JPS5836276A - Printing aid and method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a textile printing aid and a textile printing method.

More specifically, the present invention relates to a printing aid used for polyester fiber materials and a printing method.

Conventionally, in textile printing, a printing paste containing a water-soluble paste, a disperse dye, and other chemicals is printed on a fabric such as polyester, and after drying, the printing paste is heated at 110 to 140°C using high-pressure saturated steam.
The mainstream has been the so-called high-pressure steaming method, in which the film is steamed for 20 to 40 minutes to fix the film.

Recently, in order to streamline the process, atmospheric pressure high temperature steaming method or thermosol method, which allows continuous fixing, has been used. However, in both the normal pressure high temperature steaming method and the thermosol method, the dye density is significantly lower than in the high pressure steaming method.

In order to improve this problem, nonionic surfactants such as ether-type compounds at both ends of a polyoxine alkylene chain and polyoxyalkylene ethers of phenols are used. 'However, when a printing paste containing these nonionic surfactants is used, the dyed product has insufficient sharpness and deep dyeing properties because of its good permeability.

The present inventors have arrived at the present invention as a result of studies aimed at solving such problems in textile printing and dyeing. That is, the present invention provides (A) a water-soluble or water-dispersible polyoxyalkylene nonionic surfactant and (B) a hydrophilic group-containing ethylenically unsaturated monomer (bl) or (bl) and other ethylenically Water-soluble or water-dispersible (
co)polymer (referring to a polymer or/and copolymer) (
A printing aid (first invention) used in polyester fiber materials (having a molecular weight of 10,000 to 1,000,000); (A) a water-soluble or water-dispersible polyoxyalkylene nonionic surfactant; and (B) Hydrophilic group-containing ethylenically unsaturated monomer (bl) or a water-soluble or water-dispersible mixture of (bl) and another ethylenically unsaturated monomer (b2)
Using a printing paste sputum containing a printing aid (C) consisting of a co)polymer (molecular weight is 10,000 to 1,000,000) and a thickening agent [D] selected from the group consisting of acid soda-based thickening agents. This is a method for printing a polyester fiber material (second invention), which is characterized by printing.

(B) in the hydrophilic group-containing ethylenically unsaturated monomer,
Hydrophilic groups include carboxyl group, carboxylic acid anhydride group,
Carboxylic acid base, sulfonic acid group, hydroxyl group, ether group,
Examples include amide groups, amino groups, and quaternary ammonium salts.

Examples of the hydrophilic group-containing ethylenically unsaturated monomer include the following. These can also be used as a mixture of two or more types.

1. Carboxyl group-containing monomers: monoethylenically unsaturated mono- or polycarboxylic acids such as (meth)acrylic acid (meaning acrylic acid and/or methacrylic acid. The same expressions will be used hereinafter), maleic acid, Fumaric acid, itaconic acid, crotonic acid.

2. Carboxylic anhydride group-containing monomer: monoethylenically unsaturated polycarboxylic anhydride such as maleic anhydride.

8. Carboxylic acid group-containing unit: Mo/xchiL/:/
Water-soluble salts of polyunsaturated mono- or polycarboxylic acids [alkali metal salts (Na salt, Ni salt, etc.), ammonium salts, amine salts (lower alkyl amine salts such as mono-, di- or trimethylamine, ethylamine, propylamine, etc.)] Mono- and Dimata are salts of alkanolamines such as triethanolamine and propatoolamine-heterocyclic amines such as morpholine), and salts include partial salts and complex salts (metal salts and non-metal salts such as ammonium salts and amine salts). For example, sodium (meth)acrylate, triethanolamine (meth)acrylate, sodium maleate, and methylamine maleate.

4. Monomers containing sulfonic acid groups: aliphatic or aromatic vinyl sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, vinyltoluene sulfonic acid, styrene sulfonic acid, (meth)acrylic sulfonic acids [sulfopropyl (
meth)acrylate, sodium 2-hydroxy-8-(meth)acryloxypropylsulfonate].

5. Sulfonic acid group-containing monomer: 4. above. Water-soluble salts (alkali metal salts) of monomers containing sulfonic acid groups.

