CN110092870A - Dyestuff binders composition - Google Patents
Dyestuff binders composition Download PDFInfo
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- CN110092870A CN110092870A CN201910275638.9A CN201910275638A CN110092870A CN 110092870 A CN110092870 A CN 110092870A CN 201910275638 A CN201910275638 A CN 201910275638A CN 110092870 A CN110092870 A CN 110092870A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5242—Polymers of unsaturated N-containing compounds
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Coloring (AREA)
Abstract
The present invention provides a kind of dyestuff binders composition, belongs to textile dyeing and finishing technical field, contains the copolymer for including the repetitive unit as shown in the following general formula (1), (2) and (3) in dyestuff binders composition:
Description
Technical field
The invention belongs to textile dyeing and finishing technical fields, and in particular to dyestuff binders composition.
Background technique
Reactive dye are since the bright gorgeous, kind of its color and chromatography are complete, low in cost, easy to use, thus in cotton fabric
Dyeing in be widely used.Though reactive dye can form covalent bond with fiber, the stability of this bonding is simultaneously
It is not bery high, thus will lead to certain reactive dye not acid and alkali-resistance, not antioxidant, intolerant to heat treatment, to generate discoloration, take off
Phenomena such as color, staining.In addition, every dyefastness of reactive dye, for example, it is chlorine fastness, fastness to washing, fastness to perspiration, resistance to
Fastness is shone, is increasingly difficult to meet current printing and dyeing requirement.Therefore, become active dye printing using color fixing agent and/or adhesive
When necessary choice.
Active dye fixing agent and/or adhesive currently on the market is many kinds of, fastness to soaping color fixing agent such as Hangzhou
Mei Fu carrys out the CIBAFIX ECO of the MF-2036 of company, Ciba, Switzerland；The CF-2 of such as big auspicious chemistry of chlorine fastness color fixing agent
Deng.Active dye fixing agent and/or adhesive are also always that industry research hot spot is disclosed such as Japan Patent JP6-184246
It is obvious to promote effect to fabric fastness to soaping for a kind of Polycationic color fixing agent；Chinese patent CN1811052A, discloses one
Kind amphoteric water soluble color-fixing agent, effectively promotes fabric fastness to soaping and fastness to wet rubbing；For another example Chinese patent
CN105504227A discloses a kind of novel environment friendly chlorine-resistant color fixing agent, make fabric color fastness to chlorine be improved significantly.Through above-mentioned
Fabric after color fixing agent and/or adhesive treatment can effectively promote the fastness to soaping, fastness to rubbing, chlorine-resistant of reactive dye
The multinomial color fastness such as fastness, but still fade phenomenon in washing process, washing foot water color is deep, and each dyeing and finishing factory is directed to this
Kind of situation also proposes requirements one after another, and the good color fixing agent of water soak resistance energy is needed to solve this problem, to existing color fixing agent into
The more perfect supplement of row.Therefore, the resistance to bubble fastness color fixing agent for developing a kind of excellent performance has very important reality meaning
Justice.In addition, reaction is violent when existing part color fixing agent and/or adhesive polymerize, and the generation with the easy gelatin phenomenon of easy implode,
The molecular weight ranges of the color fixing agent and/or binder copolymer and/or polymer that cause reaction to generate are wider, molecular weight distribution
Index is larger, and copolymer and/or polymer property stability are poor, it is difficult to apply.
Summary of the invention
Copolymer the purpose of the present invention is to provide dyestuff binders composition, in dyestuff binders composition of the present invention
Containing more highly polar active bond, rheological characteristic is good, for being greatly improved adhesive when dyestuff binders to dye molecule
Cladding dynamics, the wear resistance of fabric and/or clothing is significantly improved with resistance to bubble fastness after dyeing, meanwhile, it is fastness to soaping, resistance to
Perspiration fastness and fastness to rubbing are good, and fabric discoloration is small, soft.
The technical solution that the present invention is taken to achieve the above object are as follows:
[1] present invention a kind of copolymer that can be used for dyestuff binders is provided comprising as the following general formula (1), (2) and
(3) repetitive unit indicated:
In formula (1), R1、R2、R3、R4And R5It is each independently selected from H, halogen atom and C1-5Alkyl,
Indicate counter ion counterionsl gegenions；
In formula (2), R6、R7、R8And R9It is each independently selected from H, halogen atom and C1-5Alkyl, and
In formula (3), R10And R12It is each independently selected from H, halogen atom and C1-5Alkyl,
R11Selected from-COO- and-CH2O-。
With molar amount, in the copolymer, general formula (1), (2) and (3) indicate repetitive unit molar ratio be 10~
90:10~90:1~10.
With Weight-average molecular meter, the weight average molecular weight of the copolymer is 5000~30000g/mol.
The copolymer copolymer chain of the invention has more branch and preferable polarity, and rheological characteristic is good, is used
Adhesive is greatly improved when dyestuff binders to the cladding dynamics of dye molecule, the silanes chain being rich in copolymer chain can
Fabric after making fixation and/or clothing obtain soft sense of touch and feel, after dyeing the wear resistance of fabric and/or clothing with it is resistance to
Bubble fastness is excellent, meanwhile, fastness to soaping, fastness to perspiration and fastness to rubbing are good, and fabric discoloration is small, soft.
[2] the present invention also provides the preparation method for the copolymer that can be used for dyestuff binders described in [1], it is included in freedom
It polymerize the monomer that following general formula (1 '), (2 ') and (3 ') indicates in the presence of base initiator:
In formula (1 '), R1、R2、R3、R4And R5It is each independently selected from H, halogen atom and C1-5Alkyl,
X-Indicate counter ion counterionsl gegenions；
In formula (2 '), R6、R7、R8And R9It is each independently selected from H, halogen atom and C1-5Alkyl, and
In formula (3 '), R10And R12It is each independently selected from H, halogen atom and C1-5Alkyl,
R11Selected from-COO- and-CH2O-。
Copolymer of the invention is by monomer, one or more general formulas (2 ') table for indicating comprising one or more general formulas (1 ')
The monomer mixture for the monomer that the monomer shown is indicated with one or more general formulas (3 ') is copolymerized in the presence of radical initiators
It is made.
