阅读说明：本技术 聚氨酯类复合活性印花糊料及其制备方法 (Polyurethane composite active printing paste and preparation method thereof ) 是由 陈松 陈震雷 宋泽华 李英超 荣启龙 高殿权 侯志文 杨勇 于 2020-06-28 设计创作，主要内容包括：本发明提供一种聚氨酯类复合活性印花糊料及其制备方法。所述复合糊料如下质量份的组分：聚氨酯增稠剂40-60份；天然种子胶20-35份,无机物5-10份。同时公开了适用于活性印花的高分子聚氨酯的分子式。经大量应用测试,本发明提供的聚氨酯类复合活性印花糊料应用于棉活性印花中,不仅印花织物手感更加柔软,更利于织物手感风格后整理,而且印花织物表观得色量高,复合糊料极高的成糊率很大程度的降低了印花成本,同时减少了废污排放量。(The invention provides a polyurethane composite active printing paste and a preparation method thereof. The composite paste comprises the following components in parts by mass: 40-60 parts of polyurethane thickener; 20-35 parts of natural seed gum and 5-10 parts of inorganic matters. Also disclosed are molecular formulas of the polymeric polyurethanes suitable for reactive printing. Through a large number of application tests, the polyurethane composite active printing paste provided by the invention is applied to cotton active printing, so that the printed fabric has softer hand feeling and is more beneficial to after-finishing of the hand feeling style of the fabric, the apparent color yield of the printed fabric is high, the pasting rate of the composite paste is extremely high, the printing cost is reduced to a great extent, and the waste discharge amount is reduced.)

1. The polyurethane composite active printing paste comprises the following components in parts by mass: 40-60 parts of polyurethane thickener, 20-35 parts of natural plant seed gum and 5-10 parts of inorganic substance.

2. The polyurethane composite reactive printing paste according to claim 1, wherein: the polyurethane thickener is a high molecular compound containing branched chains and carboxyl, and the molecular formula of the polyurethane thickener is shown as the formula 1:

in the formula 1, a, b and c all represent polymerization degrees, wherein a is any integer from 1 to 20; b is any integer of 1-10; c is any integer from 1 to 15;

R₁is a long chain fatty alcohol residue;

R₂is a high molecular polyethylene glycol residue;

A₁is a diisocyanate residue;

the natural plant seed gum is guar gum or a mixture of guar gum and tamarind gum, and the guar gum accounts for 40-50% of the mixture;

the inorganic substance is one or two of anhydrous sodium sulphate and sodium chloride.

3. The polyurethane composite reactive printing paste according to claim 2, wherein: the guar gum is a carboxymethyl guar gum with a high degree of substitution, and the degree of substitution is greater than 1.5.

4. The polyurethane composite reactive printing paste according to any one of claims 1 to 3, wherein: the polyurethane composite active printing paste is any one of the following (1) to (4):

(1) 40 parts of a polyurethane thickener; 10 parts of guar gum; 10 parts of tamarind gum; 5 parts of anhydrous sodium sulphate;

(2) 60 parts of a polyurethane thickener; 15 parts of guar gum; 20 parts of tamarind gum; 10 parts of anhydrous sodium sulphate;

(3) 50 parts of a polyurethane thickener; 27 parts of guar gum; 8 parts of anhydrous sodium sulphate;

(4) 60 parts of a polyurethane thickener; 8 parts of guar gum; 12 parts of tamarind gum; 10 parts of sodium chloride.

5. A process for preparing the polyurethane based composite reactive printing paste according to any one of claims 1 to 4, comprising: (1) adding guar gum into a powder mixer, stirring, adding a polyurethane thickener, and continuously stirring for 20-30 min;

(2) adding anhydrous sodium sulphate into the mixer, and uniformly stirring to obtain the polyurethane composite active printing paste.

6. The method of claim 5, wherein: tamarind gum can be further added in the step (2).

7. The application of the polyurethane thickener in the preparation of composite active printing paste,

the polyurethane thickener is a high molecular compound containing branched chains and carboxyl, and the molecular formula of the polyurethane thickener is shown as the formula 1:

in the formula 1, a, b and c all represent polymerization degrees, wherein a is any integer from 1 to 20; b is any integer of 1-10; c is any integer from 1 to 15;

R₁is a long chain fatty alcohol residue;

R₂is a high molecular polyethylene glycol residue;

A₁is a diisocyanate residue.

8. Use of the polyurethane composite reactive printing paste according to any one of claims 1 to 4 in cotton reactive printing.

9. Use according to claim 8, characterized in that: when the polyurethane composite active printing paste of any one of claims 1 to 4 is used for cotton active printing, the additive amount of the polyurethane composite active printing paste in color paste is 0.8 to 1.2 percent.

