CN103233371B - Printing paste and applications thereof - Google Patents

Printing paste and applications thereof Download PDF

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Publication number
CN103233371B
CN103233371B CN201310174723.9A CN201310174723A CN103233371B CN 103233371 B CN103233371 B CN 103233371B CN 201310174723 A CN201310174723 A CN 201310174723A CN 103233371 B CN103233371 B CN 103233371B
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printing
paste
agent
polyacrylic acid
printing paste
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CN103233371A (en
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钱红飞
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University of Shaoxing
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University of Shaoxing
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Abstract

The invention discloses a printing paste and applications thereof, belonging to the technical field of printing. The printing paste comprises the following ingredients by weight: 0.01-4 of active dye, 30-50 of polyacrylic acid thickening agent raw paste, 1-3 of sodium carbonate, and the balance of water. By mixing proper active dye and the printing paste materials, the technical difficulties of salt tolerance, rheological property, fixation rate and the like widely existing in the printing paste can be effectively solved, the printing colour yield and fixation rate of the active dye can be greatly improved, so that the printing paste replaces the use of a great deal of urea, thus completely realizing the non-urea printing technique, and having a remarkable effect in the industry.

Description

A kind of printing paste and application thereof
technical field:
The present invention relates to a kind of printing paste, specifically refer to a kind of printing paste, and be applicable to the application of cellulose base fiber fabric printing technology.
background technology:
REACTIVE DYES chromatogram is complete, and wet fastness is high, soft, is the primary dye of cellulose fibre stamp.Not only extensive use on cotton, viscose glue, sky silk, bast fiber fabrics, and also use in a large number on silk like fabric.At present, REACTIVE DYES mainly adopts a phase method (alkali and REACTIVE DYES with starch) direct printing technique, and printing gum mainly adopts sodium alginate, but weak point to be loose colour too heavy, after washing task weight, easily causes and is infected with whitely, affect product quality.Produce a large amount of dyeing and printing sewages simultaneously, environment is caused to having a strong impact on, and add the cost of wastewater treatment.Cause the above results, mainly cause because reactive dye color fixing rate is not high, few more than 80% of degree of fixation in actual production, most between 60-70%.
The factor affecting printing with reactive dye degree of fixation is a lot, and wherein reactive dyestuff molecule structure, reaction activity are one of principal element.Low form REACTIVE DYES reactivity is too high, is easily hydrolyzed, and High Temperature Type Reactive Dyes reactivity is low, easily causes the incomplete phenomenon of reaction.
Both at home and abroad using moderate in developing focus for selection activity, make every effort to improve degree of fixation, to improve tinctorial yield, but still undesirable, main employing is a chloro-s-triazine dyestuff and Vinyl-Sulfone Type dyestuff at present.
1, a chloro-s-triazine dyestuff:
One chloro-s-triazine dyestuff alkali resistance is high, and mill base is facile hydrolysis not, and the also not easily scission of link under alkaline environment of the covalent bond after fixation, therefore, a chloro-s-triazine REACTIVE DYES is the REACTIVE DYES of the most applicable all-in method stamp in the market.Its stability of pigment paste is high, and period of storage is long, even if under 40 DEG C of hot environments, its changes of shade is also very little afterwards to place two weeks, is also not easy to occur wind print defect even if stamp semi-products evaporate not in time.But its active group reactivity is low, require higher to steam moisture, particularly print regenerated celulose fibre fabric.Time drawing a design in laboratory, steam moisture is sufficient, and Dry Sack is rich and gaudy, but when producing greatly, because steam moisture is lower, Dry Sack often can be caused shallow, and coloured light withers secretly, and it is serious that aberration is criticized in front and back, even occurs the problems such as left, center, right aberration, cloth complexion flower.In addition, its degree of fixation is lower, most of dye fixing rate is 50% ~ 60%, and large production is even lower, when therefore doing dark color or special dark color, the easy imbibition of flower pattern, can cause a large amount of loose colours during washing, and easily cause white background staining, rope form washing also there will be the problem of cutting marks, and Printing wets fastness difference, waste water COD height waits series of problems.If any particularly wax seal enterprise of factory, often there is 12% (o.w.f) the even dye dosage of higher concentration.For pure cotton knitted fabric, most of printing and dyeing enterprise does not carry out mercerization finish, and therefore Dry Sack is more shallow.In order to improve above problem, stamp enterprise uses urea in a large number, becomes ammonia nitrogen discharge rich and influential family.