Upon polymerization, the polymerized unit that the monomer that the general formula (1 ') indicates is indicated through cyclopolymerization at general formula (1):
In formula (1 ') and (1), R1、R2、R3、R4And R5It is each independently selected from H, halogen atom and C1-5Alkyl is preferably selected from
H or-CH3,
In formula (1 ') and (1), X- indicates that counter ion counterionsl gegenions are preferably selected from Cl- or (1/ such as halogen ion or oxygen-containing acid group
2SO4)-；
The polymerized unit that the monomer polymerization that the general formula (2 ') indicates is indicated at general formula (2):
In formula (2 ') and (2), R6、R7、R8And R9It is each independently selected from H, halogen atom and C1-5Alkyl is preferably selected from H
Or-CH3；
The polymerized unit that the monomer polymerization that the general formula (3 ') indicates is indicated at general formula (3):
In formula (3) and (3 '), R10And R12It is each independently selected from H, halogen atom and C1-5Alkyl, be preferably selected from H or-
CH3, R11Selected from-COO- and-CH2O-。
The monomer of the general formula (1 ') includes but is not limited to following specific monomers:
The monomer of the general formula (2 ') includes but is not limited to following specific monomers:
The monomer of the general formula (3 ') includes but is not limited to following specific monomers:
Specifically, the preparation method of [1] described copolymer that can be used for dyestuff binders includes:
A) lotion is made in general formula (1 ') and (2 ') described monomer in the presence of emulsifier for 35~65 DEG C；
B) 60~80 DEG C of addition general formulas (3 ') monomer and initiator carry out emulsion polymerization in inert gas environment and are
?.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, the polymerization reaction time is 1~30h, preferably 2~10h, most preferably 5~8h.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, the emulsifier is optional dodecyl benzyl dimethyl ammonium chloride, octadecyltrimethylammonium chloride, cetyl three
One kind of ammonio methacrylate, aliphatic amine polyoxyethylene ether or combinations thereof object.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, the initiator is radical initiator, preferably includes thermal free radical initiator, optical free radical initiator or redox and draws
Agent is sent out, most preferably by redox initiator.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, the initiator can be O- acyl group oxime compound, alkyl phenones compound, united imidazole, triaizine compounds and acyl group
Phosphine oxide compound.Concretely but it is not limited to N- benzoyl Oxy-1-(4- phenyl sulfonyl phenyl) octane-1- ketone-2-
Imines, N- benzoyl Oxy-1-(4- phenyl sulfonyl phenyl)-3- cyclopenta propane-1- ketone-2- imines, N- acetoxyl group-
1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6-
{ 2- methyl -4- (3,3- dimethyl -2,4- dioxa cyclopentenyl methyl oxygroup) benzoyl } -9H- carbazole -3- base] ethane -
1- imines, N- acetoxyl group -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -3- cyclopenta propane -1-
Imines, 2- methyl -2- morpholinyl -1- (4- methylsulfonyl phenyl) propane -1- ketone, 2- dimethylamino -1- (4- morpholinyl benzene
Base) -2- benzyl butane -1- ketone, 2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] fourth
Alkane -1- ketone, 2,2 '-two (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-two (2,3- dichlorophenyls) -4,4 ',
5,5 '-tetraphenyl bisglyoxalines, 2,2 '-two (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-two (2- chlorphenyls) -
4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-two (2- chlorphenyl) -4,4 ', 5,5 '-four (dialkoxy phenyl) connection
Imidazoles, 2,4- bis- (trichloromethyl) -6- (4- methoxyphenyl) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxy
Base naphthalene) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- piperonyl -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6-
(4- methoxyl-styrene) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- [2- (5- methylfuran -2- base) vinyl] -
1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- [2- (furans -2- base) vinyl] -1,3,5- triazine or 2,4,6- trimethyl
Benzoyl diphenyl phosphine oxide.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, the inert gas is nitrogen.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, essentially all of monomer is all aggregated in copolymer of the invention, in the present copolymer of formation, the general formula
(1), the molar ratio for the repetitive unit that (2) and (3) indicate is 10~90:10~90:1~10, preferably 30~60:15~50:2
~5.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, essentially all of monomer is all aggregated in copolymer of the invention, in the present copolymer of formation, with Weight-average molecular
Meter, the weight average molecular weight of the copolymer are 5000~30000g/mol, preferably 15000~20000g/mol.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, essentially all of monomer is all aggregated in copolymer of the invention, is formed by present copolymer molecular weight distribution (weight
Average molecular weight (Mw)/number-average molecular weight (Mn)) it is preferably not greater than 3, more preferably not more than 2.5.
The preparation method of copolymer of the present invention for dyestuff binders is simple to operation, and polymerization reaction is mild, keeps away
The generation for having exempted from the easy gelatin phenomenon of easy implode when the polymerization of existing fixation adhesive, reacts the molecular weight ranges of the copolymer of generation
Relatively narrow, molecular weight distributing index D is not more than 3, therefore copolymer property stable homogeneous, can be used for dyestuff binders, consolidate
The fields such as toner, the more branch of copolymer and preferable polarity assign its more excellent rheological characteristic, are greatly improved bonding
To the cladding dynamics of dye molecule, the silanes chain being rich in copolymer chain can be such that the fabric after fixation and/or clothing obtains for agent
Soft sense of touch and feel, the wear resistance of fabric and/or clothing and resistance to bubble fastness are excellent after dyeing, meanwhile, resistance to jail of soaping
Degree, fastness to perspiration and fastness to rubbing are good, and fabric discoloration is small, soft.