Technical Field

The invention belongs to the technical field of textile chemistry and dyeing and finishing engineering, and particularly relates to a polyurethane composite active printing paste and a preparation method thereof.

Background

Since the advent of reactive dyes, cotton printing was favored due to its complete color spectrum. Most textile reactive printing still adopts the traditional screen printing process, including flat screen printing and rotary screen printing. Screen printing pastes are generally composed of dyes, auxiliaries and raw pastes. The thickener plays a key role in the formula of the screen printing paste, controls the rheological property, permeability and mobility of the printing paste, and is the most main factor for determining the printing quality except for dye.

At present, sodium alginate is still used as a printing paste of an active dye mainly at home and abroad, along with the development of a printing screen technology, the demand of people is improved, the performance of the sodium alginate cannot meet the market demand, and in addition, the price of the sodium alginate is continuously increased due to the application of the sodium alginate in the aspects of food, medical treatment and the like; therefore, the thickener is usually introduced to compound sodium alginate to improve the printing performance of the sodium alginate and reduce the cost, and in recent years, the research on the thickener mainly focuses on the aspects of polyacrylic acid thickener, modified guar gum, modified starch, modified cellulose and the like, but the results are less satisfactory, the salt resistance stability of the sodium polyacrylate thickener is poor, the hand feeling of the modified thickener is hard, and on the premise that the environmental protection requirement is increasingly strict, the development of low-cost and high-performance active printing paste becomes an urgent problem to be solved in the printing and dyeing industry.

Disclosure of Invention

The invention aims to provide a polyurethane composite active printing paste and a preparation method thereof, and provides a composite paste which has high pasting rate, low PVI value, high water holding capacity, high color yield and bright color.

The polyurethane composite active printing paste provided by the invention comprises the following components in parts by mass: 40-60 parts of polyurethane thickener, 20-35 parts of natural plant seed gum and 5-10 parts of inorganic substance.

The polyurethane thickener is a high molecular compound containing a branched chain and a carboxyl group, and the molecular formula of the polyurethane thickener is shown as a formula 1:

in the formula 1, a, b and c all represent polymerization degrees, wherein a is any integer from 1 to 20; b is any integer of 1-10; c is any integer from 1 to 15;

R₁is a long-chain fatty alcohol residue, and the long-chain fatty alcohol specifically can be: one of dodecanol, hexadecanol and octadecanol;

R₂is a high molecular polyethylene glycol residue, and the high molecular polyethylene glycol can be specifically: PEG4000, PEG6000, PEG8000, or the like;

A₁is a residue of a diisocyanate, which may be specifically: one of toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate;

the thickener shown in the formula 1 can be FK-168C which is purchased from Beijing Zhongjin chemical industry Co., Ltd;

the natural plant seed gum can be guar gum or a mixture of guar gum and tamarind gum, wherein the guar gum accounts for 40-50% of the mixture.

In particular, the guar may be a high degree of substitution carboxymethyl guar, in particular a degree of substitution > 1.5;

the inorganic substance can be one or two of anhydrous sodium sulphate and sodium chloride;

the carboxymethyl guar gum, the tamarind gum and the inorganic matter are all commercial products.

Further, the polyurethane composite reactive printing paste is any one of the following (1) to (4):

(1) 40 parts of a polyurethane thickener; 10 parts of guar gum; 10 parts of tamarind gum; 5 parts of anhydrous sodium sulphate;

(2) 60 parts of a polyurethane thickener; 15 parts of guar gum; 20 parts of tamarind gum; 10 parts of anhydrous sodium sulphate;

(3) 50 parts of a polyurethane thickener; 27 parts of guar gum; 8 parts of anhydrous sodium sulphate;

(4) 60 parts of a polyurethane thickener; 8 parts of guar gum; 12 parts of tamarind gum; 10 parts of sodium chloride.

The invention also provides a preparation method of the polyurethane composite active printing paste.

The preparation method of the polyurethane composite active printing paste provided by the invention comprises the following steps:

(1) adding guar gum into a powder mixer, stirring, adding a polyurethane thickener, and continuously stirring for 20-30 min;

(2) adding anhydrous sodium sulphate into the mixer, and uniformly stirring to obtain the polyurethane composite active printing paste.

The mixer in the step (1) of the method can be one of a double-helix conical mixer and a double-helix ribbon mixing stirrer.

Tamarind gum can be further added in the step (2) of the method.

The application of the polyurethane thickener in the preparation of the composite active printing paste also belongs to the protection scope of the invention.

The invention also provides application of the polyurethane composite reactive printing paste in cotton reactive printing.

When the polyurethane composite active printing paste is used for cotton active printing, the addition amount of the polyurethane composite active printing paste in color paste can be 0.8-1.2% (viscosity adjustment according to actual needs).

