CN1157303A - Fluorescent dye dispersion containing high molecular dispersing agent and its preparing method and its use - Google Patents
Fluorescent dye dispersion containing high molecular dispersing agent and its preparing method and its use Download PDFInfo
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- CN1157303A CN1157303A CN96114018A CN96114018A CN1157303A CN 1157303 A CN1157303 A CN 1157303A CN 96114018 A CN96114018 A CN 96114018A CN 96114018 A CN96114018 A CN 96114018A CN 1157303 A CN1157303 A CN 1157303A
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- Prior art keywords
- fluorescent dye
- dispersing agent
- dispersion
- dye dispersion
- macromolecule dispersing
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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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The present invention relates to a fluorescent dye water dispersion liquor for textile industry and its preparation method and application. Said dispersion liquor includes (weight portion): 1-30 portions of fluorescent dye, 1-20 portions of copolymer formed from N-vinyl pyrrolidone and vinyl carboxylate, their mixing ratio (weight ratio) is 1:0.2-1, 1-15 portions of non-ionic surfactant, 0-5portions of defoaming agent, 0-5 portions of preservative and the rest water. Said dispersion system is placed in sand mill, then the fluorescent dye is added, milled for several hours, vacuum-filtered so as to obtain the invented dispersion liquor. Said dispersion liquor can be uniformly dispersed at random proportion.
Description
The present invention relates to textile industry fluorescence dye aqueous dispersions and preparing technical field, particularly contain fluorescence dye aqueous dispersions and the preparation method and the purposes of macromolecule dispersing agent.
Most of fluorescence dyes are water insoluble or are insoluble in the organic compound of water.In actual use, consider that from economic angle fluorescence dye should be prepared into dispersion liquid as dispersion medium with water.Do not need expensive spray drying unit so on the one hand, help on the other hand in use, fluorescence dye is easy to disperse in water with various ratio.And do not bring dust, all useful to laborer's individual protect and environment protection.Therefore, in the fluorescence dye dispersion system, it is particularly important that dispersion agent just seems.It is that dispersion system disperses fluorescence dye as follows with anion surfactant, cats product or nonionogenic tenside and N-vinyl pyrrolidone and 3-7 thiazolinyl propionic acid multipolymer that European patent EP 321,393 has reported a kind of.
Wherein CN is a cyano group, o, m, p represent respectively CN at the ortho position, a position, contraposition.
German patent DE 2734204 adopts vinylformic acid and styrol copolymer or vinylformic acid and copolymer-maleic anhydride as dispersion agent, forms dispersion system with ethylene glycol, trolamine etc., disperses the fluorescence dye of (I) formula structure as mentioned above.
The common drawback of above dispersion agent is all to have carboxyl in dispersion agent, in use is subject to the soda acid influence, thereby causes quality product to descend.
The objective of the invention is to overcome the shortcoming of above dispersion agent, provide a kind of water miscible polymer of nonionic to be applied in the fluorescence dye dispersion system, to satisfy various dyeings as dispersion agent.
The object of the present invention is achieved like this:
Dispersion liquid of the present invention comprises that the ratio of following component and the total umber of the shared dispersion liquid of each component is (unit is a weight part):
Fluorescence dye 1-30 part
Copolymer 1-20 part
Nonionogenic tenside 1-15 part
Defoamer 0-5 part
Sanitas 0-5 part
Water surplus
The preferred version of dispersion liquid of the present invention is (unit is a weight part):
3～25 parts of fluorescence dyes
2～8 parts of multipolymers
1～5 part of nonionogenic tenside
0.1～2 part of defoamer
0.1～0.5 part of sanitas
Water surplus
Fluorescence dye is the compound shown in structure I, the II in the dispersion liquid.
Nonionogenic tenside is 25～40 polyoxyethylene nonylphenol ether for the oxyethane number.Multipolymer (AVP) is N-vinyl pyrrolidone and vinyl carboxylate copolymer, and wherein carboxylic acid is C
2-4Saturated carboxylic acid, molecular weight is 2000-500000, optimum is 5000-20000.Defoamer is silicone antifoam agent GYS-211 etc.Sanitas is formaldehyde, Sodium Benzoate etc.
In general, the molecular weight of AVP is big more, and the demand that joins in the dispersion liquid is more little.The ratio of N-vinyl pyrrolidone and vinyl carboxylates among the AVP improves with the vinyl carboxylates ratio, and dispersion effect is good.But ratio accounts for too greatly, its water-soluble can decline, and storage stability can variation.Therefore, the molecular weight optimal selection between the ratio optimal selection 1 of N-vinyl pyrrolidone and vinyl carboxylates: the 0.3-0.8 (weight ratio), is generally 1 at 5000-20000: 0.2-1 (weight ratio).