[3] present invention provides a kind of dyestuff binders composition comprising item [1] and [2] described copolymer, the combination
Object includes:
1) such as item [1] and [2] described copolymer (A)；
2) resin (B)；And
3) solvent (C).
In summary of the invention of the present invention and preferred embodiment, the copolymer (A) in the dyestuff binders composition be as
It can be used for the copolymer of dyestuff binders described in above-mentioned item [1] and [2]；In parts by weight, the additive amount of the copolymer (A)
It is preferred that 5~90 weight % of the dyestuff binders composition quality, more preferably 10~50 weight % are accounted for, most preferably 25~
40 weight %.
In summary of the invention of the present invention and preferred embodiment, the resin (B) in the dyestuff binders composition be can be selected from
Polypropylene, haloflex, high density polyethylene (HDPE), poly- terephthalyl alcohol, polycarbonate, polymethyl acrylate, 3,4- epoxy group
Cyclohexyl methyl (methyl) acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/(methyl) propylene
Sour benzyl ester/(methyl) acrylic copolymer, 3- methyl -3- (methyl) acryloyl group oxygroup methy oxetane/(methyl)
Acrylic/styrene copolymer, (methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic acid
Copolymer and (methyl) benzyl acrylate/tricyclodecyl (methyl) acrylate/(methyl) acrylic copolymer one kind or
At least two hybrid resin；The weight average molecular weight of the resin (B) is preferably 3000~15000g/mol, and more preferably 5000
~10000g/mol, most preferably 6000~8000g/mol；The resin (B) molecular weight distribution (weight average molecular weight (Mw)/
Number-average molecular weight (Mn)) it is preferably 1.1~5, more preferably 1.2~3；In parts by weight, the additive amount of the resin (B) is preferred
Account for 0.1~50 weight % of the dyestuff binders composition quality, more preferably 5~25 weight %, most preferably 10~20
Weight %.
In summary of the invention of the present invention and preferred embodiment, the solvent (C) in the dyestuff binders composition is at least wrapped
Include at least one of following all kinds of solvents:
C-1 ether-ether solvent: ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxyacetic acid second
Ester, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 2- methoxy methyl propionate, 2- methoxypropionate, 2- methoxy
Base propyl propionate, 2- ethoxyl ethyl propionate, 2- methoxyl group -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2 Methylpropionic acid ethyl ester,
3- methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monopropyl ether
Acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether
Acetic acid esters；
C-2 ketone solvent: 4- hydroxy-4-methyl-2-pentanone, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- heptanone, 4- first
Base -2 pentanone, cyclopentanone, cyclohexanone, isophorone；
C-3 alcoholic solvent: methanol, ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine, benzene first
Alcohol, benzyl carbinol；
C-4 aromatic hydrocarbon solvents: benzene,toluene,xylene, mesitylene.
In summary of the invention of the present invention and preferred embodiment, solvent (C) in the dyestuff binders composition can be
A kind of mixed solvent of composition is respectively selected in above-mentioned tetra- class of C-1, C-2, C-3 and C-4, it can also be in above-mentioned C-1, C-2, C-3 and C-4 tetra-
The mixed solvent of at least one composition is respectively selected in class, such as can be but be not limited to following combinations: 2- methoxy propyl propyl propionate+
Acetone+hexanol+toluene, ethyl methoxyacetate+cyclopentanone+methanol+benzene, 3- ethoxypropanoate+2- butanone+cyclopentanone+
Dimethylbenzene, methoxyacetic acid butyl ester+4-methyl-2 pentanone+ethylene glycol+dimethylbenzene, methoxyacetic acid butyl ester+ethoxyacetic acid first
Ester+acetone+butanol+toluene, diethylene glycol monoethyl ether acetic acid esters+acetone+2- butanone+propyl alcohol+butanol+toluene, 2- ethoxy-propionic acid
Ethyl ester+2- methoxyl group -2 Methylpropionic acid methyl esters+acetone+2- butanone+propyl alcohol+butanol+dimethylbenzene, 3- methoxybutyl acetic acid esters+
Acetone+2- butanone+2-HEPTANONE hexanol+cyclohexanol+toluene+dimethylbenzene, 3- ethoxyl ethyl propionate+acetone+3- heptanone+propyl alcohol+
Butanol+toluene+dimethylbenzene.
In summary of the invention of the present invention and preferred embodiment, in parts by weight, the additive amount of the solvent (C) preferably accounts for institute
State 20~50 parts by weight % of dyestuff binders composition quality, more preferably 25~40%, most preferably 30~35%.
[4] application the present invention also provides item [3] the dyestuff binders composition in dye printing and dyeing, wherein
The dyestuff binders composition such as item [3] is described；
The dyestuff is selected from anthraquinone dye or tetraazatetradecane porphyrin dyestuff.
In the application, the dyestuff binders composition comprising item [1] and item [2] described copolymer is to including anthraquinone dye
Or the dyestuff including tetraazatetradecane porphyrin dyestuff has more affine cladding ability, contains ether in copolymer straight chain and/or branch
The highly polar active bond such as key, silicon oxygen bond, carbon-carbon bond, phenyl ring, halogen atom, nitrogen-atoms, sulphur atom, ester bond, ketonic bond, can be to dyestuff
Amino, imino group, sulfonic group, ketonic bond, phenyl ring, heterocycle, metal complex group for being rich in molecule etc. have stronger absorption
Ability, the form that can be formed a film stick dyestuff on the fabric, and adhesion with higher and reproducibility can significantly improve dyestuff
Wear resistance, resistance to bubble fastness, acid and alkali-resistance, chemically-resistant medicament after printing and dyeing etc. form a film Clear & Transparent, non-discolouring, do not damage, altogether
The silanes chain being rich in polymers chain can make the fabric after fixation and/or clothing obtain soft sense of touch, fabric and/or clothing bullet
The good, good hand touch of property.