2, Vinyl-Sulfone Type dyestuff:
Although Vinyl-Sulfone Type dyestuff degree of fixation is high, it is applicable to two phase printing, is not suitable for now more general all-in method stamp.Vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) active group reactivity is high, therefore easy and fiber-reactive, but also easy and water reaction forms not alkaline-resisting covalent bond, facile hydrolysis.Particularly under a large amount of urea existent condition, be hydrolyzed more serious.Its print paste was placed no more than 2 days, and particularly when summer temperature height, more facile hydrolysis, lighter, black even becomes coffee-like, causes dyestuff to waste in a large number.Due to the existence of urea, the fabric after stamp, in the process of banking up, easily absorbs the moisture in air, causes topical dye to be hydrolyzed, thus occurs wind print defect.
In addition, adopt double-active radical dye in addition, the solubility of double-active radical dye is generally poor, as bright blue MGB, dark blue M2GE, red M2B etc., easily there is look flower, aberration when dye is dark, even occur color dot, therefore must strengthen the consumption of urea, but consumption can accelerate again too greatly the hydrolysis of dyestuff.In addition, double-active radical dye great majority are a chloro-s-triazine and vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) two active groups, therefore there is wind print problem equally, as easily there is shade bar when dark blue M2GE spells green.
Technique scheme, all indispensablely can use urea, adds the tinting strength, tinting power that urea can significantly improve dyestuff, in limited steaming time, realize higher degree of fixation during printing with reactive dye, thus improves tinctorial yield.And according to China's " national economy and social development the 12 five-year plan outline ", the target that ammonia nitrogen reduces discharging 10% is clearly proposed.Therefore market needs new dye without urea or low urea and fixation system badly, can meet the requirement of national environmental protection index, ensure again to obtain higher degree of fixation and tinctorial yield.
The factor affecting degree of fixation in addition is on the one hand printing gum.At present, the conventional sodium alginate thickener of REACTIVE DYES cellulose fibre print paste preparation, has de-advantage of sticking with paste easy to clean, there is charge repulsion, be conducive to REACTIVE DYES and transfer to cellulose fibre from mill base with REACTIVE DYES.But it is undesirable also to there is rheological characteristic, the defects such as circle (putting down) wire mark colored particularly high order number wire mark, fine chemical wastewater and large area stamp printing effect is undesirable, its tinctorial yield is also not as good as some other synthetic slurries.Sodium alginate price improves in recent years in addition, causes stamp production cost to rise.
summary of the invention:
For the problems referred to above, first aspect present invention object is to provide one and is applicable to cellulose fibre stamp, and has higher tinctorial yield, there will not be the printing paste of look flower and aberration.
The technical scheme that the present invention takes is as follows, and a kind of printing paste, is characterized in that, described printing paste comprises following composition by weight:
REACTIVE DYES 0.01-4;
Agent for polyacrylic acid thickening former paste 30-50;
Sodium bicarbonate 1-3;
Water surplus.
Preferably:
Described REACTIVE DYES be active yellow P-2RN, reactive blue P-3R, active red P-6B, active emerald green blue P-GR, reactive orange P-2R, active red P-4B, reactive black P-Q, reactive black P-GR-2 any one.
Described agent for polyacrylic acid thickening former paste compound method is as follows: take agent for polyacrylic acid thickening 16 grams, and adding water to total amount is 100 grams, carries out stirring into flat-white starchiness.
Described agent for polyacrylic acid thickening, is particularly preferably thickener 401, and as the thickener 401 that Zhejiang Jingye Biochemical Co., Ltd. produces, its solid content is 50%.
The compound method of described printing paste is as follows: take the former paste of agent for polyacrylic acid thickening according to technical recipe, take required REACTIVE DYES and sodium bicarbonate respectively again, by REACTIVE DYES and sodium bicarbonate respectively with after water-soluble solution, pour in the former paste of agent for polyacrylic acid thickening, stir.
Second aspect present invention object is to provide the application of a kind of aforementioned printing paste in cellulose fibre printing technology.
Cellulose fibre printing technology flow process is as follows:
---stamp---dries---decatize---cold wash---hot water wash------hot water wash---Warm Wash---cold wash of soaping to fabric after pre-treatment.
Wherein:
Steaming conditions: temperature 100-102 DEG C, time 8-10min.
Soaping condition: soaping agent 1-2g/L, temperature 95 DEG C, time 10-15min.
Operation principle of the present invention and beneficial effect as follows:
1, the selection of dyestuff: the present invention is by testing a large amount of REACTIVE DYES and screen, finally determine several REACTIVE DYES kind such as active yellow P-2RN, reactive blue P-3R, active red P-6B, active emerald green blue P-GR, reactive orange P-2R, active red P-4B, reactive black P-Q, reactive black P-GR-2, above-mentioned REACTIVE DYES not only salt content is low, and coordinate with printing paste thickener of the present invention there is good colour fixation, thus solve this thickener salt tolerance difference and the low technical barrier of degree of fixation.
