CN106752079A - A kind of disperse dye composition and its production and use - Google Patents
A kind of disperse dye composition and its production and use Download PDFInfo
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- CN106752079A CN106752079A CN201611257335.7A CN201611257335A CN106752079A CN 106752079 A CN106752079 A CN 106752079A CN 201611257335 A CN201611257335 A CN 201611257335A CN 106752079 A CN106752079 A CN 106752079A
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- dye composition
- disperse dye
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- trichlorophenol
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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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo dyes
-
- 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
- C09B67/0079—Azoic dyestuff preparations
-
- 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
- C09B67/008—Preparations of disperse dyes or solvent dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
- D06P1/18—Azo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
- D06P1/19—Nitro dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/004—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using dispersed dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
Abstract
A kind of disperse dye composition and its production and use, the disperse dye composition include formula (1) compound in one or more compound group into component A, disabling aromatic amine compound, chlorinated phenol, chlorobenzene and chlorotoluene, optional auxiliary material, and other inevitable impurity, its not only every environmental protection index meet the requirement of Oeko Tex Standard 100 (2016), and it is below 10ppm that the total content of aromatic amine compound is disabled in the dye composite chemical products of dyeing, all kinds of respective total contents of chlorinated phenol are below 0.5ppm, chlorobenzene chlorotoluene (COCs) total content is less than below 1ppm.Sewage aspect also meet the requirement of environmental protection after dye, at the same using it is more convenient, trust.
Description
Technical field
The present invention relates to a kind of disperse dye composition and its production and use.The disperse dye composition is applicable
Dyeing and stamp in terylene and its blend fabric.
Background technology
Although environment-friendly dye is restricted for the content of harmful material, mostly simply to weaving face fabric ring
Control is protected, i.e., the dyestuff on weaving face fabric is measured, control the content of its harmful substance, thus, however it remains dyeing institute
Harmful substance contents are high in dyestuff chemistry product, cause sewage, the sludge of printing and dyeing mill seriously beyond environmental requirement, and influence is ecological
Environment.Simultaneously because of the difference of textile printing and dyeing process, or dye dosage difference, cause containing for contained harmful substance in textile
Amount is also different, and such dyeing waste water, sludge and part do not reach the weaving face fabric of environmental requirement to being made as the printing and dyeing mill in downstream
Into larger loss.To prevent the generation of above-mentioned thing, preferably environmental protection, ensure that consumer's is healthy and safe, make enterprise
Energy sustainable development steady in a long-term, the high-environmental type product for researching and developing the chemicals environmental protection level used by a kind of dyeing is disperse dyes
The task of top priority in market, is also the only way which must be passed of enterprise's existence and development, even more the inexorable trend of disperse dyes development.
The content of the invention
The present invention is intended to provide the disperse dye composition of chemicals environmental protection level, its not only every environmental protection index meet
The requirement of Oeko-Tex Standard 100 (2016), and disable aromatic amine in the dye composite chemical products of dyeing
The content of compound (AZO), chlorinated phenol (CPs), chlorobenzene and chlorotoluene (COCs) is low.10% dye level dyeing simultaneously
Afterwards, fabric meets the requirement of the babies of Oeko-Tex Standard 100 (2016) level, particularly disables aromatic amine compound
(AZO) total content is below 5ppm, all kinds of chlorinated phenol total contents are below 0.05ppm, chlorobenzene and chlorotoluene (COCs)
Total content is below 0.1ppm, in addition, sewage aspect also meet the requirement of environmental protection after dye, while using it is more convenient, trust.