In summary of the invention of the present invention and preferred embodiment, as anthraquinone dye more preferably but be not limited to formula (4-1)~
(4-8) compound represented:
In summary of the invention of the present invention and preferred embodiment, as tetraazatetradecane porphyrin dyestuff more preferably but be not limited to formula
(5-1)~(5-10) compound represented:
In summary of the invention of the present invention and preferred embodiment, the dyestuff be also selected from oil-soluble dyes, acid dyes,
Basic dye, direct dyes, mordant dye, the amine salt of acid dyes or acid dyes the dyestuffs such as sulfamide derivative, can be with
Enumerate by Color Index (The Society of Dyers and Colourists publication) be classified as dyestuff compound,
The well known dyestuff recorded in Dyeingnote (Se Ran society).According to chemical structure, can enumerate azo dyes, cyanine dye,
Triphenhlmethane dye, Xanthene dyes, phthalocyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dye
Material, square hydrochlorate dyestuff, acridine dye, styryl dye, coumarine dye, quinoline dye nitro dye etc..More preferably have
Solvent soluble dye.
The dyestuff is including but not limited to as described below:
C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162:
C.I. solvent red 45,49,125,130,218；
C.I. solvent orange 2,7,11,15,26,56；
C.I. solvent blue 4,5,37,67,70,90；
C.I. the green C.I. solvent dye such as 1,4,5,7,34,35 of solvent；
C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,
99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、
161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、
212,214,220,221,228,230,232,235,238,240,242,243,251:
C.I. azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,
73、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、
183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、
274、277、280、281、289、308、312、315、316、339、341、345、346、349、382、383、388、394、401、
412,417,418,422,426:
C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,
169,173:
C.I. acid violet 6B, 7,9,17,19,30,102；
C.I. Blue VRS, 7,9,15,18,22,29,42,59,60,62,70,72,74,82,83,86,87,90,92,
93、100、102、103、104、113、117、120、126、130、131、142、147、151、154、158、161、166、167、
168、170、171、184、187、192、199、210、229、234、236、242、243、256、259、267、285、296、315、
335；
C.I. the C.I. acid dyes such as acid green 1,3,5,9,16,50,58,63,65,80,104,105,106,109；
C.I. directly Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,
102,108,109,129,136,138,141；
C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,
179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250；
C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107；
C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104；
C.I. directly indigo plant 1,2,6,8,15,22,25,41,57,71,76,78,80,81,84,85,86,90,93,94,95,
97、98、99、100、101、106、107、108、109、113、114、115、117、119、120、137、149、150、153、155、
156、158、159、160、161、162、163、164、165、166、167、168、170、171、172、173、188、189、190、
192、193、194、195、196、198、199、200、201、202、203、207、209、210、212、213、214、222、225、
226、228、229、236、237、238、242、243、244、245、246、247、248、249、250、251、252、256、257、
259,260,268,274,275,293；
C.I. the C.I. such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82 directly contaminate
Material；
C.I. disperse yellow 54,76 equal C.I. disperse dyes；
C.I. alkali red 1:1,10；
C.I. alkali blue 1,3,5,7,9,19,24,25,26,28,29,40,41,54,58,59,64,65,66,67,68；
C.I. the C.I. basic dyes such as Viride Nitens 1；
C.I. active yellow 2,76,116；
C.I. reactive orange 16；
C.I. the C.I. reactive dye such as active red 36；
C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65:
C.I. mordant rouge 1,2,4,9,12,14,17,18,19,22,23,24,25,26,27,30,32,33,36,37,38,
39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95:
C.I. mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,
48:
C.I. mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58:
C.I. mordant dyeing indigo plant 1,2,3,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44,
49,53,61,74,77,83,84:
C.I. the C.I. mordant dye such as viridon 1,3,4,5,10,15,26,29,33,34,35,41,43,53；
C.I. C.I. reducing dyes such as vat green 1 etc.；
More preferably blue dyes, cudbear orchil.
Above-mentioned dyestuff both can be used alone, two or more also can be used together.
In summary of the invention of the present invention and preferred embodiment, the dyestuff can also be pigment, and the pigment can be without spy
Not Xian Ding ground use well known pigment, can enumerate in Color Index (The Society of Dyers and
Colourists is published) in be classified as the pigment of pigment.
The pigment is including but not limited to as described below:
C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,
125, the yellow uitramarines such as 128,137,138,139,147,148,150,153,154,166,173,194,214；
C.I. the orange pigments such as pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73；
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,
216, the red pigments such as 224,242,254,255,264,265；
C.I. the blue pigments such as pigment blue 15,15:3,15:4,15:6,60；
C.I. the violet pigments such as pigment violet 1,19,23,27,29,32,36,38；
C.I. the viridine greens such as pigment Green 7,36,58；
C.I. the browns such as pigment brown 23,25；
C.I. black pigments such as pigment black 1,7 etc..
The pigment is preferably phthalocyanine color or dioxazines pigment, is more preferably selected from C.I. pigment blue 15: 6 and pigment violet
At least one of 23.
Above-mentioned pigment both can be used alone, two or more also can be used together.
