CN105113285A - Slurry disperse dye and preparation method and appliance - Google Patents
Slurry disperse dye and preparation method and appliance Download PDFInfo
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- CN105113285A CN105113285A CN201510598484.9A CN201510598484A CN105113285A CN 105113285 A CN105113285 A CN 105113285A CN 201510598484 A CN201510598484 A CN 201510598484A CN 105113285 A CN105113285 A CN 105113285A
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Abstract
The invention discloses a slurry disperse dye and a preparation method and an appliance, wherein the slurry disperse dye comprises liquid disperse dyes, functional prepolymers and synthetic thickeners, the synthetic thickeners and functional additives are added into the slurry disperse dye to prepare trace printing paste, and can complete printings of polyester fabrics on a common rotary screen printing machine or a screen printing machine, then printed polyester fabrics are prepared through a heat-setting stenter in 180 DEG C-210 DEG C for 45-120s. The slurry disperse dye has the advantages of short printing process when being used for polyester fabric printings, is soft in fabric handing, does not need post process, saves a lot of water and energy consumption, nearly does not have discharge amount of waste water, uses common equipment as process equipment, and is a green printing process technology.
Description
Technical field
The invention belongs to fabrics printing and dyeing technical field, be specifically related to a kind of pulp-shaped dispersed dyes and preparation method thereof and application, for short route, the energy-saving and emission-reduction printing technology of dacron.
Background technology
In the thirties in 20th century, new era of textile fabric started by synthetic fiber, in succession has multiple synthetic fiber to come out, and the development of dyestuff is always closely connected with the exploitation of fiber.In fabrics printing and dyeing industry; conventional granular dyestuff, when sizing mixing or prepare dye liquor, dyestuff dust from flying; not only hinder environmental protection; and often stick on the apparatus of batching, or suspend in preparation dye liquor foam, particularly little in solubility; the DISPERSE DYES of dispersive property difference; easily form agglomerate, be easily produce fault at stamp or dyeing, affect product quality.DISPERSE DYES is a kind of powdery or granular nonionic dye, and molecular structure is little, is applicable to the dyeing of terylene and BLENDED FABRIC thereof.But because it is not containing-COOH ,-SO
3the strong water-soluble groups such as H, in water, solubility is low, be unfavorable for dye molecule under lower temperature the absorption of fiber surface and on dye.
Polyster fibre is the maximum synthetic fiber of output, polyster fibre is except large traditional product, fibre in differentiation should be greatly developed, particularly superfine fibre, because the surface area of its unit mass to attenuate with filament number and increases, cause fast, the apparent and fastness to light decline to look shallow of dyeing kinetics, for DISPERSE DYES, level-dyeing property, covering property, enhancing and dyefastness problem must be solved; The printed articles of dacron accounts for about 40% of terylene dyeing and printing process total amount; The major way of printed polyester has direct printing, COAT PRINTING, thermal transfer printing.
Direct printing is the major way of current stamp, is a kind ofly commercial dyes, thickener and additive to be prepared into the print paste with certain viscosity, then carries out the conventional machining techniques of stamp, oven dry, decatize and multiple tracks washing; Along with the development of the synthetic thickening agent of high viscosity, low solid content, the consumption of synthetic thickening agent in print paste can be reduced, but because the compatibility of existing DISPERSE DYES and synthetic thickening agent is poor, for obtaining the print paste of certain viscosity, still need the synthetic thickening agent print paste configuring high solids content (as 5 ~ 6%), prevent the decline of stamp dielectric viscosity.Because of the increase of synthetic thickening agent consumption in print paste, cause direct printing dye utilization rate low, the massive laundering in road after PRINTED FABRIC needs, the loose colour of fabric face could be removed, improve the COLOR FASTNESS of terylene printing product, obtain soft feel, therefore, the maximum inferior position of direct printing is: because in print paste, solid contents is high, needs to evaporate process and has carried out dyestuff to the upper dye of fiber; Printed articles loose colour is serious, Boardy Feeling, needs to wash postprocessing working procedures, removes the organic matter and dyestuff that do not shift, and to the consumption very big (accounting for 70% of dyeing process) of water resource, wastewater discharge is very big, and the colourity of waste water is comparatively dark, and COD value is higher.Existing COAT PRINTING is that commercial coating, synthetic thickener and additive (adhesive and crosslinking agent) are prepared into the print paste with certain viscosity, then carries out the conventional machining techniques of stamp, oven dry, high-temperature process; Because of adhesive in COAT PRINTING and dosage of crosslinking agent larger, printing quality is bad, COLOR FASTNESS is poor, the maximum inferior position of COAT PRINTING is: the performance of adhesive and crosslinking agent determines COLOR FASTNESS and the feel of printed articles, for direct printing goods, COLOR FASTNESS is poor, and feel is harder or coarse, and the chromatogram of coating is abundant and diversified not as good as DISPERSE DYES.Because of the shortcoming of COAT PRINTING, limit the application of COAT PRINTING, small size can only be used for or to the less demanding printed articles of feel; The thermal transfer printing of existing DISPERSE DYES is that heat resistance is poor, and the DISPERSE DYES of easy heat sublimation is printed in transfer paper in advance, then by the hot pressing function of transfer paper and fabric, allows the DISPERSE DYES in transfer paper transfer to printing technique on fabric; The maximum inferior position of thermal transfer printing is: COLOR FASTNESS is poor, and depth of color is more shallow, difficult acquisition deep printing goods, and will consume the transfer paper of equal stamp quantity, causes the wasting of resources and secondary pollution (remaining in the dyestuff in transfer paper).