Therefore, the present invention provides a kind of disperse dye composition, it is characterised in that including a kind of in formula (1) compound or
Component A, disabling aromatic amine compound, chlorophenic acid, chlorophenesic acid, trichlorophenol, 2,4,6,-T, tetrachlorophenol, five of multiple compounds composition
Chlorophenol, chlorobenzene and chlorotoluene, optional auxiliary material and other inevitable impurity,
In formula (1),
R1It is hydrogen or C1-C4Alkyl amide；
R2、R3It is each independently hydrogen, C1-C4Alkyl or substituted C1-C4Alkyl, the substituted C1-C4The substitution of alkyl
Base is selected from-CN ,-OCOR ,-OCOC6H5、-COOR、-C6H5Or C1-C4Alkoxy, each R is each independently C1-C4Alkyl；
Wherein, the disabling aromatic amine compound is selected from 4- aminobphenyls (CAS NO.92-67-1), benzidine (CAS
NO.92-87-5), 4- chloro-o-toluidines (CAS NO.95-69-2), 2- naphthylamines (CAS NO.91-59-8), adjacent amino azo first
Benzene (CAS NO.97-56-3), 2- amino -4- nitrotoleunes (CAS NO.99-55-8), parachloroanilinum (CAS NO.106-47-
8), 2,4- diamino anisoles (CAS NO.615-05-4), 4,4 '-MDA (CAS NO.101-77-9), 3,
3 '-dichloro-benzidine (CAS NO.91-94-1), 3,3 '-dimethoxy benzidine (CAS NO.119-90-4), 3,3 '-diformazan
Base benzidine (CAS NO.119-93-7), 3,3 '-dimethyl -4,4 '-MDA (CAS NO.838-88-0), 2-
Methoxyl group -5- methylanilines (CAS NO.120-71-8), 4,4 '-diaminourea -3,3 '-dichloro diphenyl methane (CAS NO.101-
14-4), 4,4 '-benzidine ether (CAS NO.101-80-4), 4,4 '-diaminodiphenyl sulfide (CAS NO.139-65-
1), ortho-aminotoluene (CAS NO.95-53-4), 2,4 di amino toluene (CAS NO.95-80-7), 2,4,5- trimethylanilines
(CAS NO.137-17-7), o-aminoanisole (CAS NO.90-04-0), P-aminoazobenzene (CAS NO.60-09-3),
One or more in 2,4- dimethylanilines (CAS NO.95-68-1), 2,6- dimethylanilines (CAS NO.87-62-7).
According to EN14362:The method of 2012 (gas chromatograph-mass spectrometer (GC-MS) GC-MS and high performance liquid chromatograph HPLC)
Detected, the total content that aromatic amine compound is disabled described in dye composite of the invention is 0-10ppm.That is, the present invention
Dye composite in can be free of the aromatic amine compound, or contain one kind in the aromatic amine compound or many
Kind, but the total content of the aromatic amine compound is no more than 10ppm.
The chlorophenic acid be selected from 2- chlorophenols, 3- chlorophenols, one or more of 4- chlorophenols；The chlorophenesic acid
It is selected from 2,6- chlorophenesic acids, 2,4 dichloro phenol, 2,5- chlorophenesic acids, 3,5- chlorophenesic acids, 2,3- chlorophenesic acids, 3,4- bis-
One or more in chlorophenol；The trichlorophenol, 2,4,6,-T is selected from 2,4,6- trichlorophenol, 2,4,6,-Ts, 2,3,6- trichlorophenol, 2,4,6,-Ts, 2,3,5- tri-
One or more in chlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts, 2,3,4- trichlorophenol, 2,4,6,-Ts, 3,4,5- trichlorophenol, 2,4,6,-Ts；The tetrachlorobenzene
Phenol is selected from one or more in 2,3,4,6- tetrachlorophenols, 2,3,5,6- tetrachlorophenols, 2,3,4,5- tetrachlorophenols；
With reference to ISO17070:The method of 2015 (gas chromatograph-mass spectrometer (GC-MS) GC-MS) is measured, dye of the invention
Each total content is 0- for chlorophenic acid described in feed composition, chlorophenesic acid, trichlorophenol, 2,4,6,-T, tetrachlorophenol, pentachlorophenol
0.5ppm.In dye composite i.e. of the invention can be free of chlorinated phenol, or containing chlorinated phenol in one or more,
But the respective total content of the chlorophenic acid, chlorophenesic acid, trichlorophenol, 2,4,6,-T, tetrachlorophenol, pentachlorophenol is no more than 0.5ppm.
The chlorobenzene and chlorotoluene are selected from monochloro-benzene, dichloro-benzenes, trichloro-benzenes, tetrachlorobenzene, pentachlorobenzene, hexachloro-benzene, a chlorine
One or more in toluene, dichlorotoleune, benzotrichloride, toluene tetrachloride, toluene pentachloride；
It is measured with reference to the method for GB/T24167-2009 (solvent extraction, gas chromatograph-mass spectrometer (GC-MS) GC-MS),
The total content of chlorobenzene and chlorotoluene described in dye composite of the invention is 0-1ppm.Can in dye composite i.e. of the invention
With without the chlorobenzene and chlorotoluene, or contain one or more in the chlorobenzene and chlorotoluene, but the chlorobenzene and chlorine
The total content of toluene is no more than 1ppm.
Preferably, the component A is selected from one or more in formula (1-1)~(1-6) compound,
Preferably, the auxiliary material includes auxiliary agent and water；
Preferably, the auxiliary agent and the weight ratio of component A are 0.25~6.5:1；
Preferably, described auxiliary agent includes one or more following：Dispersant, dyeing auxiliaries, surfactant, kill
Microbial inoculum；
Preferably, the dispersant is selected from naphthalene sulfonic acid-formaldehyde condensation product (dispersing agent NNO), methyl naphthalene sulfonic acid and formaldehyde condensation
In thing (Dispersant MF), benzyl naphthalene sulfonic acid-formaldehyde condensation product (dispersing agent CNF) or lignosulfonates (83A, lignin 85A)
One or more；
Preferably, the dyeing auxiliaries is glauber salt.
