complex is selected from the formula III compound
Wherein, Ln represents lanthanon,
N represents 3 or 4, and m represents the number of 0-4,
If n is 3, then m represents the number of 0-4, and L is selected from the compound of formula V-XII
Perhaps,
If n is 4, then m represents 1, and L is formula H-N
+(R
7)
3Positively charged ion,
R
2Be hydrogen or C
1-C
6Alkyl and
R
1And R
3Independently of one another is hydrogen, C
1-C
6Alkyl, CF
3, C
5-C
24Aryl or C
4-C
24Heteroaryl,
R
4, R
5And R
6Independently of one another is hydrogen, halogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl, C
1-C
6Alkoxyl group, amino, dialkyl amido or cyclic amino group, and R
7Be hydrogen, C
1-C
6Alkyl, C
5-C
24Aryl, C6-C
24Aralkyl or vinyl.
4. according to the method for claim 1, it is characterized in that inner complex is selected from formula IV compound
L
m-Ln
3+[R
1-O]
n (IV)，
Wherein, Ln represents lanthanon,
N represents 3 or 4, and m represents the number of 0-4,
If n is 3, then m represents the number of 0-4, and L is selected from the compound of formula V-XII
Perhaps,
If n is 4, then m represents 1, and L is formula H-N
+(R
7)
3Positively charged ion,
R
2Be hydrogen or C
1-C
6Alkyl and
R
1And R
3Independently of one another is hydrogen, C
1-C
6Alkyl, CF
3, C
5-C
24Aryl or C
4-C
24Heteroaryl,
R
4, R
5And R
6Independently of one another is hydrogen, halogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl, C
1-C
6Alkoxyl group, amino, dialkyl amido or cyclic amino group, and R
7Be hydrogen, C
1-C
6Alkyl, C
5-C
24Aryl, C
6-C
24Aralkyl or vinyl.
5. according to the method for claim 2, it is characterized in that: component (a) is the compound of formula II, and wherein L is the compound of formula V, VI, VII, VIII, IX, X, XI or XII, wherein R
4, R
5And R
6Be hydrogen, methyl, amino, pyrrolidyl or dimethylamino, or L is formula H-N
+(R
7)
3Positively charged ion, R wherein
7Be C
1-C
6Alkyl.
6. according to the method for claim 1, it is characterized in that: component (b) for water, one or more can with the miscible organic solvent of water or water and one or more can with the mixture of the miscible organic solvent of water.
7. according to the method for claim 6, it is characterized in that: can be fatty alcohol, ether alcohol, glycol, aliphatic ketone, carboxylicesters, carboxylic acid amide, aliphatic nitrile, aliphatic polyether or aliphatics sulfoxide with the miscible organic solvent of water.
8. according to the method for claim 6, it is characterized in that: can be selected from ethanol, butoxy ethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, acetonitrile, Polyethylene glycol dimethyl ether and methyl-sulphoxide with the miscible organic solvent of water.
9. according to the method for claim 1, it is characterized in that:, contain the component (a) of 0.01-20.0% weight and the component (b) of 80.0-99.99% weight in the composition in the total amount of component (a)+(b).
10. according to the method for claim 1, it is characterized in that: said composition also contains additional (c): one or more tinting materials.
11. a method for preparing luminescent plastics is characterized in that: in the weight of polymeric material, 0.01-10.0% weight according to the formula II of the method for claim 2 or formula III compound according to the method for claim 3 in the presence of extrude this plastic material.
12. luminous textile fibres according to the preparation of the method for claim 1.
13. luminescent plastics according to the preparation of the method for claim 11.
14. according to the process of claim 1 wherein that polymer fiber is paper fibre or synthon.