The invention has the benefit that
1) copolymer chain of the copolymer of the invention has more branch and preferable polarity, and rheological characteristic is good, will
Its cladding dynamics for being used to be greatly improved adhesive when dyestuff binders to dye molecule, the silanes being rich in copolymer chain
Chain can make the fabric after fixation and/or clothing obtain soft sense of touch and feel, the wear resistance of fabric and/or clothing after dyeing
It is excellent with resistance to bubble fastness, meanwhile, fastness to soaping, fastness to perspiration and fastness to rubbing are good, and fabric discoloration is small, and feel is soft
It is soft；
2) preparation method of the copolymer of the present invention for dyestuff binders is simple to operation, and polymerization reaction is mild,
The generation for avoiding the easy gelatin phenomenon of easy implode when the polymerization of existing fixation adhesive, reacts the molecular weight model of the copolymer of generation
Enclose relatively narrow, molecular weight distributing index D is not more than 3, therefore copolymer property stable homogeneous, can be used for dyestuff binders,
The fields such as color fixing agent；
3) the dyestuff binders composition of the copolymer is to the dye including anthraquinone dye or tetraazatetradecane porphyrin dyestuff
Material has more affine cladding ability, contains more highly polar active bond in copolymer straight chain and/or branch, can be to dyestuff
Amino, imino group, sulfonic group, ketonic bond, phenyl ring, heterocycle, metal complex group for being rich in molecule etc. have stronger absorption
Ability, the form that can be formed a film stick dyestuff on the fabric, and adhesion with higher and reproducibility can significantly improve dyestuff
Wear resistance, resistance to bubble fastness, acid and alkali-resistance, chemically-resistant medicament after printing and dyeing etc. form a film Clear & Transparent, non-discolouring, do not damage.
Present invention employs above-mentioned technical proposals to provide dyestuff binders composition, compensates for the deficiencies in the prior art, if
Meter is rationally, easy to operate.
Specific embodiment
Although the detailed description of many different embodiments is set forth below, it is to be understood that, the scope of law of the invention by
The text for being appended hereto claim listed by this patent is defined.Detailed description should be interpreted it is exemplary only and simultaneously
Non-depicted each possible embodiment, because each possible embodiment of description is if possible also unpractical.It can
A variety of alternate embodiments are realized using current techniques or the technology developed after this patent submitting day, they will fall
Enter in the scope of the claims.
Unless term uses sentence " as used herein, term ' _ _ _ _ ' is limited to mean herein ... " in this patent
Or similar sentence is clearly defined, the meaning for being otherwise not intended to explicitly or implicitly limit the term is usual or general beyond its
Logical meaning, and this term should not be construed as limited to based on any part in the patent (in addition to the language of claim
Other than speech) in the range of any statement made.Any term just enumerated in this patent the attached claims with
The single consistent mode of meaning is subject to for reference in this patent, and doing so is only for clarity so as not to keeping reader mixed
Confuse, and is not intended to imply that ground or this claim terms is otherwise restricted to this single meaning.
Present invention is further described in detail with reference to embodiments:
Embodiment 1:
The present embodiment provides a kind of copolymers that can be used for dyestuff binders comprising such as the following general formula (1), (2) and (3)
The repetitive unit of expression:
In formula (1), R1、R2、R3、R4And R5It is H,Indicate counter ion counterionsl gegenions Cl-；
In formula (2), R6、R7、R8And R9It is H, and
In formula (3), R10And R12It is H, R11It is-CH2O-。
With molar amount, in the copolymer, the molar ratio for the repetitive unit that general formula (1), (2) and (3) indicates is 35:
45:20。
With Weight-average molecular meter, the weight average molecular weight of the copolymer is 15000~20000g/mol.
The copolymer copolymer chain of the invention has more branch and preferable polarity, and rheological characteristic is good, is used
Adhesive is greatly improved when dyestuff binders to the cladding dynamics of dye molecule, the silanes chain being rich in copolymer chain can
Fabric after making fixation and/or clothing obtain soft sense of touch and feel, after dyeing the wear resistance of fabric and/or clothing with it is resistance to
Bubble fastness is excellent, meanwhile, fastness to soaping, fastness to perspiration and fastness to rubbing are good, and fabric discoloration is small, soft.
The present embodiment also provides the preparation method of the above-mentioned copolymer that can be used for dyestuff binders, it is included in free radical and draws
It polymerize the monomer that following general formula (1 '), (2 ') and (3 ') indicates in the presence of hair agent:
In formula (1 '), R1、R2、R3、R4And R5It is H, X-Indicate Cl-；
In formula (2 '), R6、R7、R8And R9It is all H；
In formula (3 '), R10And R1It is all H, R11It is-CH2O-。
Copolymer of the invention is by indicating that monomer, general formula (2 ') indicate that monomer and general formula (3 ') indicate single comprising general formula (1 ')
The monomer mixture of body is copolymerized in the presence of radical initiators to be made.Preparation method specifically includes:
A) lotion is made in general formula (1 ') and (2 ') described monomer in the presence of emulsifier for 45 DEG C；
B) 65 DEG C of addition general formulas (3 ') monomer and initiator carry out emulsion polymerization in inert gas environment to obtain the final product.
In the preparation method of the copolymer, the polymerization reaction time is 10h, and the initiator is N- benzoyl oxygen
Base -1- (4- phenyl sulfonyl phenyl) octane -1- ketone -2- imines, the molecular weight distribution (weight average molecular weight for obtaining copolymer
(Mw)/number-average molecular weight (Mn)) it is 2.2.
The present embodiment also provides the dyestuff binders composition comprising above-mentioned copolymer, and the items of the composition are with weight
Part meter occupies the amount of the composition and includes:
1) the 15 above-mentioned copolymer of weight %；
2) 35 weight % resin；And
3) 50 weight % solvent.
Wherein, the resin be polycarbonate, the solvent be weight ratio be 1:1:1:1 2- methoxy propyl propyl propionate+
Acetone+hexanol+toluene mixed solvent.
Embodiment 2:
[1] the present embodiment provides a kind of copolymers that can be used for dyestuff binders comprising as the following general formula (1), (2) and
(3) repetitive unit indicated:
In formula (1), R1=R2=R3=-H, R4=-CH3, R5=-Cl,Indicate counter ion counterionsl gegenions Cl-；
In formula (2), R6=R7=R8=-CH3, R9=-CH2CH2CH3；
In formula (3), R10=-Cl, R12=-CH (CH2CH3)CH3, R11=-COO-.