Preferably, the disperse dye composition can be the liquid after being ground with sand mill or grinder, and solid content is
Powdery or graininess are made for behind 20~50%, or disperse dye composition spray drying, solid content is 87~96%.
The present invention also provides the method for preparing the disperse dye composition, it is characterised in that comprise the following steps：By 2,
6- Dichloro-4-nitroaniline diazotising, adds water and/or ice dilutes below 5 DEG C, plus the stirring of diatomite, activated carbon or bentonite,
Filtering, then coupling reaction is carried out with formula Y compounds, obtain product I；Product I or product I contaminates with the mixture of auxiliary material as dispersion
Feed composition；
Wherein R1、R2、R3As defined in claim 1-3.
Preferably, the preparation method is comprised the following steps：
(1) to sulfuric acid is added in diazonium kettle, nitrosyl sulfuric acid is added, control temperature is no more than 40 DEG C, cools to 20~30
DEG C, 2,6- Dichloro-4-nitroanilines are added, finish, at 20-30 DEG C, 4-8 hours is incubated, diazo liquid is obtained, in diazonium dilution kettle
Add water, ice to cool to less than 5 DEG C, be pressed into diazo liquid, control dilution temperature is no more than 5 DEG C, addition diatomite, activated carbon or
Bentonite, stirs 30~60 minutes, and filtering, filtrate squeezes into coupling kettle；
(2) to ice, urea (or sulfamic acid) and emulsifying agent is added in coupling kettle, stir 15-60 minutes, add froth breaking
Agent, control temperature is added dropwise formula Y compounds below 10 DEG C, and time for adding 2~5 hours, 10~15 DEG C of controlling reaction temperature is protected
Temperature reaction 2-5 hours, is slowly warmed up to 50~85 DEG C and turns crystalline substance, and filtering, washing obtain product I；Product I or product I and auxiliary material
Mixture is used as disperse dye composition；
Preferably, the emulsifying agent is selected from one or more in AEO.
In above-mentioned preparation method, one or more in products therefrom I and optional auxiliary material can be mixed, carry out grain
Sub-ization treatment, is made slurry or is dried, and disperse dye composition is obtained；
Or various in products therefrom I are carried out into particlized treatment respectively, then mixed, it is made slurry or is done
It is dry, disperse dye composition is obtained.
Preferably, the particlized treatment is carried out using sand mill or grinder.
Preferably, it is described dry using spray drying.
The present invention also provides the disperse dye composition for the dyeing of fabric or the purposes of stamp；Preferably, it is described
Fabric is terylene or polyester blended fabric.
The present invention also provides a kind of fabric, it is characterised in that dyeed using the disperse dye composition or stamp
Prepare；Preferably, the fabric is terylene or polyester blended fabric.
Invention effect
Disperse dye composition of the invention is the disperse dye composition of chemicals environmental protection level, its not only every environmental protection refer to
Reference symbol closes the requirement of Oeko-Tex Standard 100 (2016), and is disabled in the dye composite chemical products of dyeing
The total content of aromatic amine compound is below 10ppm, chlorophenic acid, chlorophenesic acid, trichlorophenol, 2,4,6,-T, tetrachlorophenol, pentachlorophenol
Respective total content no more than 0.5ppm, chlorobenzene and chlorotoluene (COCs) total content be below 1ppm.Sewage aspect after dye
Meet the requirement of environmental protection, at the same using it is more convenient, trust.
On the other hand, in the case of disperse dye composition meet the requirement of environmental protection of the invention, no matter downstream printing and dyeing enterprise pair
How dyeing and printing process is changed, or the maximum of dye dosage uses, the environmental protection of guarantee textile that can be comprehensive.Using this
After the disperse dye composition of invention is dyeed to fabric, fabric meets Oeko-Tex Standard 100 (2016) after dye
The requirement of baby's level, the total content for particularly disabling aromatic amine compound can reach below 5ppm, chlorophenic acid, chlorophenesic acid,
The respective total content of trichlorophenol, 2,4,6,-T, tetrachlorophenol, pentachlorophenol is below 0.05ppm, and the total content of chlorobenzene and chlorotoluene is
Below 0.1ppm.Dyeing and printing sewage, sludge meet the requirement of environmental protection, save environmental protection treatment cost simultaneously, are that enterprise development and protection are given birth to
Solid foundation is established in state environment and sustainable development.