In existing direct printing mill base, all adopt commercial dispersants dyestuff, because the compatibility of commercial dispersants dyestuff and synthetic thickening agent is poor, greatly reduce the viscosity of thickener, cause the rheological property of print paste poor; Therefore, need exploitation one and the good liquid dispersion dyestuff of synthetic thickening agent compatibility, just can prevent dyestuff sedimentation, improve print paste viscosity.And adopt commercially available DISPERSE DYES, no matter be powder solid or liquid dispersion dyestuff, all need to strengthen thickener consumption, the requirement to printing paste viscosity when could meet stamp.
Along with today that requirement that is energy-saving and cost-reducing, energy-saving and emission-reduction more and more comes into one's own, the dacron printing technique that necessary research and development are new, need that both there is the advantage that stamp work flow is short, little to water resources consumption amount and wastewater discharge is little, there is again the advantage of the excellent and fabrics feel soft of stamp COLOR FASTNESS; Need to avoid the shortcoming that direct printing is large to water resources consumption amount and wastewater discharge is large simultaneously, also will avoid the shortcoming that COAT PRINTING feel is harder or coarse, COLOR FASTNESS is poor.
Summary of the invention
The object of this invention is to provide a kind of liquid dispersion dyestuff and the pulp-shaped dispersed dyes based on this liquid dispersion dyestuff; For direct printing, effective, energy consumption is low, water consumption is few.
To achieve the above object of the invention, the technical solution used in the present invention is:
A kind of liquid dispersion dyestuff, prepares by with under type, former dyestuff, active grinding agent and water is mixed, grinds 12 ~ 20 hours, obtained liquid dispersion dyestuff; By mass percentage, the raw material of described liquid dispersion dyestuff consists of:
Former dyestuff 10 ~ 30%
Active grinding agent 1.0 ~ 3.5%
All the other are water;
Described active grinding agent is 1 by mass ratio: anion surfactant and the non-ionic surface active agent of (0.5 ~ 2) form;
In described liquid dispersion dyestuff, the particle size range of solid particle is 800nm ~ 3 μm.
In technique scheme, described anion surfactant is one or both the mixture in the formaldehyde condensation products of alcohol ether phosphate salt, alcohol ether carboxylate, Tryfac 5573 sylvite, methyl naphthalene sulfonic acid sodium; Described non-ionic surface active agent is one or both the mixture in the derivative of aliphatic acid polyethenoxy ether, fatty alcohol-polyoxyethylene ether, glycerin mono-fatty acid ester, isomery fatty alcohol-polyoxyethylene ether.
Preferably, described alcohol ether phosphate salt is isomerous tridecanol polyoxyethylene ether phosphate kalium salt or isomery undecyl alcohol polyoxyethylene ether phosphate sylvite; Described alcohol ether carboxylate is isomerous tridecanol polyoxyethylene ether carboxylic acid sodium salt, isomery undecyl alcohol polyoxyethylene ether carboxylic acid sodium salt or isooctyl acid polyoxyethylene ether carboxylic acid sodium salt; Described aliphatic acid polyethenoxy ether is oleic acid polyoxyethylene, stearic acid polyoxyethylene ether, tall oil acid polyoxyethylene ether, castor oil acid polyoxyethylene ether, hydrogenated castor oleic acid polyoxyethylene ether or laurate polyoxyethylene ether; Described isomery fatty alcohol-polyoxyethylene ether is isomerous tridecanol polyoxyethylene ether.
Preferred further, in described aliphatic acid polyethenoxy ether, the number of oxyethylene group is 10 ~ 20; In described fatty alcohol-polyoxyethylene ether, the number of oxyethylene group is 9 ~ 20; The number of the oxyethylene group of described isomerous tridecanol polyoxyethylene ether is 10 ~ 20; The number of the oxyethylene group of described alcohol ether phosphate salt or alcohol ether carboxylate is 6 ~ 8.
Such as described alcohol ether phosphate salt is isomerous tridecanol polyoxyethylene ether (6) phosphate kalium salt, isomerous tridecanol polyoxyethylene ether (8) phosphate kalium salt, isomery undecyl alcohol polyoxyethylene ether (6) phosphate kalium salt, isomery undecyl alcohol polyoxyethylene ether (8) phosphate kalium salt; Described alcohol ether carboxylate is isomerous tridecanol polyoxyethylene ether (6) carboxylic acid sodium salt, isomerous tridecanol polyoxyethylene ether (8) carboxylic acid sodium salt, isomery undecyl alcohol polyoxyethylene ether (6) carboxylic acid sodium salt, isomery undecyl alcohol polyoxyethylene ether (8) carboxylic acid sodium salt, isooctyl acid polyoxyethylene ether (6) carboxylic acid sodium salt, isooctyl acid polyoxyethylene ether (8) carboxylic acid sodium salt; Described aliphatic acid polyethenoxy ether is oleic acid polyoxyethylene (8), stearic acid polyoxyethylene ether (9), stearic acid polyoxyethylene ether (20), laurate polyoxyethylene ether (12), laurate polyoxyethylene ether (24); Described fatty alcohol-polyoxyethylene ether is fatty alcohol (C12-18) polyoxyethylene ether (9), fatty alcohol (C12-18) polyoxyethylene ether (10), fatty alcohol (C12-18) polyoxyethylene ether (15), fatty alcohol (C12-18) polyoxyethylene ether (20); Described isomery fatty alcohol-polyoxyethylene ether is isomerous tridecanol polyoxyethylene ether (10), isomerous tridecanol polyoxyethylene ether (12), castor oil polyoxyethylene ether (10), castor oil polyoxyethylene ether (12), castor oil polyoxyethylene ether (20).The adjuvant used good hydrophilic property of the present invention, is beneficial to dye dispersion, improves direct printing effect.