With molar amount, in the copolymer, the molar ratio for the repetitive unit that general formula (1), (2) and (3) indicates is 60:
35:5。
With Weight-average molecular meter, the weight average molecular weight of the copolymer is 25000~30000g/mol.
The copolymer copolymer chain of the invention has more branch and preferable polarity, and rheological characteristic is good, is used
Adhesive is greatly improved when dyestuff binders to the cladding dynamics of dye molecule, the silanes chain being rich in copolymer chain can
Fabric after making fixation and/or clothing obtain soft sense of touch and feel, after dyeing the wear resistance of fabric and/or clothing with it is resistance to
Bubble fastness is excellent, meanwhile, fastness to soaping, fastness to perspiration and fastness to rubbing are good, and fabric discoloration is small, soft.
[2] the present invention also provides the preparation method for the copolymer that can be used for dyestuff binders described in [1], it is included in freedom
It polymerize the monomer indicated such as following formula (1 ' -2), (2 ' -2) and (3 ' -2) in the presence of base initiator.
Upon polymerization, the polymerized unit that the monomer that the formula (1 ' -2) indicates is indicated through cyclopolymerization at general formula (1-2)；Institute
State the polymerized unit that the monomer polymerization of formula (2 ' -2) expression is indicated at general formula (2-2)；The monomer that the general formula (3 ' -2) indicates is poly-
Synthesize the polymerized unit that general formula (3-2) is indicated.
Specifically, the preparation method of [1] described copolymer that can be used for dyestuff binders includes:
A) lotion is made in formula (1 ' -2) and (2 ' -2) described monomer in the presence of emulsifier for 35~65 DEG C；
B) 60~80 DEG C of addition general formulas (3 ' -2) monomer and initiator carry out emulsion polymerization in inert gas environment
To obtain the final product.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, the polymerization reaction time is 10h.
In summary of the invention of the present invention and preferred embodiment, the preparation method of the copolymer that can be used for dyestuff binders
In, the initiator is 2,4- bis- (trichloromethyl) -6- [2- (5- methylfuran -2- base) vinyl] -1,3,5-triazines.
In the preferred embodiment, essentially all in the preparation method of the copolymer that can be used for dyestuff binders
Monomer be all aggregated in copolymer of the invention, be formed by present copolymer molecular weight distribution (weight average molecular weight (Mw)/
Number-average molecular weight (Mn)) it is not more than 2.5.
The preparation method of copolymer of the present invention for dyestuff binders is simple to operation, and polymerization reaction is mild, keeps away
The generation for having exempted from the easy gelatin phenomenon of easy implode when the polymerization of existing fixation adhesive, reacts the molecular weight ranges of the copolymer of generation
Relatively narrow, molecular weight distributing index D is not more than 3, therefore copolymer property stable homogeneous, can be used for dyestuff binders, consolidate
The fields such as toner, the more branch of copolymer and preferable polarity assign its more excellent rheological characteristic, are greatly improved bonding
To the cladding dynamics of dye molecule, the silanes chain being rich in copolymer chain can be such that the fabric after fixation and/or clothing obtains for agent
Soft sense of touch and feel, the wear resistance of fabric and/or clothing and resistance to bubble fastness are excellent after dyeing, meanwhile, resistance to jail of soaping
Degree, fastness to perspiration and fastness to rubbing are good, and fabric discoloration is small, soft.
[3] present invention provides a kind of dyestuff binders composition comprising item [1] and [2] described copolymer, the combination
Object includes:
1) such as item [1] and [2] described copolymer (A)；
2) resin (B)；And
3) solvent (C).
In the preferred embodiment, the copolymer (A) in the dyestuff binders composition is such as above-mentioned item [1] and [2]
The copolymer that can be used for dyestuff binders；In parts by weight, the additive amount of the copolymer (A) preferably accounts for the dyestuff
40 weight % of adhesive composition quality.
In the preferred embodiment, the resin (B) in the dyestuff binders composition can be 3,4- expoxycyclohexyl
Methyl (methyl) acrylate/(methyl) acrylic copolymer and (methyl) glycidyl acrylate/(methyl) acrylic acid benzyl
The hybrid resin that base ester/(methyl) acrylic copolymer is mixed by weight 1:1；The weight average molecular weight of the resin (B)
Preferably 12000~15000g/mol；Molecular weight distribution (the weight average molecular weight (Mw)/number-average molecular weight of the resin (B)
It (Mn)) is 3；In parts by weight, the additive amount of the resin (B) preferably accounts for 40 weights of the dyestuff binders composition quality
Measure %.
In the preferred embodiment, the solvent (C) in the dyestuff binders composition is the diethylene glycol (DEG) of 1:1:1:1:1:1
Monoethyl ether acetate+acetone+2- butanone+propyl alcohol+butanol+toluene mixed solvent.
In the preferred embodiment, in parts by weight, the additive amount of the solvent (C) preferably accounts for the dyestuff binders group
Close 20 parts by weight % of amount of substance.