Specific embodiment
Make further exemplary illustration to the present invention with reference to embodiment, but protection scope of the present invention is not limited to
This.
2,6- Dichloro-4-nitroanilines employed in following preparation examples and contrast preparation example are commercially available product.
Preparation example 1：
(1) to sulfuric acid is added in diazonium kettle, stirring is opened, then is slowly added into nitrosyl sulfuric acid, control temperature is no more than 40
DEG C, finish, 23 DEG C are cooled to, 2,6- Dichloro-4-nitroanilines are slowly uniformly added into, finish, 4 hours are incubated at 25-30 DEG C, obtain
Diazo liquid, adds water, ice to cool to less than 5 DEG C in diazonium dilution kettle, and press-in diazo liquid is diluted, control dilution temperature
No more than 5 DEG C, pressure finishes, and adds diatomite, stirs 30 minutes, and filtering, filtrate squeezes into coupling kettle.
(2) coupling kettle stirring is opened, ice, urea and peregal is added, is stirred 15 minutes, add isooctanol, control temperature
Below 10 DEG C, coupling component N- methyl-N-benzyl aniline is added dropwise, time for adding 4 hours is finished, controlling reaction temperature 10~
15 DEG C, drop finishes insulation reaction 2 hours, is slowly warmed up to 60 DEG C and turns crystalline substance, and filtering, washing are obtained product (I-1).Products therefrom I-1
In containing as component A formula (1-1) compound.
Preparation example 2：
(1) to sulfuric acid is added in diazonium kettle, stirring is opened, then is slowly added into nitrosyl sulfuric acid, control temperature is no more than 40
DEG C, finish, 25 DEG C are cooled to, 2,6- Dichloro-4-nitroanilines are slowly uniformly added into, finish, 8 hours are incubated at 25-30 DEG C, obtain
Diazo liquid, adds water, ice to cool to less than 5 DEG C in diazonium dilution kettle, and press-in diazo liquid is diluted, control dilution temperature
No more than 5 DEG C, pressure finishes, and adds diatomite, stirs 60 minutes, and filtering, filtrate squeezes into coupling kettle.
(2) coupling kettle stirring is opened, ice, urea and peregal is added, is stirred 60 minutes, add isooctanol, control temperature
Below 10 DEG C, coupling component N- cyanoethyl-N- Acetoxyethyl aniline is added dropwise, time for adding 5 hours is finished, control reaction
10~15 DEG C of temperature, drop finishes insulation reaction 3 hours, is slowly warmed up to 80 DEG C and turns crystalline substance, and filtering, washing are obtained product (I-2).Institute
Contain formula (1-2) compound as component A in product I-2.
Preparation example 3-6：
Using the method for preparation example 1, except that, (1) is by the coupling component N- methyl-N-benzyl benzene in preparation example 1
Amine is substituted using the coupling component shown in table 1；(2) preparation example 3 and 4 is respectively by the diatomite in preparation example 1 using work
Property charcoal, bentonite substitute.
Table 1
Component A preparation example 3-6 contained in products therefrom (I-3)-(I-6) successively is followed successively by formula (1-3)-(1-6) chemical combination
Thing.
Contrast preparation example 1：
(1) to sulfuric acid is added in diazonium kettle, stirring is opened, then is slowly added into nitrosyl sulfuric acid, control temperature is no more than 40
DEG C, finish, 23 DEG C are cooled to, 2,6- Dichloro-4-nitroanilines are slowly uniformly added into, finish, 4 hours are incubated at 25-30 DEG C, obtain
Diazo liquid, adds water, ice to cool to less than 5 DEG C in diazonium dilution kettle, and press-in diazo liquid is diluted, control dilution temperature
No more than 5 DEG C, pressure finishes, and stirs 30 minutes, squeezes into coupling kettle.
(2) coupling kettle stirring is opened, urea and peregal is added, is stirred 15 minutes, add isooctanol, control temperature is 10
Below DEG C, coupling component N, N- dicyanoethyl-aniline is added dropwise, time for adding 4 hours is finished, 10~15 DEG C of controlling reaction temperature,
Drop finishes insulation reaction 2 hours, is slowly warmed up to 60 DEG C and turns crystalline substance, and filtering, washing are obtained product (I ' -5).The product (I ' -5)
In contain formula (1-5) compound..
Contrast preparation example 2：
By 135 grams of water and 40 grams of chloro- tetranitroanilines of (percentage amount 0.19mol) 2,6- bis- and 30% sodium hydroxide solution
25 grams (0.19mol), normal pressure is warmed up to 60 degree, and stirs 3 hours at this temperature, terminates rear suction filtration washing, then with coupling group
Divide the coupling of N- cyanoethyl-N- Acetoxyethyls aniline, prepare product (I ' -2).In course of reaction, there is chlorine atom and leave away, part
Material becomes the problem of tarry impurity, and preparation is difficult to be smoothed out.