Preferably, described former dyestuff is containing the former dyestuff of anthraquinone ring, the former dyestuff containing heterocycle structure, the former dyestuff containing heterocycle azo structure or the former dyestuff containing monoazo structure.Concrete structure formula is:
。
Pulp-shaped dispersed dyes can be prepared by aforesaid liquid DISPERSE DYES, in liquid dispersion dyestuff, add the function performed polymer that whole mass fraction is the synthetic thickening agent of 0.01 ~ 0.03%, whole mass fraction is 0.5 ~ 2.0% successively, in room temperature through being uniformly mixed, obtained pulp-shaped dispersed dyes; Being prepared as of described function performed polymer, is added to the water monomer, modifier and emulsifying agent, preparation emulsion; Initator is added to the water, prepares initiator solution; Then by quality accounting, the initiator solution of the emulsion of 30 ~ 60% amounts with 30 ~ 60% amounts is mixed, prepares mixed liquor; The temperature regulating mixed liquor is 70 ~ 75 DEG C; Then under agitation remaining emulsion and remaining initiator solution are dropped in mixed liquor, be added dropwise to complete, then react 110 ~ 130 minutes, obtain function performed polymer; In described emulsion, the mass fraction of monomer, modifier and emulsifying agent is respectively 15 ~ 24%, 2 ~ 5%, 1.5 ~ 3%, and all the other are water; Described monomer is made up of butyl acrylate, acrylonitrile, acrylic acid, N hydroxymethyl acrylamide; Described modifier is made up of ethylene glycol dimethacrylate, tetramethylol methane tetraacrylate, isotridecyl acrylate; Described emulsifying agent is made up of dodecyl sodium sulfate, SP-80 and isomerous tridecanol polyoxyethylene ether; Described initator is persulfate.
In pulp-shaped dispersed dyes of the present invention, the mass fraction of synthetic thickening agent is 0.01 ~ 0.03%, the mass fraction of function performed polymer is 0.5 ~ 2.0%, and all the other are liquid dispersion dyestuff.Synthetic thickening agent is commercially available prod, and primary structure is the copolymer of acrylic acid and acrylate.
In technique scheme, function performed polymer contains reactive functionality, can change fibrous material to the adsorptivity of dyestuff and reactivity, strengthens printing quality; Function performed polymer of the present invention, by monomer, modifier, emulsifying agent and water, under initator exists, obtains through emulsion polymerisation; In described emulsion, the mass fraction of monomer is 15 ~ 24%, and the mass fraction of modifier is 2 ~ 5%, and the mass fraction of emulsifying agent is 1.5 ~ 3%; With the quality of emulsion for benchmark, in described monomer, the mass fraction of acrylonitrile is 2.4 ~ 2.6%, acrylic acid mass fraction is 0.4 ~ 0.6%, the mass fraction of N hydroxymethyl acrylamide is 0.4 ~ 0.6%, all the other are butyl acrylate; With the quality of emulsion for benchmark, in described modifier, the mass fraction of ethylene glycol dimethacrylate is 0.7 ~ 1.2%, the mass fraction of tetramethylol methane tetraacrylate is 0.1 ~ 0.3%, and all the other are isotridecyl acrylate; With the quality of emulsion for benchmark, in described emulsifying agent, the mass fraction of emulsifying agent SP-80 is 0.4 ~ 0.6%, the mass fraction of isomerous tridecanol polyoxyethylene ether is 0.4 ~ 0.6%, and all the other are dodecyl sodium sulfate.In technique scheme, emulsion comprises the compound of multiple compositing monomer, modifier and emulsifying agent, the mass fraction of each compound calculate all with the gross mass of emulsion for benchmark, what namely embody is all the mass fraction of each compound in emulsion.In such as emulsion, when the gross mass mark of emulsifying agent is 2%, when the mass fraction of SP-80 be 0.6%, the mass fraction of isomerous tridecanol polyoxyethylene ether be 0.5% time, the mass fraction of dodecyl sodium sulfate is 0.9%.
Function performed polymer prepared by the present invention, rheological characteristic is good, and processability is good, has the effect extremely significantly reduced the retention rate of DISPERSE DYES, effectively can not only promote that DISPERSE DYES is transferred on polyster fibre, increase the fastness of PRINTED FABRIC; Can also fabrics feel soft be ensured, large area printed articles can be applied to, overcome bonding agent in existing COAT PRINTING and crosslinking agent COLOR FASTNESS is poor, feel is coarse defect.
The present invention adopts anion surfactant and the former dyestuff of non-ionic surface active agent process first, overcoming that prior art thinks can only by the technology prejudice of the former dyestuff of MF compounds process, avoid the adverse effect of finishing agent to the performance of other components such as thickener, only need a small amount of thickener can ensure the viscosity of pulp-shaped dispersed dyes, avoid the problem that solution dyestuff easily produces sedimentation, be conducive to the stability of stamp process, levelability, dye utilization rate is high; Also avoid that the printed articles feel that prior art uses organic additive to cause in a large number is poor, problem not environmentally simultaneously.Therefore, the invention also discloses the application of aforesaid liquid DISPERSE DYES in dacron stamp.