For details on water-soluble salts such as ammonium salts and amine salts, please refer to the section for water-soluble salts in the section on carboxylic acid group-containing monomers).

6. Hydroxyl group-containing monomer: monoethylenically unsaturated alcohol such as (meth)allyl alcohol.

Monoethylenically unsaturated esters or ethers of polyols (alkylene glycols, glycerin, polyalkylene gelcols, etc.) such as hydroxypropyl (meth)acrylate.

Polyoxyethylene-oxypropylene (random or block) glycono-u(meth)allyl ether.

7. Amide group-containing monomer = (meth)acrylamide;
N-alkyl (meth)acrylamide, such as N-hexylacrylamide iN, N-dialkyl (meth)acrylamide, such as N,N-dimethylacrylamide, N,N-di n-'! or i-propylacrylamide; N-hydroxyalkyl (meth)acrylamide such as N-methylol (meth)acrylamide) IN
-Hydroxyethyl (meth)acrylamide iN,N-
Dihydroxyalkyl (meth)acrylamides such as N,N-dihydroxyethyl (meth)acrylamides and vinyl lactams such as N-vinylpyrrolidone.

8,7 Mino group-containing monomer: amino group-containing ester of monoethylenically unsaturated mono- or dicarboxylic acid (dialkylaminoalkyl ester, dihydroxyalkylaminoalkyl ester).

(morpholinoalkyl ester, etc.) For example, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, morpholinoethyl (meth)
Acrylates, dimethylaminoethyl fumarate; heterocyclic vinyl compounds such as vinylpyridines (2-vinylpyridine, 4-vinylpyridine, N-vinylpyridine), N-vinylimidazole.

9. Quaternary ammonium base-containing monomer: N, N.

N-) Realkyl-N-(meth)acryloyloxyalkyl ammonium salts jd: N, N.

N-)riethyl-N-(meth)acryloyloxyethylammonium chloride, 2-hydroxy-3-(meth)
Acryloyloxypropyltrimethylammonium chloride.

Among the above-mentioned monoethylenically unsaturated monomers having a hydrophilic group, carboxyl group-containing monomers are preferred, and acrylic acid is particularly preferred.

Methacrylic acid and combinations thereof.

Other ethylenically unsaturated monomers (b2) optionally used with (bl) include lower alkyl (0f-04) esters of unsaturated carboxylic acids [methyl (meth)acrylate, ethyl (meth)acrylate ], esters of monoethylenically unsaturated alcohols (vinyl acetate,
(allyl acetate, etc.) and nitrile group-containing monomers ((meth)acrylonitrile, etc.). Among these, preferred are lower alkyl (01-04) esters of unsaturated carboxylic acids and esters of monoethylenically unsaturated alcohols, and particularly preferred are methyl, ethyl or butyl acrylate and vinyl acetate.

In the (co)polymer (B), usually 20 mol% or more, preferably 8O-4=4-mol% in ethyl containing a hydrophilic group.
It is. If the amount of ethylenically unsaturated monomer units having a hydrophilic group is less than 20 mol %, deep dyeing properties and sharpness will be insufficient.

The (co)polymer may be produced by any conventional method.

For example, when using a water-soluble monomer, dissolve the monomer in water and use a hydrogen peroxide-based or ammonium persulfate-based redox catalyst, or a water-soluble azo catalyst such as azobiscyanovaleric acid. The polymerization is usually carried out at a temperature of 10 to 100°C, preferably 20 to 90°C.

During polymerization, a water-soluble organic solvent (methanol, ethanol, acetone, N,N-dimethylformamide, dimethyl sulfoxide, etc.) may be added as necessary. Furthermore, when using a monomer that does not dissolve in water, a water-dispersible polymer or copolymer can be produced by carrying out emulsion polymerization. That is, usually water is used as a medium, an emulsifier or a protective colloid is used, monomers are monomerized, and the monomers are polymerized at the above temperature using the above redox catalyst or water-soluble azo catalyst.