2, the preparation of thickener: printing paste thickener of the present invention, adopts agent for polyacrylic acid thickening, has that tinctorial yield is high, rheological characteristic good, lower-price characteristic.
3, the cooperation of dyestuff and thickener: because the salt tolerance of agent for polyacrylic acid thickening is poor, makes the viscosity of mill base thickener reduce thinning after meeting salt, so that flower pattern flushing phenomenon occurs during stamp, thus limits its application.Therefore, in order to improve the rheological characteristic of mill base, and the flower pattern diffusion flushing, the unsharp problem of profile that overcome caused by REACTIVE DYES salt content height, the present invention is by the selection of REACTIVE DYES, and the content of thickener in raising mill base, the viscosity of further increase mill base, thus the rheological characteristic and the salt tolerance problem that solve printing paste of the present invention.
4, the printing paste of preparation of the present invention, in suitable cellulose fibre printing technology, by the control to Steaming conditions and soaping condition, proper extension steaming time, increase the reaction set chance of mill base humidity and dyestuff and fiber, have further larger lifting to the fixation rate of REACTIVE DYES.
5, the present invention is by the cooperation of REACTIVE DYES and printing paste thickener, efficiently solve the technical barriers such as salt tolerance, rheological characteristic and the degree of fixation extensively existed in printing paste, the tinctorial yield of printing with reactive dye and fixation rate is made to have raising by a relatively large margin, thus instead of the use of a large amount of urea, realize the printing technology without urea completely, there is outstanding effect in the industry.
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
accompanying drawing illustrates:
Fig. 1 is that Conventional decal slurry adopts the apparent shade depth value of active yellow P-2RN printing with reactive dye to contrast with printing paste of the present invention;
Fig. 2 is that Conventional decal slurry adopts the apparent shade depth value of active red P-6B printing with reactive dye to contrast with printing paste of the present invention;
Fig. 3 is that Conventional decal slurry adopts the apparent shade depth value of reactive brilliant bule P-3B printing with reactive dye to contrast with printing paste of the present invention;
Fig. 4 is that Conventional decal slurry adopts the apparent shade depth value of reactive black P-GR-2 printing with reactive dye to contrast with printing paste of the present invention;
In figure:
Front, reverse side refer to the apparent shade depth value of PRINTED FABRIC positive and negative;
Tradition refers to and adopts Conventional decal slurry prescription (adding urea, sodium alginate thickener);
New 6 min refer to and adopt the printing technology of printing paste of the present invention under steaming time 6 min;
New 8min refers to and adopts the printing technology of printing paste of the present invention under steaming time 8 min;
New 10 min refer to and adopt the printing technology of printing paste of the present invention under steaming time 10 min;
New 12 min refer to and adopt the printing technology of printing paste of the present invention under steaming time 12 min.
detailed description of the invention:
Embodiment 1: printing paste technology preparation:
REACTIVE DYES 0.01-4g
Thickener 401 former paste 30-50g
Sodium bicarbonate 1-3g
Water surplus
100g。
The compound method of printing paste: take thickener 401 former paste 30-50 gram according to technology preparation, separately take the REACTIVE DYES needed for technology preparation and sodium bicarbonate respectively, REACTIVE DYES and sodium bicarbonate use appropriate water-soluble solution respectively, to entering in the former paste of thickener 401, and add the water of surplus, stir.
REACTIVE DYES is chosen as active yellow P-2RN, reactive blue P-3R, active red P-6B, active emerald green blue P-GR, reactive orange P-2R, active red P-4B, reactive black P-Q or reactive black P-GR-2.
The former paste prescription of thickener 401:
Thickener 401 16 grams
Water surplus
100 grams.
The former paste compound method of thickener 401: take 16 grams of thickeners 401, adding suitable quantity of water to total amount is 100 grams, carries out stirring into flat-white starchiness.
Embodiment 2: the printing paste Performance Detection of different formulations.
According to printing paste prepared by embodiment 1 method, select different REACTIVE DYES respectively, detect the rheological characteristic of the saliferous rate of its REACTIVE DYES, viscosity, thickener, cotton knitted fabric carries out stamp, carry out printing technology Contrast on effect with traditional printing paste.
1, method of testing:
1.1: viscosity test: with NDJ-1 type viscometer determining.