Further, the invention also discloses the application of above-mentioned pulp-shaped dispersed dyes in dacron direct printing; Specifically comprise the following steps, be the water mixing of the synthetic thickening agent of 0.5 ~ 1.5%, the paste liquid DISPERSE DYES of 0.5 ~ 3.5%, the functional additive of 0.5 ~ 1.0% and surplus by whole mass fraction, stir, obtained print paste; Dacron is through described print paste stamp post-drying; Again through high-temperature process, i.e. dacron stamp; The temperature of described high-temperature process is 180 DEG C ~ 210 DEG C, and the time is 45 ~ 120 seconds; Described functional additive is ethylene glycol monobutyl ether and/or γ-piperazinopropyl methyl dimethoxysilane.When preparing print paste, with the mass fraction of gross mass each component for radix calculates of synthetic thickening agent, paste liquid DISPERSE DYES, functional additive and water.
The short route printing method of dacron provided by the invention, integrates " low water resources consumption, low sewage discharge, excellent COLOR FASTNESS, soft feel ", solves the deficiency of existing printing technique; By obtained print paste, first on rotary screen printing machine or screen printing machine, the stamp to dacron and oven dry can be completed; High-temperature process is carried out again on tentering heat setter.
Because technique scheme is used, the present invention compared with prior art has following advantages:
(1) the present invention adopts the grinding technique simultaneously with anion and non-ionic surface active agent first, prepares the pulp-shaped dispersed dyes that particle size range is 800nm ~ 3 μm; The mass concentration of the active principle of the print paste prepared by this pulp-shaped dispersed dyes is lower, but dye utilization rate and the rate of transform high; And the viscosity of stamp medium is higher, have good rheological characteristic, meet the requirement of stamp medium to viscosity, therefore, the print paste amount on fabric is little, is a kind of micro-stamp mode, can be applicable to the requirement of lithographic plate screen printing, garden wire mark flower.
(2) when the print paste that paste liquid DISPERSE DYES disclosed by the invention and function prepolymer, synthetic thickening agent are prepared is used for dacron stamp, dacron is dried through printing, only need again through high-temperature heat treatment (as adopted conventional heat setter), without the need to evaporating process and post processing (as soap, reduction cleaning) through high temperature again, soft, that COLOR FASTNESS is excellent printed polyester goods just can be prepared; Flow process is short, and water resources consumption amount and wastewater discharge are extremely low, is a kind of green stamp process technology.
(3) printed articles that obtains of stamp process disclosed by the invention is without the need to washing post processing, COLOR FASTNESS is high, and washing variable color fastness reaches 4-5 level (washing temperature is 50 degree), and washing staining fastness reaches 4 grades (washing temperature is 50 degree), dry friction COLOR FASTNESS reaches 4-5 level, and wet friction COLOR FASTNESS reaches 4 grades; Printed articles soft, reaches the level of direct printing fabric; And not containing APEO, not containing formaldehyde; Overcome existing direct printing and must wash post processing, defect not environmentally.
(4) rate of transform of paste liquid DISPERSE DYES disclosed by the invention is all higher than 96%, namely DISPERSE DYES from print paste to fibrous inside transfer and the rate of transform of set all higher than 96%, and remaining DISPERSE DYES is under the effect of synthetic thickening agent, function performed polymer and functional additive, can combine with fiber securely; Therefore, PRINTED FABRIC need not again through reduction cleaning and washing step, water-saving and emission-reducing, and printing quality is good, and pattern is full, it is color gorgeous to dazzle, block face is even, COLOR FASTNESS is high, achieves beyond thought technique effect.
(5) paste liquid DISPERSE DYES disclosed by the invention is very little on the impact of synthetic thickening agent etc., avoid the defect that existing DISPERSE DYES makes thickener viscosity decline to a great extent, therefore in print paste, thickener consumption is little, viscosity is higher, there is good rheological characteristic, meet the requirement of stamp medium to viscosity, particularly avoid the adverse effect of large amount of organic to printed articles feel.
(6) in the print paste prepared of paste liquid DISPERSE DYES disclosed by the invention, active principle content is very low, well below the solid content of existing print paste, but the dyestuff rate of transform is high, all dyestuffs are printed on dacron, the printed articles pattern obtained is full, it is color gorgeous to dazzle, block face is even, COLOR FASTNESS is high, achieves beyond thought technique effect; Particularly evaporate process and washing post processing without the need to high temperature, still there is excellent COLOR FASTNESS, wash durability, Dry Sack rate is high, solve prior art and have to pass through the difficult problem that high temperature evaporates process and washing post processing, not only save the water consumption of dacron stamp processing about 70%, more decrease organic discharge, benefit the nation and the people, be conducive to stamp to environmental protection and energy saving future development.
(7) raw material preparing paste liquid DISPERSE DYES disclosed by the invention forms rationally, and process of lapping is controlled, and mix with all the other components when the paste liquid DISPERSE DYES obtained prepares print paste, compatibility is good; Printing method is simple, only needs part existing equipment, and be easy to operation, the time is short, integrates " low water resources consumption, low sewage discharge, excellent COLOR FASTNESS, soft feel ", is applicable to large area suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the printed articles figure of embodiment ten;
Fig. 2 is the printed articles figure of embodiment 11;
Fig. 3 is the printed articles figure of comparative example one;
Fig. 4 is the printed articles figure of comparative example two.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Raw materials all in embodiment is all commercially available prod, as commodity are called H90 synthetic thickening agent and PTF-A synthetic thickening agent; Former dyestuff is as follows:
(1) containing the former dyestuff of anthraquinone ring:
(2) containing the former dyestuff of heterocycle structure:
(3) containing the former dyestuff of heterocycle azo structure:
(4) containing the former dyestuff of monoazo structure:
Embodiment one
18.0g butyl acrylate, 2.5g acrylonitrile, 0.5g acrylic acid, 0.5gN-n-methylolacrylamide, 0.2g tetramethylol methane tetraacrylate, 1.0g ethylene glycol dimethacrylate, 2.0g isotridecyl acrylate, 0.5g emulsifying agent SP-80,1.0g dodecyl sodium sulfate, 0.5g isomerous tridecanol polyoxyethylene ether (12) and 60.5g water are mixed, and fully stirs into emulsion.By 1.0g ammonium persulfate at room-temperature dissolution in 11.8g water, and fully stir into initiator solution.The half of getting a half-sum initiator solution quality of quality of the emulsion adds in reaction unit, heats while stirring, is warming up to 70 DEG C.When temperature reaches 70 DEG C, under stirring, drip the mixed liquor of a half-sum initiator solution quality of remaining quality of the emulsion at leisure, time for adding is 120min simultaneously.After being added dropwise to complete, continue to stir 120min at 74 DEG C ± 2 DEG C, obtained function performed polymer A.