15. be used to prepare the purposes of security document, card, check or banknote according to the method for claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02405931 | 2002-10-30 | ||
| EP02405931.3 | 2002-10-30 | ||
| EP03405448.6 | 2003-06-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1708571A CN1708571A (en) | 2005-12-14 |
| CN100362078C true CN100362078C (en) | 2008-01-16 |
Family
ID=35581837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801025415A Expired - Fee Related CN100362078C (en) | 2002-10-30 | 2003-10-21 | Process for incorporation of UV-luminescent compounds in polymeric materials |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100362078C (en) |
| BR (1) | BR0315835A2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150132575A1 (en) * | 2013-11-14 | 2015-05-14 | Honeywell International Inc. | Luminescent fibers, articles including the same, and methods of forming the same |
| WO2021134777A1 (en) * | 2020-01-03 | 2021-07-08 | 南通纺织丝绸产业技术研究院 | Chemical fiber textile production chain anti-counterfeiting method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0066854A1 (en) * | 1981-06-05 | 1982-12-15 | GAO Gesellschaft für Automation und Organisation mbH | Security paper and method for its manufacture |
| US4655788A (en) * | 1984-06-22 | 1987-04-07 | Michel Jalon | Security fibers and other materials made luminescent by a dyeing process, processes for their manufacture and their applications |
| US4833311A (en) * | 1986-08-19 | 1989-05-23 | Petrel | Security markings, material provided with security marks, and apparatus to detect the security mark |
-
2003
- 2003-10-21 CN CNB2003801025415A patent/CN100362078C/en not_active Expired - Fee Related
- 2003-10-21 BR BRPI0315835 patent/BR0315835A2/pt unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0066854A1 (en) * | 1981-06-05 | 1982-12-15 | GAO Gesellschaft für Automation und Organisation mbH | Security paper and method for its manufacture |
| US4655788A (en) * | 1984-06-22 | 1987-04-07 | Michel Jalon | Security fibers and other materials made luminescent by a dyeing process, processes for their manufacture and their applications |
| US4833311A (en) * | 1986-08-19 | 1989-05-23 | Petrel | Security markings, material provided with security marks, and apparatus to detect the security mark |
| US4891505A (en) * | 1986-08-19 | 1990-01-02 | Petrel | Security markings, material provided with security marks, and apparatus to detect the security mark |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0315835A2 (en) | 2009-01-20 |
| CN1708571A (en) | 2005-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Abou-Melha | Preparation of photoluminescent nanocomposite ink toward dual-mode secure anti-counterfeiting stamps | |
| KR101015026B1 (en) | Ink compositions containing lanthanide complexes | |
| WO2005014928A2 (en) | Taggant security system for paper products as a deterrent to counterfeiting | |
| Ahmed et al. | Preparation of photochromic and photoluminescent nonwoven fibrous mat from recycled polyester waste | |
| KR101076621B1 (en) | - Process for incorporation of UV-luminescent compounds in polymeric materials | |
| CN101910360B (en) | Organic fluorescent compositions | |
| Sayeb et al. | Investigation of photochromic pigment used for smart textile fabric | |
| WO2008078949A1 (en) | Functional fiber for preventing forgery | |
| CN100362078C (en) | Process for incorporation of UV-luminescent compounds in polymeric materials | |
| Alsharief et al. | Immobilization of strontium aluminate nanoparticles onto plasma-pretreated nonwoven polypropylene fibers by screen-printing toward photochromic textiles | |
| Al-Qahtani et al. | Information encryption strategy for optical security authentication using phosphor-encapsulated poly (N-isopropylacrylamide) nanoparticles | |
| Alharbi et al. | Photoluminescent cellulose nanofibers-reinforced alginate hydrogel with color-tunable and self-healing properties for authentication applications | |
| Gulrajani | Disperse dyes | |
| RU2618742C2 (en) | Polymer bound vat dyes | |
| CN103270119A (en) | Surface-modified pigment preparations | |
| El‐Newehy et al. | Dual‐mode security authentication of SrAl2O4: Eu, Dy phosphor encapsulated in electrospun cellulose acetate nanofibrous films | |
| Hossan | Optical authentication strategy using sodium alginate nanoparticles encapsulating lanthanide-doped aluminate | |
| Al-Qahtani et al. | Recycled poly (propylene-co-methy1 methacrylate) as printing binder for photoluminescent textiles | |
| RU2581882C1 (en) | Marking composition and method of marking and identifying valuable document | |
| KR101151611B1 (en) | Solvent sensitive fibers and manufacturing method of security paper their in these fibers | |
| Al-Qahtani et al. | Photochromic cellulose nanofibers-reinforced polyacrylic acid self-healable hydrogel toward dual-mode security authentication stamp | |
| KR20180042769A (en) | Evenly dyeing textile products with fluorescent pigment and its manufacturing method at low temperature | |
| HUTAKAMOL et al. | Enhancing the color shade and depth of linen fabrics dyed with Caesalpinia sappan L. wood extract using metallic salt mordants | |
| RU2568707C1 (en) | Fibrous polymer for paper protection against counterfeit, method of its production, paper protected against counterfeit including said material and article (important document) | |
| KR101064642B1 (en) | Functional Fabrics Including Ultraviolet Light Reacting Pigments |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080116 Termination date: 20131021 |