Embodiment 3:
Embodiment 3 is substantially the same manner as Example 2, the difference is that in embodiment 3, the dyestuff binders that can be used for
Shown in the copolymerization units of copolymer such as following formula (1-3), (2-3) and (3-3):
Embodiment 4:
Embodiment 4 is substantially the same manner as Example 2, the difference is that in embodiment 4, the dyestuff binders that can be used for
Shown in the copolymerization units of copolymer such as following formula (1-4), (2-4) and (3-4):
Embodiment 5:
Embodiment 5 is substantially the same manner as Example 2, the difference is that in embodiment 5, the dyestuff binders that can be used for
Shown in the copolymerization units of copolymer such as following formula (1-5), (2-5) and (3-5):
Embodiment 6:
Embodiment 6 is substantially the same manner as Example 2, the difference is that in embodiment 6, the dyestuff binders that can be used for
Shown in the copolymerization units of copolymer such as following formula (1-6), (2-6) and (3-6):
Embodiment 7:
Embodiment 7 is substantially the same manner as Example 2, the difference is that in embodiment 7, the dyestuff binders that can be used for
Shown in the copolymerization units of copolymer such as following formula (1-7), (2-7) and (3-7):
Embodiment 8:
Embodiment 8 is substantially the same manner as Example 2, the difference is that in embodiment 8, the dyestuff binders that can be used for
Shown in the copolymerization units of copolymer such as following formula (1-8), (2-8) and (3-8):
Embodiment 9:
Embodiment 9 is substantially the same manner as Example 2, the difference is that in embodiment 10, it is described to can be used for dyestuff binders
Copolymer copolymerization units such as following formula (1-9), (2-9) and (3-9) shown in:
Embodiment 10:
Embodiment 10 is substantially the same manner as Example 2, the difference is that in embodiment 10, it is described to can be used for dyestuff binders
Copolymer copolymerization units such as following formula (1-10), (2-10) and (3-10) shown in:
Comparative Example V 11:
Comparative Example V 11 is substantially the same manner as Example 2, the difference is that in Comparative Example V 11, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V11) and (3-V11) are shown:
The general formula (1-V11) and
The molar ratio for the repetitive unit that (3-V11) is indicated is 95:5.
Comparative Example V 12:
Comparative Example V 12 is substantially the same manner as Example 2, the difference is that in Comparative Example V 12, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V12) and (3-V12) are shown:
The general formula (1), (2) and
(3) molar ratio of the repetitive unit indicated is 35:45:20.
Comparative Example V 13:
Comparative Example V 13 is substantially the same manner as Example 2, the difference is that in Comparative Example V 13, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V13) and (3-V13) are shown:
The general formula (1-V13) and
The molar ratio for the repetitive unit that (3-V13) is indicated is 80:20.
Comparative Example V 14:
Comparative Example V 14 is substantially the same manner as Example 2, the difference is that in Comparative Example V 14, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V14) and (3-V14) are shown:
The general formula (1-V14) and
The molar ratio for the repetitive unit that (3-V14) is indicated is 35:65.
Comparative Example V 15:
Comparative Example V 15 is substantially the same manner as Example 2, the difference is that in Comparative Example V 15, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (2-V15) and (3-V15) are shown:
The general formula (2-V15) and (3-
V15) molar ratio of the repetitive unit indicated is 80:20.
Comparative Example V 16:
Comparative Example V 16 is substantially the same manner as Example 2, the difference is that in Comparative Example V 16, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (2-V16) and (3-V16) are shown:
The general formula (2-V16) and (3-V16) table
The molar ratio of the repetitive unit shown is 45:55.
Comparative Example V 17:
Comparative Example V 17 is substantially the same manner as Example 2, the difference is that in Comparative Example V 17, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V17) and (2-V17) are shown:
The general formula (1-V17) and (2-
V17) molar ratio of the repetitive unit indicated is 55:45.
Comparative Example V 18:
Comparative Example V 18 is substantially the same manner as Example 2, the difference is that in Comparative Example V 18, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V18) and (2-V18) are shown:
The general formula (1-V18) and (2-V18) table
The molar ratio of the repetitive unit shown is 35:65.
Comparative Example V 19:
Comparative Example V 19 is substantially the same manner as Example 2, the difference is that in Comparative Example V 19, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V19) and (2-V19) are shown:
The general formula (1-V19) and (2-V19) table
The molar ratio of the repetitive unit shown is 55:45.
Comparative Example V 20:
Comparative Example V 20 is substantially the same manner as Example 2, the difference is that in Comparative Example V 20, it is described to can be used for
The copolymerization units of the copolymer of dyestuff binders such as following formula (1-V20) and (2-V20) are shown:
The general formula (1-V20) and (2-V20) are indicated
Repetitive unit molar ratio be 35:65.
Test case:
Fabric: by the red complete cotton knitted fabric of reactive dyeing, dyeing dyestuff used is C.I. solvent red 49, dye
Colour saturation is 5%o.w.f.；
Dyestuff binders formula: the dyestuff binders dosage in 11~V20 of Examples 1 to 10 and Comparative Example V is
1.2%o.w.f., bath raio 1:20；
Color fixing process: dipping dyestuff binders (1.2%o.w.f., working liquid ph 5, bath raio 1:20,40 DEG C ×
30min) → dehydration → drying.
Properties of textile measures standard:
The resistance to bubble fastness of A: Tide 1 gram/L, bath raio 1:50 are heated to 90 DEG C, are put into cloth specimen after color fixing agent processing,
5min is shaken in dyeing oscillator, the working solution shade after taking out cloth specimen, according to " GB/T250-2008 textile color jail
Spend test evaluation discoloration gray scale " measurement；
B fastness to soaping: according to " GB/T 3921-2008 textile color stability tests fastness to soaping " measurement；
C colour fastness to perspiration: according to " GB/T 3922-2013 textile color stability tests colour fastness to perspiration " measurement；
D antifriction fastness: according to " GB/T 3920-2008 textile color stability tests colour fastness to rubbing " measurement；
E discoloration: according to " GB/T 250-2008 textile color stability test evaluation discoloration gray scale " measurement；
F feel: more people's digital palpations for examination of trauma are used, 5 one group of people scorings, taking average score is evaluation result, and 5 points best, and 1 point most
Difference.
Dyestuff binders and commercially available color fixing agent application effect pair in 11~V20 of Examples 1 to 10 and Comparative Example V
Than as shown in table 1.
1 application effect of table
As can be seen from Table 1, the dyestuff binders in the preferred embodiment of the present invention are in application, the resistance to bubble fastness of fabric is resistance to
Mill fastness (dry and wet) and other every fastness all show good promotion effect, and discoloration is small, good hand touch, obvious excellent
In commercially available color fixing agent.