The preparation of dye dispersion liquid:
The copolymer 1-20 part that will contain AVP, nonionogenic tenside 1-15 part, silicone antifoam agent 0-5 part, the dispersion system that sanitas 0-5 part is formed is put into the sand mill that has been equipped with a certain amount of all size granulated glass sphere in advance, adds the water-fast fluorescence dye of 1-30 part (I) or (II) or (I+II) again, supply the water of surplus then, amount to 100 parts, grind a few hours, the dyestuff granularity is observed in sampling under biomicroscope.When reaching the 1-2 micron, can stop to grind.Vacuum filtration promptly gets dispersion liquid.
The preparation of AVP: AVP by N-vinyl pyrrolidone and vinyl carboxylates with 1: the ratio synthetic copolymer of 0.2-1 (weight ratio).Its reaction formula is as follows:
AVP
(m+n (polymerization degree)=20-5000,1=1～3)
When 1=1, multipolymer is AVP-1; Vinyl-acetic ester
During 1=2, multipolymer is AVP-2; Propionate
During 1=3, multipolymer is the AVP-3. vinyl butyrate
Because the polymerization velocity of N-vinyl pyrrolidone and vinyl carboxylates is variant, the former is more a lot of soon than latter reaction speed, and polymerization exotherm severity, and this is an experimental fact.Therefore, in the reaction process design, consider this point.Otherwise,, just be difficult to good water solubility, the multipolymer that molecular weight is suitable according to the method for routine.In order to make reaction system is the homogeneous system, adds a certain amount of ethanol.The present invention adopts in reaction system, at first vinyl carboxylates is joined in the reaction system, at a certain temperature, in the certain hour, several times N-vinyl pyrrolidone and vinyl carboxylates is joined in the reaction system.To obtain suitable polymers.Reaction ratio is as follows:
N-vinyl pyrrolidone 1500 (weight part)
Vinyl carboxylates 300-1500 part
Water 2000-5000 part
Ethanol 500-3000 part
Initiator 2-25 part
Initiator is different two fourth hydrogen or the benzoyl peroxides of azo.
The preparation method is as follows:
With vinyl carboxylates 300-1500 part; ethanol 500-3000 part joins in the reactor; stir; be heated to 60-80 ℃; under the nitrogen protection; what will prepare in advance in 2-6 hour contains 1500 parts of N-vinyl pyrrolidones, and the mixing solutions gradation of water 2000-5000 part and initiator 2-25 part joins in the reactor.Continue reaction 2-10 hour.Promptly get polymer A VP.Control the multipolymer that various reacting material ratio and different reaction conditionss can obtain different sized molecules amounts.Molecular weight is measured by gel chromatography.
Above-mentioned fluorescent dye dispersion (claiming white dyes again) is used for textile and dyeing industry, has improved brightening trevira greatly.
The advantage of dispersion liquid of the present invention is to have good rheological and storage stability.At room temperature place no layering and precipitating phenomenon more than 6 months.Dispersion liquid can be with the arbitrary proportion homodisperse in water.Because the N-vinyl pyrrolidone is the multipolymer of forming with vinyl carboxylates, so whole system is a nonionic, so it is little influenced by acid-basicity, can satisfy various dyeings.In tint applications, no matter be to contaminate, or pad dyeing, the cloth that is brightened all can obtain high whiteness value.
Dispersion liquid prepares example 1
(diameter is 1-1.5mm 100 grams on the hybrid glass pearl that 250 all sizes that restrain are housed, 1.5-2mm 100 grams, 2-3mm 50 grams) in the small-sized sand milling device (volume is 500ml), add fluorescence dye (I) (CN is at the ortho position) 10 grams, polyoxyethylene nonylphenol ether (oxyethane several 25) 1 gram, (ratio of N-vinyl pyrrole ketone and propionate is (weight ratio) 1: 0.3 to the AVP-2 aqueous copolymers solution, molecular weight is about 20000, solid content is 25%) 3 grams, silicone antifoam agent GYS-211,0.5 gram, sanitas (37% formalin) 0.2 gram and water 85.3 grams.Open and stir, grind more than 10 hours, the dyestuff granularity is observed in sampling under biomicroscope.When reaching 1-2 μ, stop to grind.Vacuum filtration promptly gets dispersion liquid 1.At room temperature place no layering and precipitating phenomenon more than six months.