Contrast preparation example 3：
100gDMF, 125g 2,6- Dichloro-4-nitroanilines is added to be warmed up to 90 DEG C in 500ml flasks, insulation 3 is small
When, 60 DEG C are cooled to, 100g methyl alcohol is added, continue to cool to less than 15 DEG C, filtering, methyl alcohol washing, washing is dried, and obtains refined
2,6- Dichloro-4-nitroanilines, then with the coupling of coupling component N- cyanoethyl-N- Acetoxyethyls aniline, product (I " -2) is obtained,
Contain formula (1-2) compound in the product (I " -2).
Embodiment 1：
By 100 grams of products (I-5) and 92 grams of lignin 85A, add water 288 grams and stir, ground with sand mill
Mill, is then spray-dried, and obtains final product orange fine work disperse dye composition.
Comparative example 1：
According to the identical method of embodiment 1, except that, by the product (I-5) in embodiment 1 using contrast preparation example
1 product for preparing (I ' -5) is substituted.
The dyestuff finished product of embodiment 1 and comparative example 1 is carried out into following test, specific method of testing is as follows：
(1) to the dye product of embodiment 1 and comparative example 1 respectively according to EN14362:2012 (gas chromatography-mass spectrographies
Instrument GC-MS and high performance liquid chromatograph HPLC), with reference to ISO17070:2015 (gas chromatograph-mass spectrometer (GC-MS) GC-MS), reference
The method of GB/T24167-2009 (solvent extraction, gas chromatograph-mass spectrometer (GC-MS) GC-MS), carries out dividing for AZO, CPs, COCs
Analysis test, test result is shown in Table 2：
Table 2
| Title | AZO | CPs | COCs |
| Embodiment 1 | ND | 0.25ppm (chlorophenesic acid) | 0.8ppm |
| Comparative example 1 | 54ppm | 113.25ppm (chlorophenesic acid) | 16.0ppm |
Note：(1) detection limit in dye composite product
AZO：ND=is not detected, detection limit=10ppm, hundred a ten thousandths of ppm==mg/kg=mg/kgs, similarly hereinafter；
CPs：ND=is not detected, detection limit=0.05ppm, hundred a ten thousandths of ppm==mg/kg=mg/kgs, under
Together；
COCs：ND=is not detected, detection limit=0.1ppm, hundred a ten thousandths of ppm==mg/kg=mg/kgs, under
Together；
(2) data of CPs are the detection data of the class of content highest one in five class chlorinated phenols, similarly hereinafter.
From Table 2, it can be seen that every environmental protection index of the disperse dye composition product of the acquisition of embodiment 1 is better than contrast
The disperse dye composition product that example 1 is obtained.
(2) according to the method for GB/T2394-2006, the disperse dyes combination of 1 gram of embodiment 1 and comparative example 1 is weighed respectively
In produce product to the water of 500ml, disperse dyes suspension is made, draws 100ml disperse dyes suspension, dye bath is adjusted with acetic acid
PH to 5, is then warmed up to 60 DEG C, while being respectively put into 2g polyster fibres carries out high-temperature pressure dyeing, is warmed up in 35 minutes
130 DEG C, 45 minutes are incubated, are cooled to 80 DEG C of samplings.According to EN14362:2012 (gas chromatograph-mass spectrometer (GC-MS) GC-MS and height
Effect liquid phase chromatogram instrument HPLC), with reference to ISO17070:2015 (gas chromatograph-mass spectrometer (GC-MS) GC-MS), reference GB/T24167-
The method of 2009 (solvent extractions, gas chromatograph-mass spectrometer (GC-MS) GC-MS), the analysis to Textile AZO, CPs, COCs after dye
Test, test result is shown in Table 3：
Table 3
| Title | AZO | CPs | COCs |
| Embodiment 1 | ND | ND | ND |
| Comparative example 1 | 6ppm | 23.2ppm (chlorophenesic acid) | 1.8ppm |
Note：Detection limit in textile：
AZO：ND=is not detected, detection limit=5ppm, hundred a ten thousandths of ppm==mg/kg=mg/kgs, similarly hereinafter；
CPs：ND=is not detected, detection limit=0.05ppm, hundred a ten thousandths of ppm==mg/kg=mg/kgs, under
Together；
COCs：ND=is not detected, detection limit=0.1ppm, hundred a ten thousandths of ppm==mg/kg=mg/kgs, under
Together；
As can be seen that every environmental protection index of embodiment 1 is better than comparative example 1 from table 2 and 3, and the dispersion of embodiment 1 contaminates
After feed composition is used for textile dyeing as dyestuff, AZO, CPs, COCs are not detected after dye on fabric.