Embodiment two
By former for 12.0g dyestuff (2), 0.6g isomerous tridecanol polyoxyethylene ether (8) phosphate kalium salt, 0.6g stearic acid polyoxyethylene ether (9), the mixing of 86.8g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.02gH90 synthetic thickening agent and 2.0g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes A.
Embodiment three
By former for 15.0g dyestuff (4), 1.0g isomerous tridecanol polyoxyethylene ether (6) phosphate kalium salt, 2.0g isomerous tridecanol polyoxyethylene ether (12), the mixing of 82.0g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.02gH90 synthetic thickening agent and 1.5g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes B.
Embodiment four
By former for 18.0g dyestuff (6), 1.0g isomery undecyl alcohol polyoxyethylene ether (8) phosphate kalium salt, 0.5g fatty alcohol (C
12-18) polyoxyethylene ether (9), the mixing of 80.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.03gPTF-A synthetic thickening agent and 2.0g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes C.
Embodiment five
By former for 22.0g dyestuff (8), 1.0g isomerous tridecanol polyoxyethylene ether (8) carboxylic acid sodium salt, 1.0g stearic acid polyoxyethylene ether (20), the mixing of 76.0g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.02gPTF-A synthetic thickening agent and 1.5g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes D.
Embodiment six
By former for 28.0g dyestuff (10), 1.0g isomerous tridecanol polyoxyethylene ether (6) carboxylic acid sodium salt, 1.5g fatty alcohol (C
12-18) polyoxyethylene ether (15), the mixing of 69.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.02gH90 synthetic thickening agent and 0.8g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes E.
Embodiment seven
By former for 15.0g dyestuff (14), 1.0g isomery undecyl alcohol polyoxyethylene ether (6) carboxylic acid sodium salt, 2.0g isomerous tridecanol polyoxyethylene ether (10), the mixing of 82.0g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.025gH90 synthetic thickening agent and 1.6g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes F.
Embodiment eight
By the formaldehyde condensation products of former for 20.0g dyestuff (22), 0.5g Tryfac 5573 sylvite, 1.5g methyl naphthalene sulfonic acid sodium, 0.5g isomerous tridecanol polyoxyethylene ether (12), 0.5g fatty alcohol (C
12-18) polyoxyethylene ether (20), the mixing of 77.0g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.028gH90 synthetic thickening agent and 0.6g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes G.
Embodiment nine
By the formaldehyde condensation products of former for 15g dyestuff (34), 1.0g isooctyl acid polyoxyethylene ether (6) carboxylic acid sodium salt, 1.0g methyl naphthalene sulfonic acid sodium, 1.5g isomerous tridecanol polyoxyethylene ether (12), the mixing of 81.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.015gH90 synthetic thickening agent and 1.5g function performed polymer A, through fully stirring, obtained pulp-shaped dispersed dyes H.
Embodiment ten
1gH90 synthetic thickening agent, 0.8g pulp-shaped dispersed dyes A, 0.5g ethylene glycol monobutyl ether and 97.7g water are mixed, stirs, obtained micro-direct printing mill base A.
On lithographic plate screen printing machine, get micro-print paste A, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 190 DEG C, 60 seconds time, the printed polyester fabric of obtained red phase.
Embodiment 11
1.5gH90 synthetic thickening agent, 1.2g pulp-shaped dispersed dyes B, 0.8g ethylene glycol monobutyl ether and 96.5g water are mixed, stirs, obtained micro-print paste B.
On lithographic plate screen printing machine, get micro-print paste B, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 200 DEG C, 45 seconds time, the printed polyester fabric of obtained blue phase.
Embodiment 12
1.5gH90 synthetic thickening agent, 2.0g pulp-shaped dispersed dyes C, 1.0g ethylene glycol monobutyl ether and 95.5g water are mixed, stirs, obtained micro-print paste C.
On lithographic plate screen printing machine, get micro-print paste C, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 185 DEG C, 100 seconds time, the printed polyester fabric of obtained yellow phase.
Embodiment 13
0.7gH90 synthetic thickening agent, 0.5g pulp-shaped dispersed dyes D, 0.5g γ-piperazinopropyl methyl dimethoxysilane and 98.3g water are mixed, stirs, obtained micro-print paste D.
On lithographic plate screen printing machine, get micro-print paste D, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 205 DEG C, 45 seconds time, the printed polyester fabric of obtained yellow phase.
Embodiment 14
1gPTF-A synthetic thickening agent, 0.8g pulp-shaped dispersed dyes E, 0.7g ethylene glycol monobutyl ether and 97.5g water are mixed, stirs, obtained micro-print paste E.
On lithographic plate screen printing machine, get micro-print paste E, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 190 DEG C, 60 seconds time, the printed polyester fabric of obtained red phase.