The mensuration of 1.2:PVI: namely η 60/ η 6 ratio represents the PVI value of former paste, η 60, η 6 are 60,6r/min time former paste viscosity number.This value is less, and illustrate that slurry increases its viscosity with shear stress and declines faster, when scraping, mill base is easily through the screen cloth of high order number, and decorative pattern fineness is high.
1.3: the mensuration of surperficial color depth value: adopt Datacolor SF600 to survey color matching system, to measure the reflectivity of fabric under D65 light source, 10 ° of visual angles, calculate apparent shade depth value K/S from albedometer, K/S value is larger, and color is denseer, and tinctorial yield is high; Otherwise then lighter, tinctorial yield is low.
2, the printing paste of different activities preparation of dyestuff:
In the commercialization preparation process of REACTIVE DYES, add with a large amount of neutral electrolytes, the existence of these salt, will the use of agent for polyacrylic acid thickening be affected.Therefore, this test prepares prescription and method by adopting identical mill base, viscosity test is carried out to the mill base that the 26 commercially available REACTIVE DYES being only applicable to stamp are prepared, the salt content of REACTIVE DYES can be judged: viscosity is lower from surveyed data, REACTIVE DYES salt content is higher, otherwise then salt content is low.Concrete outcome is in table 1.
Table 1: the printing paste viscosity number of different activities preparation of dyestuff.
Note: the printing paste prescription in form 1 is by weight percentage: REACTIVE DYES 2%, the former paste 30% of thickener 401, sodium bicarbonate 2%, adds water to 100%.
As can be seen from Table 1:
In K type REACTIVE DYES: reactive orange K-GN, active red K-3B, active purple k-3r have higher viscosity, known these several dyestuff salt content are lower.In P type REACTIVE DYES, reactive orange P-2R, active yellow P-2RN, active red P-4B, active red P-6B, reactive blue P-3R, active emerald green blue P-GR, reactive black P-Q, reactive black P-GR-2 these several viscosity numbers are higher, and salt content is less.
And in actual production, dyestuff needs mutual colorant match to apply, to obtain various color and luster, and during colorant match, dyestuff preferably belongs to identical type, just has good compatibility, produces stable coloured light.As can be seen from above-mentioned data, the kind that in P type REACTIVE DYES, salt content is low has possessed red, yellow, primary colors and black varieties, can meet the colorant match needs of actual production.Therefore preferably adopt P type REACTIVE DYES, stable coloured light can be had.
3, the printing paste Performance Detection of the former paste of agent for polyacrylic acid thickening (for thickener 401) is adopted:
Below with Conventional decal slurry (adopt sodium alginate thickener) for comparative example, carry out rheological characteristic and apparent shade depth value with printing paste of the present invention (adopting the former paste of thickener 401) and detect and analyze.
3.1 rheological characteristics:
To adopt the printing paste of the former paste of sodium alginate for comparative example, adopt the printing paste of the former paste of thickener 401 to contrast with the present invention, and measure its PVI value respectively, to reflect their rheological characteristic, the results are shown in Table 2:
Table 2, the former paste of thickener 401 compare with the rheological characteristic of the former paste of sodium alginate
The former paste prescription of sodium alginate:
Sodium alginate 16 grams
Calgon 0.8 gram
Water surplus
100 grams
Sodium alginate is former pastes Preparation Method: take 16 grams of sodium alginate thickeners, slowly adds while stirring and has been dissolved with in the ormal weight hydrothermal solution of calgon, until transparent pasty state.
The mill base preparation method of sodium alginate thickener: the former paste of sodium alginate taking ormal weight in mill base prescription, another REACTIVE DYES and the sodium bicarbonate taking ormal weight respectively, after dissolving, injects the former paste of alginic acid by suitable quantity of water, add the water of surplus, stir in mill base.
As can be seen from 2 table data:
The PVI value of the printing paste of the former paste of thickener 401 and preparation is all lower than sodium alginate, the mill base that thickener 401 is prepared as thickener is described, more meticulous decorative pattern can be printed, be applicable to printing hydrophilic cellulose fiber fabric, be beneficial to mill base and textiles is soaked, permeates.
3.2 stamp tinctorial yield:
Adopt the printing paste of embodiment 1 preparation (without urea, the former paste of thickener 401), starch with Conventional decal and (add urea, sodium alginate thickener) be applied to cellulose fibre printing technology, respectively with active yellow P-2RN, active red P-6B, reactive brilliant bule P-3B, the REACTIVE DYES that these four salt content of reactive black P-GR-2 are lower carries out printing tests, and measure the apparent shade depth value of PRINTED FABRIC positive and negative respectively, simultaneously, detect printing paste of the present invention respectively and (adopt 6 min respectively under different steaming time condition, 8 min, 10 min, the change of printing with reactive dye tinctorial yield 12min), the results are shown in Figure 1, Fig. 2, Fig. 3 and Fig. 4.