The invention has the following benefits:

1) the polyurethane thickener provided by the invention is a high molecular compound with a branched chain, has a three-dimensional structure association, has higher thickening capacity and a lower PVI value, is easier to print patterns with high definition in cotton reactive printing, greatly reduces the printing cost by compounding the carboxymethyl guar gum and the tamarind gum with high pasting rate, and simultaneously reduces the waste discharge amount.

2) The polyurethane composite paste provided by the invention contains a large amount of carboxyl and a small amount of hydroxyl, and does not react with reactive dye, the color yield can be improved by about 20% at most compared with that of sodium alginate, the cost of dye and chemical materials is saved, and meanwhile, the existence of carboxyl provides a convenient condition for de-pasting, so that the printed fabric has softer hand feeling, and the post-finishing of the hand feeling style of the fabric is facilitated.

3) The polyurethane composite paste provided by the invention not only meets the requirement of environmental protection, but also has a printing effect which is comprehensively better than that of sodium alginate sold in the market, and meanwhile, the cost can be saved by 20-30%, and the polyurethane composite paste is a high-cost-performance composite active paste capable of completely replacing the sodium alginate.

Drawings

FIG. 1 is a paste yield curve of each paste in example 5 of the present invention.

Detailed Description

The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, biomaterials, etc. used in the following examples are commercially available unless otherwise specified.

The polyurethane thickener used in the examples described below was FK-168C, available from Peking Middo chemical Co., Ltd;

the acrylic composite paste used in the following examples was a mixture of an acrylic thickener F-RP and sodium alginate in a mass ratio of 1:2, the acrylic thickener F-RP being available from Pasteur;

the test method of the printing performance indexes of the composite paste and the sodium alginate prepared in the following examples is as follows:

printing experiment

1. Material distribution: the textile used is pure cotton plain weave fabric which is desized, boiled and bleached

2. Printing formula:

name (R)	Printing prescription
		Dye material	5％
Anti-dyeing salt	3％
		Urea	5％
Baking soda	3％
		Water (W)	x％
Paste material	y％
		Total of	100％

Note: the amount of each material is the percentage of the total amount of the color paste

3. Printing process

Paste preparation → color paste preparation (color paste viscosity 800Pa.s) → flat screen printing (screen 120 mesh, magnetic rod pressure 35, vehicle speed 25) → drying (100 ℃. 4min) → steaming (103 ℃. 8min) → cold water soap boiling (4 min; dessicant FK-0134. about.1 g/l) → cold water soap drying (80 ℃.) → standing for 10min → test.

4. Index testing

4.1 viscosity measurement

Weighing the paste according to a certain proportion, dispersing the paste into cold water under the stirring of a stirrer, continuously stirring for 1h, puffing for 4h, and then testing at different rotating speeds by using an NDJ-8S viscometerViscosity of raw paste, and according to formula PVI η₆₀/η₁₀The PVI value of the raw paste is calculated.

4.2 Water holding Property test

First, a 1% concentration base paste was prepared, and then a 10cm by lcm length and width piece of insert marked quantitative filter paper was inserted into the paste at lcm (just as the paste was lined with the score lines). Immediately after the insertion, the time was started, and the water height was recorded at 30 min.

4.3 storage stability and salt stability testing

Placing the prepared raw paste into a constant-temperature water bath kettle at 40 ℃, preparing salt tolerance determination paste according to the proportion of 50% of the raw paste, 4% of baking soda and 46% of deionized water, placing the raw paste and the salt tolerance determination paste into a constant-temperature water bath kettle at 25 ℃, respectively testing the viscosity of the raw paste and the salt tolerance determination paste before and after 24 hours, and calculating the viscosity reduction rate, wherein the larger the viscosity reduction rate is, the poorer the storage stability or the salt tolerance stability of the raw paste is.

4.4 Depasting Rate test

The paste removal rate is one of important indexes for representing the hand feeling of the printed fabric, the paste removal rate is not only related to the printing process, but also depends on the characteristics of paste, the printed fabric with high paste removal rate has soft hand feeling, and the paste removal rate is expressed as (m ═ m [% ]₂-m₃)/(m₂-m₁) Calculating the rate of paste removal by 100%, wherein m₁、m₂、m₃The dry weight/g of the fabric before printing, after printing and after soaping are respectively.

4.5 apparent color yield and permeability test

Using colorimeters at D₆₅Respectively testing the color depth (K/S) of the front surface of the printed fabric under the conditions of a light source and a standard of 10 DEG_{Is just}) And reverse color depth (K/S)_{Inverse direction}) The greater the K/S value, the deeper the apparent color yield, and the% permeability by formula (K/S) (%)_{Inverse direction})/(K/S_{Is just}) 100% the permeability of the paste was calculated.

4.6 color fastness to rubbing test

Grading with reference to GB/T3920-2008 'color fastness to rubbing' test for textile color fastness