Embodiment 15
1.5gPTF-A synthetic thickening agent, 1.2g pulp-shaped dispersed dyes F, 0.5g ethylene glycol monobutyl ether, 0.5g γ-piperazinopropyl methyl dimethoxysilane and 96.3g water are mixed, stirs, obtained micro-print paste F.
On lithographic plate screen printing machine, get micro-print paste F, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 185 DEG C, 100 seconds time, the printed polyester fabric of obtained yellow phase.
Embodiment 16
1.5gPTF-A synthetic thickening agent, 2.0g pulp-shaped dispersed dyes G, 0.2 ethylene glycol monobutyl ether, 0.3g γ-piperazinopropyl methyl dimethoxysilane and 96.0g water are mixed, stirs, obtained micro-print paste G.
On lithographic plate screen printing machine, get micro-print paste G, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 205 DEG C, 45 seconds time, the printed polyester fabric of obtained orange phase.
Embodiment 17
0.7gPTF-A synthetic thickening agent, 0.5g pulp-shaped dispersed dyes H, 0.3 ethylene glycol monobutyl ether, 0.6g γ-piperazinopropyl methyl dimethoxysilane and 97.9g water are mixed, stirs, obtained micro-print paste H.
On lithographic plate screen printing machine, get micro-print paste H, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 195 DEG C, 50 seconds time, the printed polyester fabric of obtained blue phase.
Comparative example one
By former for 12.0g dyestuff (2), 3.6g commercial dispersants MF and the mixing of 84.4g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-A.
1gH90 synthetic thickening agent, 0.8g DISPERSE DYES R-A and 98.2g water are mixed, is stirred well to pulpous state, obtained print paste R-A.
On lithographic plate screen printing machine, get print paste R-A, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 190 DEG C, 60 seconds time, the printed polyester fabric of obtained red phase.
Comparative example two
By former for 15.0g dyestuff (4), 4.5g commercial dispersants MF and the mixing of 80.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-B.
1.5gH90 synthetic thickening agent, 1.2g DISPERSE DYES R-B and 97.3g water are mixed, is stirred well to pulpous state, obtained print paste R-B.
On lithographic plate screen printing machine, get print paste R-B, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 200 DEG C, 45 seconds time, the printed polyester fabric of obtained blue phase.
Comparative example three
By former for 18.0g dyestuff (6), 5.4g commercial dispersants MF and the mixing of 76.6g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-C.
1.5gH90 synthetic thickening agent, 2.0g DISPERSE DYES R-C and 96.5g water are mixed, stirs, obtained micro-print paste R-C.
On lithographic plate screen printing machine, get print paste R-C, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 185 DEG C, 100 seconds time, the printed polyester fabric of obtained yellow phase.
Comparative example four
By former for 22.0g dyestuff (8), 6.6g commercial dispersants MF and the mixing of 71.4g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-D.
0.7gH90 synthetic thickening agent, 0.5g DISPERSE DYES R-D and 98.8g water are mixed, stirs, obtained micro-print paste R-D.
On lithographic plate screen printing machine, get print paste R-D, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 205 DEG C, 45 seconds time, the printed polyester fabric of obtained yellow phase.
Comparative example five
By former for 28.0g dyestuff (10), 8.4g commercial dispersants MF and the mixing of 63.6g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-E.
1.0gPTF-A synthetic thickening agent, 0.8g DISPERSE DYES R-E and 98.2g water are mixed, stirs, obtained micro-print paste R-E.
On lithographic plate screen printing machine, get print paste R-E, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 190 DEG C, 60 seconds time, the printed polyester fabric of obtained red phase.
Comparative example six
By former for 15.0g dyestuff (14), 4.5g commercial dispersants MF and the mixing of 80.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-F.
1.5gPTF-A synthetic thickening agent, 1.2g DISPERSE DYES R-F, 1.6g function performed polymer A and 95.7g water are mixed, stirs, obtained micro-print paste R-F.
On lithographic plate screen printing machine, get print paste R-F, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 185 DEG C, 100 seconds time, the printed polyester fabric of obtained yellow phase.
Comparative example seven
By former for 20.0g dyestuff (22), 6.0g commercial dispersants MF and the mixing of 74.0g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-G.
By 1.5gPTF-A synthetic thickening agent, 2.0g DISPERSE DYES R-E, 0.6g commercial binder FY-161(home products) and the mixing of 95.9g water, stir, obtained micro-print paste R-G.
On lithographic plate screen printing machine, get print paste R-G, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 205 DEG C, 45 seconds time, the printed polyester fabric of obtained orange phase.
Comparative example eight
By former for 15.0g dyestuff (34), 4.5g commercial dispersants MF and the mixing of 80.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-H.
0.7gPTF-A synthetic thickening agent, 0.5g DISPERSE DYES R-H and 98.8g water are mixed, stirs, obtained micro-print paste R-H.
On lithographic plate screen printing machine, get print paste R-H, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 195 DEG C, 50 seconds time, the printed polyester fabric of obtained blue phase.
Comparative example nine
By former for 15.0g dyestuff (34), 4.5g commercial dispersants MF and the mixing of 80.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-I.
0.7gPTF-A synthetic thickening agent, 0.5g DISPERSE DYES R-I, 1.5g function performed polymer A and 97.3g water are mixed, stirs, obtained micro-print paste R-I.
On lithographic plate screen printing machine, get print paste R-I, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 195 DEG C, 50 seconds time, the printed polyester fabric of obtained blue phase.
Comparative example ten
By former for 12.0g dyestuff (2), 3.6g commercial dispersants MF and the mixing of 84.4g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-J.