Embodiment 2：
By product (I-2) obtained in 100 grams of preparation examples 2 and 74 grams of Dispersant MFs, 100 grams of lignin 85A, add water 411 grams
Stir, be ground with sand mill, be then spray-dried, obtain final product orange fine work disperse dye composition.
Comparative example 2
According to the identical method of embodiment 2, except that, by the product (I-2) in embodiment 2 using contrast preparation example
3 products for preparing (I " -2) substituted.
The dyestuff finished product of embodiment 2 and comparative example 2 is carried out into following test, specific method of testing is as follows：
(1) to the dye product of embodiment 2 and comparative example 2 respectively according to EN14362:2012 (gas chromatography-mass spectrographies
Instrument GC-MS and high performance liquid chromatograph HPLC), with reference to ISO17070:2015 (gas chromatograph-mass spectrometer (GC-MS) GC-MS), reference
The method of GB/T24167-2009 (solvent extraction, gas chromatograph-mass spectrometer (GC-MS) GC-MS), carries out dividing for AZO, CPs, COCs
Analysis test, test result is shown in Table 4：
Table 4
| Title | AZO | CPs | COCs |
| Embodiment 2 | ND | ND | 0.7ppm |
| Comparative example 2 | ND | 12.25ppm (chlorophenesic acid) | 1.5ppm |
(2) according to the method for GB/T2394-2006, the disperse dyes combination of 1 gram of embodiment 2 and comparative example 2 is weighed respectively
In produce product to the water of 500ml, disperse dyes suspension is made, draws 100ml disperse dyes suspension, dye bath is adjusted with acetic acid
PH to 5, is then warmed up to 60 DEG C, while being respectively put into 2g polyster fibres carries out high-temperature pressure dyeing, is warmed up in 35 minutes
130 DEG C, 45 minutes are incubated, are cooled to 80 DEG C of samplings.According to EN14362:2012 (gas chromatograph-mass spectrometer (GC-MS) GC-MS and height
Effect liquid phase chromatogram instrument HPLC), with reference to ISO17070:2015 (gas chromatograph-mass spectrometer (GC-MS) GC-MS), reference GB/T24167-
The method of 2009 (solvent extractions, gas chromatograph-mass spectrometer (GC-MS) GC-MS), the analysis to Textile AZO, CPs, COCs after dye
Test, test result is shown in Table 5：
Table 5
| Title | AZO | CPs | COCs |
| Embodiment 2 | ND | ND | ND |
| Comparative example 2 | ND | ND | 0.3ppm |
As can be seen that every environmental protection index of embodiment 2 is better than comparative example 2 from table 4 and 5, and the dispersion of embodiment 2 contaminates
After feed composition is used for textile dyeing as dyestuff, AZO, CPs, COCs are not detected after dye on fabric.
Embodiment 3-10
According to the identical method of embodiment 1, according to the compositing formula in table 6, the disperse dye composition such as institute of table 6 is made
Show.
Table 6：
The dyestuff finished product of embodiment 3-10 is carried out into following test, specific method of testing is as follows：
(1) to the dye product of embodiment 3-10 respectively according to EN14362:2012 (gas chromatograph-mass spectrometer (GC-MS) GC-
MS and high performance liquid chromatograph HPLC), with reference to ISO17070:2015 (gas chromatograph-mass spectrometer (GC-MS) GC-MS), reference GB/
The method of T24167-2009 (solvent extraction, gas chromatograph-mass spectrometer (GC-MS) GC-MS), the analysis for carrying out AZO, CPs, COCs is surveyed
Examination, test result is shown in Table 7：
Table 7
| Title | AZO | CPs | COCs |
| Embodiment 3 | ND | 0.11ppm (chlorophenesic acid) | 0.3ppm |
| Embodiment 4 | ND | 0.18ppm (chlorophenesic acid) | 0.4ppm |
| Embodiment 5 | ND | 0.32ppm (chlorophenesic acid) | 0.5ppm |
| Embodiment 6 | ND | 0.16ppm (chlorophenesic acid) | 0.3ppm |
| Embodiment 7 | ND | ND | 0.2ppm |
| Embodiment 8 | ND | 0.08ppm (chlorophenesic acid) | 0.2ppm |
| Embodiment 9 | ND | ND | ND |
| Embodiment 10 | ND | 0.06ppm (chlorophenesic acid) | 0.2ppm |
The disperse dye composition product as obtained in the method for preparation example of the present invention and embodiment, although batch is different, ring
Protect index and slightly have difference, but all below required limitation, and environmental protection index is unrelated with institute's adding assistant and Ginding process.