Dispersion liquid prepares example 2
Fluorescence dye (I) (CN is at the ortho position) 8 grams, fluorescence dye (II) 2 grams, polyoxyethylene nonylphenol ether (oxyethane several 40) 3 grams, AVP-1 (ratio of N-vinyl pyrrole ketone and vinyl-acetic ester is 1: 0.6, and molecular weight is about 7000, and solid content is 35%), 5 grams, silicone antifoam agent GYS-211,0.6 gram, sanitas (37% formalin) 0.3 gram and water 81.1 grams.Prepare dispersion liquid 2 by example 1 same condition and method.
AVP synthesizes example 1
The mechanical stirring reflux condensing tube is being housed, and dropping funnel in 1000 milliliters of four-hole bottles of thermometer (inserting a large size stainless steel syringe needle from the soft rubber ball of fixed thermometer, so that logical nitrogen), adds vinyl-acetic ester 50 grams, and ethanol 100 grams fully stir evenly.In advance miscible N-vinyl pyrrolidone 150 grams are arranged in that dropping funnel is mid-, water 300 grams and azo-bis-isobutyl cyanide 0.5 restrain.Reaction flask is heated to 60 ℃ in oil bath, and feeds nitrogen, mixing solutions gradation in 2 hours is splashed in the reaction flask, keep the reaction solution slight boiling condition by dropping funnel.Drip and finish, continued back flow reaction 5 hours.Promptly get 1: 0.33 N-vinyl pyrrole ketone and vinyl acetate copolymer (AVP-1).
AVP synthesizes example 2
In the 100L enamel reaction still; add 7.5 kilograms of propionate numbers; 10 kilograms of ethanol; fully stir; in header tank, place 10 kilograms of N-vinyl pyrrolidones that are mixed in advance; 30 kg water and 50 gram initiators (benzoyl peroxide) are heated to 70 ℃ with reactor, and logical nitrogen protection.Solution reaches slight boiling condition in still, begins the mixing solutions in the header tank is splashed in the reactor, and keeping reaction solution is slight boiling condition, drips off in 6 hours.Continuation was reacted 8 hours down at 70 ℃, promptly got the multipolymer (AVP-2) of a viscosity.
By the fluorescent dye dispersion of above-mentioned examples preparation and the domestic commercial whitening agent DT of the China simultaneous test that dyes.1 consumption
Dispersion liquid 16 grams per liters
Dispersion liquid 26 grams per liters
DT 30 grams per liters (power part: 100%, Chinese the Ministry of Chemical Industry standard) 2 dyeings
3 detected results (whiteness) dispersion liquid, 1 132.3 dispersion liquids, 2 131.5DT 118.1
Coloration result shows that Zhi Bei fluorescent dye dispersion has high whitening effect to polyster fibre as stated above.
Claims (10)
1. a fluorescent dye dispersion that contains macromolecule dispersing agent comprises fluorescence dye, multipolymer, and nonionogenic tenside is characterized in that described dispersion liquid is (weight part):
Fluorescence dye 1-30 part,
Copolymer 1-20 part
Nonionogenic tenside 1-15 part
Defoamer 0-5 part
Sanitas 0-5 part
The described multipolymer of water surplus is (weight ratio):
The copolymer 1 that N-vinyl pyrrolidone and vinyl carboxylates are formed: 0.2-1.
2. a kind of fluorescent dye dispersion that contains macromolecule dispersing agent as claimed in claim 1 is characterized in that described vinyl carboxylates is a vinyl-acetic ester, propionate, vinyl butyrate.
3. a kind of fluorescent dye dispersion that contains macromolecule dispersing agent as claimed in claim 1 is characterized in that described molecular weight of copolymer is 2000-500000.
4. a kind of fluorescent dye dispersion that contains macromolecule dispersing agent as claimed in claim 3 is characterized in that the best 5000-20000 of being of described molecular weight of copolymer.
5. a kind of fluorescent dye dispersion that contains macromolecule dispersing agent as claimed in claim 1 is characterized in that described nonionogenic tenside is the Nonyl pheno ester of oxyethane quantity 25-40.