By 1gH90 synthetic thickening agent, 0.6g DISPERSE DYES R-J, 1.5g commercial coating stamp adhesive S0503(home products) and the mixing of 97.3g water, stir, obtained micro-print paste R-J.
On lithographic plate screen printing machine, get print paste R-J, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 190 DEG C, 60 seconds time, the printed polyester fabric of obtained red phase.
Comparative example 11
By former for 15.0g dyestuff (4), 4.5g commercial dispersants MF and the mixing of 80.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g DISPERSE DYES R-K.
By 1.5gH90 synthetic thickening agent, 1.0g DISPERSE DYES R-K, 1.5g commercial binder FY-161(home products) and the mixing of 96.0g water, be stirred well to pulpous state, obtained print paste R-K.
On lithographic plate screen printing machine, get print paste R-K, dacron is printed, after printing completes, then on lithographic plate screen printing machine, drying unit is dried, and finally on stentering boarding machine, carries out high-temperature heat treatment, temperature is 200 DEG C, 45 seconds time, the printed polyester fabric of obtained blue phase.
Comparative example 12
By the formaldehyde condensation products of former for 15g dyestuff (34), 1.0g isooctyl acid polyoxyethylene ether (6) carboxylic acid sodium salt, 1.0g methyl naphthalene sulfonic acid sodium, 1.5g isomerous tridecanol polyoxyethylene ether (12), the mixing of 81.5g water, in sanding apparatus, be ground to dye particle is 1 ~ 3 μm, obtained 100g liquid dispersion dyestuff.In aforesaid liquid DISPERSE DYES, add 0.015gH90 synthetic thickening agent and 1.5g commercial coating stamp adhesive S0503(home products), through fully stirring, obtained paste liquid DISPERSE DYES R-L.
0.7gPTF-A synthetic thickening agent, 0.5g paste liquid DISPERSE DYES R-L, 0.3 ethylene glycol monobutyl ether, 0.6g γ-piperazinopropyl methyl dimethoxysilane and 97.9g water are mixed, stirs, obtained micro-print paste R-L.
On lithographic plate screen printing machine, get micro-print paste R-L, dacron is printed, after printing completes, on lithographic plate screen printing machine, drying unit is dried again, and finally on stentering boarding machine, carry out high-temperature heat treatment, temperature is 195 DEG C, 50 seconds time, the printed polyester fabric of obtained blue phase.
Printing technology flow process:
1) printing technology A(present invention process): dacron → stamp → oven dry → high-temperature process → printed polyester goods.
2) printing technology B: dacron → stamp → oven dry → high-temperature process → reduction cleaning (sodium hydrosulfite 3g/L, soda ash 1g/L, 85 DEG C × 20min) → washing (60 DEG C × 20min) → washing (room temperature × 10min) → oven dry → printed polyester goods.
Above-mentioned stamp example adopts printing technology B to carry out direct printing and compares.
The washing fastness of printed polyester fabric adopts AATCC61-2010 standard testing, and temperature is 50 DEG C, and colour fastness to rubbing adopts AATCC8-2001 standard testing, observes the figure clarity of PRINTED FABRIC, the results are shown in Table 1 and table 2.
Table 1 embodiment printing quality
Table 2 comparative example printing quality
Test result shows, contrast is through reduction cleaning and washing process (printing technology B), though adopt the PRINTED FABRIC of product of the present invention without reduction cleaning and washing process, still can reach with through the reduction cleaning excellent COLOR FASTNESS identical with washing process, and fabrics feel soft, printing flower pattern is clear, is a kind of new printing technique of energy-saving and cost-reducing, energy-saving and emission-reduction.Adopt the commercialization grinding technique of commercial dispersants dyestuff, namely adopt the liquid dispersion dyestuff of dispersing agent MF grinding, need, by reduction cleaning and washing process (printing technology B), just can prepare the printed polyester goods that COLOR FASTNESS is suitable, but PRINTED FABRIC to be unintelligible; As without reduction cleaning and washing process, then the COLOR FASTNESS of printed polyester goods is very poor, and PRINTED FABRIC is unintelligible.
Embodiment PRINTED FABRIC is not containing formaldehyde and APEO, and fabrics feel soft, measuring bending length according to GB/T18318-2001 " mensuration of textile fabric bending length " is 3.1 ~ 3.2cm, the rate of transform of dyestuff is all higher than 96%, in simulation stamp medium, the residual rate of dyestuff is all lower than 3%, is a kind of new printing technique of energy-saving and cost-reducing, energy-saving and emission-reduction.
Fig. 1 ~ Fig. 4 is respectively the printed articles figure adopting printing technology A, Fig. 1 and Fig. 2 is respectively the printing effect of embodiment ten and embodiment 11; Fig. 3 and Fig. 4 is respectively the printing effect of comparative example one and comparative example two.
Can clearly see, the mutually red and blue phase decalcomania of embodiment ten and embodiment 11, the svelteness of its stamp, without imbibition phenomenon; The mutually red and blue phase decalcomania of comparative example one and comparative example two, the lines of its stamp are unintelligible, have extremely significantly imbibition phenomenon.
Claims (10)
1. a liquid dispersion dyestuff, is characterized in that: described liquid dispersion dyestuff prepares by with under type, former dyestuff, active grinding agent and water is mixed, grinds 12 ~ 20 hours, obtained liquid dispersion dyestuff; By mass percentage, the raw material of described liquid dispersion dyestuff consists of:
Former dyestuff 10 ~ 30%
Active grinding agent 1.0 ~ 3.5%
All the other are water;
Described active grinding agent is 1 by mass ratio: anion surfactant and the non-ionic surface active agent of (0.5 ~ 2) form;
In described liquid dispersion dyestuff, the particle diameter of solids is 800nm ~ 3 μm.