(2) according to the method for GB/T2394-2006,1 gram of disperse dye composition product of embodiment 3-10 is weighed respectively
Into the water of 500ml, disperse dyes suspension is made, draws 100ml disperse dyes suspension, dye bath pH is adjusted to 5 with acetic acid,
Then 60 DEG C are warmed up to, while being respectively put into 2g polyster fibres carries out high-temperature pressure dyeing, 130 DEG C were warmed up in 35 minutes,
Insulation 45 minutes, is cooled to 80 DEG C of samplings.According to EN14362:2012 (gas chromatograph-mass spectrometer (GC-MS) GC-MS and efficient liquid phases
Chromatograph HPLC), with reference to ISO17070:GB/T24167-2009 is (molten for 2015 (gas chromatograph-mass spectrometer (GC-MS) GC-MS), reference
Agent is extracted, gas chromatograph-mass spectrometer (GC-MS) GC-MS) method, to Textile AZO after dye, the analysis test of CPs, COCs, survey
Test result is shown in Table 8：
Table 8
| Title | AZO | CPs | COCs |
| Embodiment 3 | ND | ND | ND |
| Embodiment 4 | ND | ND | ND |
| Embodiment 5 | ND | ND | ND |
| Embodiment 6 | ND | ND | ND |
| Embodiment 7 | ND | ND | ND |
| Embodiment 8 | ND | ND | ND |
| Embodiment 9 | ND | ND | ND |
| Embodiment 10 | ND | ND | ND |
As can be seen that every environmental protection index of embodiment 3-10 is preferable from table 7 and 8, and it is used for textile as dyestuff
After dyeing, AZO, CPs, COCs are not detected after dye on fabric.
In summary, every environmental protection index of disperse dye composition of the invention reaches Oeko-Tex Standard
100 (2016) in dyestuff on fabric to the limitation of AZO, CPs, COCs, and as dyestuff be used for textile dyeing after, knitted after dye
AZO, CPs, COCs are not detected on thing, environment is may better secure, ensures that consumer's is healthy and safe.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
Plant simple variant and belong to protection scope of the present invention.
Claims (10)
1. a kind of disperse dye composition, it is characterised in that including one or more compound group in formula (1) compound into group
Divide A, disabling aromatic amine compound, chlorophenic acid, chlorophenesic acid, trichlorophenol, 2,4,6,-T, tetrachlorophenol, pentachlorophenol, chlorobenzene and chloromethane
Benzene, optional auxiliary material and other inevitable impurity,
In formula (1),
R1It is hydrogen or C1-C4Alkyl amide；
R2、R3It is each independently hydrogen, C1-C4Alkyl or substituted C1-C4Alkyl, the substituted C1-C4The substitution base choosing of alkyl
From-CN ,-OCOR ,-OCOC6H5、-COOR、-C6H5Or C1-C4Alkoxy, each R is each independently C1-C4Alkyl；
Wherein, the aromatic amine compound is selected from 4- aminobphenyls, benzidine, 4- chloro-o-toluidines, 2- naphthylamines, adjacent amino idol
N-formyl sarcolysine benzene, 2- amino -4- nitrotoleunes, parachloroanilinum, 2,4- diamino anisoles, 4,4 '-MDA, 3,3 ' -
Dichloro-benzidine, 3,3 '-dimethoxy benzidine, 3,3 '-dimethylbenzidine, 3,3 '-dimethyl -4,4 '-diaminourea hexichol
Methane, 2- methoxyl group -5- methylanilines, 4,4 '-diaminourea -3,3 '-dichloro diphenyl methane, 4,4 '-benzidine ether, 4,
4 '-diaminodiphenyl sulfide, ortho-aminotoluene, 2,4 di amino toluene, 2,4,5- trimethylanilines, o-aminoanisole, to ammonia
One or more in base azobenzene, 2,4- dimethylanilines, 2,6- dimethylanilines；
The chlorophenic acid be selected from 2- chlorophenols, 3- chlorophenols, one or more of 4- chlorophenols；The chlorophenesic acid is choosing
From 2,6- chlorophenesic acids, 2,4 dichloro phenol, 2,5- chlorophenesic acids, 3,5- chlorophenesic acids, 2,3- chlorophenesic acids, 3,4- dichloro-benzenes
One or more in phenol；The trichlorophenol, 2,4,6,-T is selected from 2,4,6- trichlorophenol, 2,4,6,-Ts, 2,3,6- trichlorophenol, 2,4,6,-Ts, 2,3,5- trichloro-benzenes
One or more in phenol, 2,4,5- trichlorophenol, 2,4,6,-Ts, 2,3,4- trichlorophenol, 2,4,6,-Ts, 3,4,5- trichlorophenol, 2,4,6,-Ts；The tetrachlorophenol is
Selected from one or more in 2,3,4,6- tetrachlorophenols, 2,3,5,6- tetrachlorophenols, 2,3,4,5- tetrachlorophenols；
The chlorobenzene and chlorotoluene be selected from monochloro-benzene, dichloro-benzenes, trichloro-benzenes, tetrachlorobenzene, pentachlorobenzene, hexachloro-benzene, monochlorotoluene,
One or more in dichlorotoleune, benzotrichloride, toluene tetrachloride, toluene pentachloride；
Also, the total content of the disabling aromatic amine compound is 0-10ppm, the chlorophenic acid, chlorophenesic acid, trichloro-benzenes
Each total content is 0-0.5ppm for phenol, tetrachlorophenol, pentachlorophenol, and the total content of chlorobenzene and chlorotoluene is 0-1ppm.