The average molecular weight of the (co)polymer (B) used in the present invention is 10,000 to 1,000,000, preferably 50,000 to 500,000.

If the average molecular weight is less than 10,000, the sharpness of the printed product will be insufficient, and if it exceeds 1,000,000, the desizing properties will be poor.

Examples of the polyoxyalkylene nonionic surfactant (A) include the following compounds. The number of carbon atoms in the alkyl group and fatty acid below is usually 6 to 20, preferably 8 to 1.
8, and the number of moles of AO added is usually 2 to 1001, preferably 2 to 50.

'(1) Holioxyalkylene alkylaryl ether: AO adduct of alkylphenol or alkylnaphthol having at least one alkyl group, such as octylphenol pool, dodecylphenol FiOQ (
l, dinonylphenol KOa, etc. [In the above and below, AO represents alkylene oxide, EO represents ethylene oxide, and PO represents propylene oxide. Moreover, the number within 0 indicates the number of moles. ].

(2) Holoxyalkylene alkyl ether: AO adduct of aliphatic alcohol (linear or branched natural or synthetic alcohol) For example, octyl alcohol EO
αQ1 decyl alcohol P O (5), coconut oil reduction 7
JL/D-LBO (5), carbon number 11, 18.1
5 synthetic mixed alcohol EO (5) P OQυ, oleyl alcohol come, ShiFJo (t2, etc. [Note: carbon number 11
, 18.15 synthetic mixture 7 Ru: I-k E O (5)
P Oαυ is obtained by sequentially adding 105 moles of Po and 11 moles of Po to the alcohol. ].

(3) Polyoxyalkylene polyhydric alcohol fatty acid ester: polyhydric alcohol or its intramolecular anhydride (glycerin,
AO adducts of esters of trimethylolpropane, pentaerythritol, sorbitan, sorbitol, sucrose, etc.) and fatty acids, such as sorbitan monolaurate E
000, sorbitan monooleate (EO(I)/PO
α1], sorbitan monostearate EO (to), sorbitan trioleate god, oleic acid monoglyceride POQO1 soybean oil fatty acid monopentaerythritol ester PO (3), (Note: Sorbitan monooleate (EO [/POQ (e) is sorbitan (4) Polyoxyalkylene styrenated aryl ether: Monocyclic phenol (such as a phenol having one or more alkyl groups) or polyoxyalkylene styrenated aryl ether. Ring phenol (2 aromatic rings)
Phenylphenol, such as phenylphenol,
cumylphenol.

AO adducts of reaction products (referred to as styrenated phenols) with 1 to 20 mol of alkylnaphthol tostyrene, such as styrenated (2 mol) phenol EoQ4
, ``Styrenated (4 mol) phenol E o'QQ P
O01) Note: Styrenated phenol (2 mol) BOQI is a compound with a structure in which 8010 mol is added to styrenated phenol obtained by reacting phenol and styrene at a molar ratio of 1:2. ).

(5) Polyoxyalkylene fatty acid ester: esterified product of fatty acid and darylkylene glycol, or AO adduct of fatty acid, such as mono- or diester of oleic acid and polyethylene glycol (molecular weight 600), stearic acid KO (4), etc.

(6) Polyoxyalkylene fatty acid amide: AO adduct of fatty acid amide, such as oleic acid amide EOαQ0 (7) Polyoxyalkylene alkylamine: AO adduct of alkylamine, such as stearylamine F! 0(
3).

(8) Polyoxyalkyl mercaptan: AO adduct of alkyl mercaptan, such as cetyl mercaptan B
O(5).

(9) Polyoxyethylene polyoxypropylene glycol: Pluronic type nonionic surfactant, for example,
EO adduct of polypropylene glycol (hereinafter referred to as PPG) (average molecular weight (i) 900-2900)
EO is usually 10 to 80% by weight, preferably 4% by weight in the molecule.
It accounts for 0 to 80% by weight. ) For example, PPG (West 1, 20
E040 wt% adduct of 0), PPG (-1,750)
A 50 wt % adduct of E O of W and an 80 wt % K O adduct of PPGCi2,050).