2. liquid dispersion dyestuff according to claim 1, is characterized in that: described anion surfactant is one or both the mixture in the formaldehyde condensation products of alcohol ether phosphate salt, alcohol ether carboxylate, Tryfac 5573 sylvite, methyl naphthalene sulfonic acid sodium; Described non-ionic surface active agent is one or both the mixture in the derivative of aliphatic acid polyethenoxy ether, fatty alcohol-polyoxyethylene ether, glycerin mono-fatty acid ester, isomery fatty alcohol-polyoxyethylene ether.
3. liquid dispersion dyestuff according to claim 2, is characterized in that: described alcohol ether phosphate salt is isomerous tridecanol polyoxyethylene ether phosphate kalium salt or isomery undecyl alcohol polyoxyethylene ether phosphate sylvite; Described alcohol ether carboxylate is isomerous tridecanol polyoxyethylene ether carboxylic acid sodium salt, isomery undecyl alcohol polyoxyethylene ether carboxylic acid sodium salt or isooctyl acid polyoxyethylene ether carboxylic acid sodium salt; Described aliphatic acid polyethenoxy ether is oleic acid polyoxyethylene, stearic acid polyoxyethylene ether, tall oil acid polyoxyethylene ether, castor oil acid polyoxyethylene ether, hydrogenated castor oleic acid polyoxyethylene ether or laurate polyoxyethylene ether; Described isomery fatty alcohol-polyoxyethylene ether is isomerous tridecanol polyoxyethylene ether.
4. liquid dispersion dyestuff according to claim 3, it is characterized in that: in described aliphatic acid polyethenoxy ether, the number of oxyethylene group is 10 ~ 20; In described fatty alcohol-polyoxyethylene ether, the number of oxyethylene group is 9 ~ 20; The number of the oxyethylene group of described isomerous tridecanol polyoxyethylene ether is 10 ~ 20; The number of the oxyethylene group of described alcohol ether phosphate salt or alcohol ether carboxylate is 6 ~ 8.
5. liquid dispersion dyestuff according to claim 1, is characterized in that: the structural formula of described former dyestuff is the one in following structural formula:
。
6. a pulp-shaped dispersed dyes, is characterized in that, described pulp-shaped dispersed dyes is mixed to get by any one liquid dispersion dyestuff, function performed polymer and synthetic thickening agent described in Claims 1 to 5;
Being prepared as of described function performed polymer, is added to the water monomer, modifier and emulsifying agent, preparation emulsion; Initator is added to the water, prepares initiator solution; Then by quality accounting, the initiator solution of the emulsion of 30 ~ 60% amounts with 30 ~ 60% amounts is mixed, prepares mixed liquor; The temperature regulating mixed liquor is 70 ~ 75 DEG C; Then under agitation remaining emulsion and remaining initiator solution are dropped in mixed liquor, be added dropwise to complete, then react 110 ~ 130 minutes, obtain function performed polymer; In described emulsion, the mass fraction of monomer, modifier and emulsifying agent is respectively 15 ~ 24%, 2 ~ 5%, 1.5 ~ 3%, and all the other are water; Described monomer is made up of butyl acrylate, acrylonitrile, acrylic acid, N hydroxymethyl acrylamide; Described modifier is made up of ethylene glycol dimethacrylate, tetramethylol methane tetraacrylate, isotridecyl acrylate; Described emulsifying agent is made up of dodecyl sodium sulfate, SP-80 and isomerous tridecanol polyoxyethylene ether; Described initator is persulfate;
In described pulp-shaped dispersed dyes, the mass fraction of synthetic thickening agent is 0.01 ~ 0.03%, the mass fraction of function performed polymer is 0.5 ~ 2.0%, and all the other are liquid dispersion dyestuff.
7. pulp-shaped dispersed dyes according to claim 6, it is characterized in that: with the quality of emulsion for benchmark, in described monomer, the mass fraction of acrylonitrile is 2.4 ~ 2.6%, acrylic acid mass fraction is 0.4 ~ 0.6%, the mass fraction of N hydroxymethyl acrylamide is 0.4 ~ 0.6%, all the other are butyl acrylate; With the quality of emulsion for benchmark, in described modifier, the mass fraction of ethylene glycol dimethacrylate is 0.7 ~ 1.2%, the mass fraction of tetramethylol methane tetraacrylate is 0.1 ~ 0.3%, and all the other are isotridecyl acrylate; With the quality of emulsion for benchmark, in described emulsifying agent, the mass fraction of emulsifying agent SP-80 is 0.4 ~ 0.6%, the mass fraction of isomerous tridecanol polyoxyethylene ether is 0.4 ~ 0.6%, and all the other are dodecyl sodium sulfate.
8. any one liquid dispersion dyestuff application in dacron stamp described in Claims 1 to 5.
9. the application of pulp-shaped dispersed dyes described in claim 6 in dacron direct printing.
10. application according to claim 9, it is characterized in that: specifically comprise the following steps, be the water mixing of the synthetic thickening agent of 0.5 ~ 1.5%, the pulp-shaped dispersed dyes of 0.5 ~ 3.5%, the functional additive of 0.5 ~ 1.0% and surplus by mass fraction, stir, obtained print paste; Dacron is through described print paste stamp post-drying; Again through high-temperature process, i.e. dacron stamp; The temperature of described high-temperature process is 180 DEG C ~ 210 DEG C, and the time is 45 ~ 120 seconds; Described functional additive is ethylene glycol monobutyl ether and/or γ-piperazinopropyl methyl dimethoxysilane.
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