2. disperse dye composition according to claim 1, it is characterised in that the component A is selected from formula (1-1)~(1-
6) one or more in compound,
3. disperse dye composition according to claim 1 and 2, it is characterised in that the auxiliary material includes auxiliary agent and water；
Preferably, the auxiliary agent and the weight ratio of component A are 0.25~6.5:1；
Preferably, described auxiliary agent includes one or more following：Dispersant, dyeing auxiliaries, surfactant, sterilization
Agent；
Preferably, the dispersant is selected from naphthalene sulfonic acid-formaldehyde condensation product, condensation compound of methyl naphthalene sulfonic acid and formaldehyde, benzyl naphthalene sulfonic acids first
One or more in aldehyde condensate, lignosulfonates；
Preferably, the dyeing auxiliaries is glauber salt；
Preferably, the solid content of the slurry is 18~50%；
Preferably, the disperse dye composition being dried to obtain is powdery or graininess, and solid content is 87~96%.
4. the preparation method of the disperse dye composition any one of a kind of claim 1-3, it is characterised in that including with
Lower step：By 2,6- Dichloro-4-nitroaniline diazotising, add water and/or ice dilute below 5 DEG C, plus diatomite, activated carbon or
Bentonite is stirred, filtering, then carries out coupling reaction with formula Y compounds, obtains product I；The mixing of product I or product I and auxiliary material
Thing is used as disperse dye composition；
Wherein R1、R2、R3As defined in claim 1-3.
5. preparation method according to claim 4, it is characterised in that comprise the following steps：
(1) to sulfuric acid is added in diazonium kettle, nitrosyl sulfuric acid is added, control temperature is no more than 40 DEG C, cools to 20~30 DEG C, plus
Enter 2,6- Dichloro-4-nitroanilines, finish, at 20-30 DEG C, be incubated 4-8 hours, obtain diazo liquid, added in diazonium dilution kettle
Water, ice cools to less than 5 DEG C, is pressed into diazo liquid, and control dilution temperature is no more than 5 DEG C, adds diatomite, activated carbon or swelling
Soil, stirs 30~60 minutes, and filtering, filtrate squeezes into coupling kettle；
(2) to ice, urea (or sulfamic acid) and emulsifying agent is added in coupling kettle, stir 15-60 minutes, add defoamer, control
Temperature processed is added dropwise formula Y compounds, time for adding 2~5 hours, 10~15 DEG C of controlling reaction temperature, insulation reaction below 10 DEG C
2-5 hours, slowly it is warmed up to 50~85 DEG C and turns crystalline substance, filtering, washing obtains product I；The mixture of product I or product I and auxiliary material
As disperse dye composition；
Preferably, the emulsifying agent is selected from one or more in AEO.
6. the preparation method according to claim 4 or 5, it is characterised in that by one or more in products therefrom I and appoint
The auxiliary material mixing of choosing, carries out particlized treatment, is made slurry or is dried, and disperse dye composition is obtained；
Or various in products therefrom I are carried out into particlized treatment respectively, then mixed, it is made slurry or is dried,
Disperse dye composition is obtained.
7. the preparation method according to any one of claim 4-6, it is characterised in that the particlized treatment is using being sanded
Machine or grinder are carried out；
Preferably, it is described dry using spray drying.
8. the disperse dye composition any one of claim 1-3 is used for the dyeing of fabric or the purposes of stamp.
9. purposes according to claim 8, it is characterised in that the fabric is terylene or polyester blended fabric.
10. a kind of fabric, it is characterised in that the fabric is using the disperse dye composition described in claim any one of 1-3
Dyeed or stamp is prepared；Preferably, the fabric is terylene or polyester blended fabric.
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