6. a kind of fluorescent dye dispersion that contains macromolecule dispersing agent as claimed in claim 1 is characterized in that the preferred version of described dispersion liquid is (unit is a weight part):
3～25 parts of fluorescence dyes
2～8 parts of multipolymers
1～5 part of nonionogenic tenside
0.1～2 part of defoamer
0.1～0.5 part of sanitas
Water surplus
7. a kind of fluorescent dye dispersion that contains macromolecule dispersing agent as claimed in claim 1 is characterized in that described fluorescence dye is the compound shown in structure I, the II:
Wherein CN is a cyano group, o, m, p represent respectively CN at the ortho position, a position, contraposition
8. method for making that contains the fluorescent dye dispersion of macromolecule dispersing agent; it is characterized in that (weight part): with vinyl carboxylates 300-1500 part; ethanol 500-3000 part adds in the reactor; stir the companion evenly; be heated to 60-80 ℃; under the nitrogen protection; what will prepare in advance in 2-6 hour contains 1500 parts of N-vinyl pyrrolidones; the mixing solutions gradation of water 2000-5000 part and initiator 2-25 part adds in the reactor, continues reaction and gets copolymer A VP after 2-10 hour, gets 1-20 part; nonionogenic tenside 1-15 part; silicone antifoam agent 0-5 part, the dispersion system that sanitas 0-5 part is formed is put into the sand mill that has been equipped with a certain amount of all size granulated glass sphere in advance; add the water-fast fluorescence dye of 1-30 part (I) or (II) or (I+II) again; supply the water of surplus then, amount to 100 parts, grind a few hours; when reaching the 1-2 micron; promptly stop to grind, vacuum filtration promptly gets fluorescent dye dispersion.
9. a kind of fluorescent dye dispersion method for making that contains macromolecule dispersing agent as claimed in claim 8 is characterized in that described initiator is azo two isobutyl nitrogen, benzoyl peroxide.
10. a purposes that contains the fluorescent dye dispersion of macromolecule dispersing agent is characterized in that described fluorescent dye dispersion is used for textile and dyeing industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114018A CN1058978C (en) | 1996-12-31 | 1996-12-31 | Fluorescent dye dispersion containing high molecular dispersing agent and its preparing method and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114018A CN1058978C (en) | 1996-12-31 | 1996-12-31 | Fluorescent dye dispersion containing high molecular dispersing agent and its preparing method and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1157303A true CN1157303A (en) | 1997-08-20 |
| CN1058978C CN1058978C (en) | 2000-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96114018A Expired - Fee Related CN1058978C (en) | 1996-12-31 | 1996-12-31 | Fluorescent dye dispersion containing high molecular dispersing agent and its preparing method and its use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051069A (en) * | 2010-10-24 | 2011-05-11 | 绍兴文理学院 | Nonionic disperse system liquid-shaped disperse dye and preparation method thereof |
| WO2018181556A1 (en) * | 2017-03-29 | 2018-10-04 | 旭化成株式会社 | Photosensitive resin composition |
| CN109476786A (en) * | 2016-08-05 | 2019-03-15 | 东丽株式会社 | Copolymer and seperation film, Medical Devices and the blood purification for having used it |
-
1996
- 1996-12-31 CN CN96114018A patent/CN1058978C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051069A (en) * | 2010-10-24 | 2011-05-11 | 绍兴文理学院 | Nonionic disperse system liquid-shaped disperse dye and preparation method thereof |
| CN102051069B (en) * | 2010-10-24 | 2013-05-29 | 绍兴文理学院 | Nonionic disperse system liquid-shaped disperse dye and preparation method thereof |
| CN109476786A (en) * | 2016-08-05 | 2019-03-15 | 东丽株式会社 | Copolymer and seperation film, Medical Devices and the blood purification for having used it |
| CN109476786B (en) * | 2016-08-05 | 2021-08-03 | 东丽株式会社 | Copolymer, and separation membrane, medical device, and blood purifier using same |
| AU2017305070B2 (en) * | 2016-08-05 | 2022-03-10 | Toray Industries, Inc. | Copolymer, and separation membrane, medical device, and blood purifier using the copolymer |
| WO2018181556A1 (en) * | 2017-03-29 | 2018-10-04 | 旭化成株式会社 | Photosensitive resin composition |
| JPWO2018181556A1 (en) * | 2017-03-29 | 2019-08-08 | 旭化成株式会社 | Photosensitive resin composition |
| CN110325913A (en) * | 2017-03-29 | 2019-10-11 | 旭化成株式会社 | Photosensitive polymer combination |
| CN110325913B (en) * | 2017-03-29 | 2022-11-01 | 旭化成株式会社 | Photosensitive resin composition |
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| Publication number | Publication date |
|---|---|
| CN1058978C (en) | 2000-11-29 |
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