The prior art of routine techniques dawn known to those skilled in the art in above-described embodiment, therefore herein no longer in detail
It repeats.
The above embodiments are only used to illustrate the present invention, and not limitation of the present invention, the ordinary skill people of this field
Member can also make a variety of changes and modification without departing from the spirit and scope of the present invention.Therefore, all equivalent
Technical solution also belong to scope of the invention, scope of patent protection of the invention should be defined by the claims.
Claims (10)
1. a kind of copolymer that can be used for dyestuff binders, it is characterised in that including as the following general formula (1), (2) and (3) indicates
Repetitive unit:
Wherein, in formula (1), R1、R2、R3、R4And R5It is each independently selected from H, halogen atom and C1-5Alkyl,Expression contend with from
Son；
In formula (2), R6、R7、R8And R9It is each independently selected from H, halogen atom and C1-5Alkyl；
In formula (3), R10And R12It is each independently selected from H, halogen atom and C1-5Alkyl, R11Selected from-COO- and-CH2O-；Its
In the copolymer, the molar ratio for the repetitive unit that general formula (1), (2) and (3) indicates is 10~90:10~90:1~10.
2. copolymer according to claim 1, it is characterised in that:
The R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R12It each independently represents selected from H and-CH3,
It is describedIndicate halogen ion or oxygen-containing acid group.
3. copolymer according to claim 1 or 2, it is characterised in that:
The weight average molecular weight of the copolymer is 5000~30000g/mol,
The molecular weight of copolymer distribution (weight average molecular weight (Mw)/number-average molecular weight (Mn)) is not more than 3.
4. copolymer according to claim 3, it is characterised in that:
The weight average molecular weight of the copolymer is 15000~20000g/mol,
The molecular weight of copolymer distribution (weight average molecular weight (Mw)/number-average molecular weight (Mn)) is not more than 2.5.
5. the preparation method of any one of Claims 1 to 4 copolymer, it is characterised in that be included in the presence of initiator and gather
Close the monomer that following general formula (1 '), (2 ') and (3 ') indicates:
Wherein, in formula (1 '), R1、R2、R3、R4And R5It is each independently selected from H, halogen atom and C1-5Alkyl, X-Expression contend with from
Son；
In formula (2 '), R6、R7、R8And R9It is each independently selected from H, halogen atom and C1-5Alkyl；
In formula (3 '), R10And R12It is each independently selected from H, halogen atom and C1-5Alkyl, R11Selected from-COO- and-CH2O-。
6. according to the method described in claim 5, it is characterized in that specifically:
A) lotion is made in general formula (1 ') and (2 ') described monomer in the presence of emulsifier for 35~65 DEG C；
B) 60~80 DEG C of addition general formulas (3 ') monomer and initiator carry out emulsion polymerization in inert gas environment to obtain the final product.
7. according to the method described in claim 6, it is characterized by:
The emulsifier is optional dodecyl benzyl dimethyl ammonium chloride, octadecyltrimethylammonium chloride, cetyl
One kind of trimethyl ammonium chloride, aliphatic amine polyoxyethylene ether or combinations thereof object；And/or
The initiator is radical initiator；And/or
The inert gas is nitrogen.
8. the dyestuff binders composition comprising any one of claim 1~7 copolymer, characterized by comprising:
1) copolymer as described in any one of claim 1~7；
2) resin；And
3) solvent.
9. dyestuff binders composition according to claim 9, it is characterised in that in parts by weight,
The additive amount of the copolymer preferably accounts for 5~90 weight % of the dyestuff binders composition quality；
The additive amount of the resin preferably accounts for 0.1~50 weight % of the dyestuff binders composition quality；
The additive amount of the solvent preferably accounts for 20~50 parts by weight % of the dyestuff binders composition quality.
10. application of the dyestuff binders composition of claim 8 or 9 in dye printing and dyeing, it is characterised in that:
The dyestuff binders composition is as described in claim 8 or 9；
The dyestuff is selected from anthraquinone dye or tetraazatetradecane porphyrin dyestuff.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521561A (en) * | 2020-12-15 | 2021-03-19 | 太仓宝霓实业有限公司 | Water-based organic silicon color fixing agent polymer and preparation method thereof |
| CN115989286A (en) * | 2020-09-01 | 2023-04-18 | 住友化学株式会社 | Compound (I) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619117A (en) * | 2008-07-03 | 2010-01-06 | 上海雅运纺织助剂有限公司 | Formaldehyde-free color fixing agent for reactive dyes and preparation method and application thereof |
| JP2013177566A (en) * | 2012-01-30 | 2013-09-09 | Mitsubishi Gas Chemical Co Inc | Modifier for resin |
| CN103709326A (en) * | 2013-12-27 | 2014-04-09 | 福建清源科技有限公司 | Preparation method of cationic organic silicon modified poly(diallyldimethylammonium chloride) fixing agent |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619117A (en) * | 2008-07-03 | 2010-01-06 | 上海雅运纺织助剂有限公司 | Formaldehyde-free color fixing agent for reactive dyes and preparation method and application thereof |
| JP2013177566A (en) * | 2012-01-30 | 2013-09-09 | Mitsubishi Gas Chemical Co Inc | Modifier for resin |
| CN103709326A (en) * | 2013-12-27 | 2014-04-09 | 福建清源科技有限公司 | Preparation method of cationic organic silicon modified poly(diallyldimethylammonium chloride) fixing agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115989286A (en) * | 2020-09-01 | 2023-04-18 | 住友化学株式会社 | Compound (I) |
| CN115989286B (en) * | 2020-09-01 | 2023-09-29 | 住友化学株式会社 | Compounds of formula (I) |
| CN112521561A (en) * | 2020-12-15 | 2021-03-19 | 太仓宝霓实业有限公司 | Water-based organic silicon color fixing agent polymer and preparation method thereof |
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