Printing technology flow process:
---stamp---dries---decatize---cold wash---hot water wash------hot water wash---Warm Wash---cold wash of soaping to fabric after pre-treatment.
Steaming conditions: 100-102 DEG C, 8-10min.
Soaping condition: soaping agent 1-2g/L, 95 DEG C, 10-15min.
Conventional decal slurry prescription:
REACTIVE DYES 2 grams
The former paste of sodium alginate 50 grams
10 grams, urea
Sodium bicarbonate 3 grams
Water is appropriate
100 grams.
Steam temperature: 100-102 DEG C; Steaming time: 6 min.
Printing paste prescription of the present invention:
REACTIVE DYES 2 grams
The former paste of thickener 401 50 grams
Sodium bicarbonate 3 grams
Water is appropriate
100 grams.
Steam temperature: 100-102 DEG C; Steaming time is selected respectively: 6 min, 8 min, 10 min, 12min.
Statistical analysis:
As can be seen from Fig. 1 ~ Fig. 4:
Adopt new technology namely without urea printing technology, when steaming time is enough, all can obtain even better apparent shade depth value close to Conventional decal technique.Wherein the steaming time of active yellow P-2RN, active red P-6B, these three REACTIVE DYES of reactive brilliant bule P-3B is the apparent shade depth value that 8min just can reach Conventional decal technique substantially, and reactive black P-GR-2 needs longer steaming time and 10min.In addition, from the K/S value of fabric backing and the K/S value ratio in front, new technology has printthrough more better than traditional handicraft, and its ratio is higher.
In sum, using the former paste of thickener 401 as printing gum, printing paste REACTIVE DYES being screened to rear preparation, be applied to cellulose base fiber fabric printing technology, coordinate proper extension steaming time, when not having urea to add, can obtain the tinctorial yield close with Conventional decal technique, and the rheological characteristic of printing paste, printthrough are better than Conventional decal technique, thus really achieve without urea printing technique.

Claims (3)

1. a printing paste, is characterized in that, described printing paste comprises following composition by weight percentage:
REACTIVE DYES 0.01-4;
Agent for polyacrylic acid thickening former paste 30-50;
Sodium bicarbonate 1-3;
Water surplus;
Described REACTIVE DYES be active red P-6B, active emerald green blue P-GR, active red P-4B, reactive black P-Q or reactive black P-GR-2 any one;
The former paste of described agent for polyacrylic acid thickening refers to agent for polyacrylic acid thickening and water to configure by weight 16:84 and forms; Described agent for polyacrylic acid thickening is thickener 401;
The compound method of described printing paste is as follows: take the former paste of agent for polyacrylic acid thickening according to technical recipe, take required REACTIVE DYES and sodium bicarbonate respectively again, by REACTIVE DYES and sodium bicarbonate respectively with after water-soluble solution, pour in the former paste of agent for polyacrylic acid thickening, stir.
2. a kind of printing paste according to claim 1, is characterized in that: described agent for polyacrylic acid thickening former paste compound method is as follows: take agent for polyacrylic acid thickening 16 grams, and adding water to total amount is 100 grams, carries out stirring into flat-white starchiness.
3. the application of printing paste described in claim 1 in cellulose fibre printing technology, comprises the following steps:---stamp---dries---decatize---cold wash---hot water wash------hot water wash---Warm Wash---cold wash of soaping to the fabric after pre-treatment; Wherein: Steaming conditions: temperature 100-102 DEG C, time 8-10min; Soaping condition: soaping agent 1-2g/L, temperature 95 DEG C, time 10-15min.
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CN103469618B (en) * 2013-09-06 2016-04-13 浙江华东纺织印染有限公司 A kind of without urea printing with reactive dye mill base, manufacture method and dyeing method
CN103556500B (en) * 2013-11-04 2016-02-17 绍兴文理学院 A kind of print paste and preparation method thereof and application
CN106012605B (en) * 2016-05-31 2018-07-17 山东洁晶集团股份有限公司 One kind being applied to cotton, synthetic cotton printing thickener and preparation method thereof
CN107476042A (en) * 2016-06-08 2017-12-15 福建福田纺织印染科技有限公司 A kind of reactive printing new technology based on EST soaping agents
CN107415449B (en) * 2017-07-10 2019-10-29 安徽万方织染有限公司 A kind of efficient printing system and method for warp knit textile cloth
CN109594364B (en) * 2018-11-29 2021-03-23 太仓宝霓实业有限公司 Reactive printing urea substitute and preparation method thereof

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