Polyoxyalkylene ethers of GO oils: AO adducts of castor oil or hydrogenated castor oil, such as castor oil EO
@, hydrogenated castor oil EOIPOQυ.

Polyoxyalkylene ethers of polyhydric alcohols with a valence of 0 η or more: sorbitan or AO adducts of sucrose, such as sorbitan PO..., sucrose EOOOPOQO0@polyoxyalkylene ethers whose amine system is a lyol: Tetronic type nonionic surfactants, such as EO adduct of polyoxypropylene alkylene diamine (+
804.704.707 (manufactured by Wyandotte), etc.).

Among these nonionic surfactants, preferred are polyoxyalkylene alkylaryl ether, polyoxyalkylene polyhydric alcohol fatty acid dixyl, and polyoxyalkylene ether of trivalent or higher polyhydric alcohol.

The auxiliary agent of the present invention consists of (A) and (B).

The ratio of (A) and (B) is solid content and is usually based on weight (A)
: (B) =1:0.1-8 preferably (A) :
(B)=1:0. s~2. (B) is 0
．． If there is less than 1, the sharpness of the printed finished product will decrease.8
As the size increases, the desizing properties decrease.

The auxiliary agent of the present invention can be used as an auxiliary agent for printing polyvarnish/chill based fiber materials. Examples of polyester fibers include polyester fibers (for example, polyethylene terephthalate fibers) and mixed fibers of polyester fibers (1) and other fibers (for example, cotton, wool, rayon, acrylic, nylon, acetate).

t t: Ho! ] Materials for the ester fiber include cotton, thread, tow, top, skein, and knitted fabric of the fiber.

Dyes used for printing and dyeing these fiber materials include disperse dyes or blended dyes of disperse dyes and acid dyes, reactive dyes and direct dyes. As the disperse dye, both azo dye and anthraquinone dye can be used.

When printing is carried out using the auxiliary agent of the present invention, the auxiliary agent is contained or added to the printing paste. An example of the formulation of a printing paste containing or adding the auxiliary agent of the present invention is as follows (% is weight %).

Original glue or aqueous sizing solution Usually 50-70% (usually 6-15% aqueous sizing solution) Dye Usually 0.05-70%
lO% Auxiliary agent of the present invention Usually 0.05-3%
Other drugs Appropriate amount of water
Remainder In the above, the content or addition amount of the auxiliary agent of the present invention in the printing paste cherry is preferably 0.1 to more than 0.1% by weight.

As the base glue, a glue (D) selected from the group consisting of locust bean gum, quabean gum, etherified starch, carboxydimethylcellulose, and alginate sorter is used. If a paste other than the above is used, print suitability 2 color development.

Desizing properties become poor. Semi-emulsion glues made by adding mineral spirits or the like to these glues can also be used. Other agents added to the printing paste include antifoaming agents such as octyl alcohol, tributyl phosphate, and silicone emulsion, reduction inhibitors such as sodium m-nitrobenzenesulfonate or sodium chlorate, and tartaric acid and citric acid. Examples include PH adjusting agents such as.

If the amount of the auxiliary agent of the present invention in the printing paste is less than 0.005%, it is difficult to obtain a print that is thick, clear, and has excellent sharpness, and if it is more than 8%, the desizing properties are poor.

Printing can be carried out by a conventional method, for example, by printing a printing paste onto a polyester fiber material and fixing it after drying. The printing method may be any conventional printing method, including screen printing, rotary screen printing, roll printing, and the like. Drying is usually at 100℃.
This can be done in 1 to 5 minutes. Examples of fixing treatment methods include normal pressure high temperature steaming method and thermosol method, but high pressure steaming method is also applicable. After fixing, it is washed with water, desized, then soaped, and then washed with water and dried.

The auxiliary agent of the present invention exhibits an excellent effect as a deep dyeing agent, and when a polyester fiber material is printed with a printing paste containing the auxiliary agent of the present invention, it can be printed using a normal pressure high temperature steaming method.

When printing is carried out using the thermosol method, a print that is dense, clear, and has excellent sharpness can be obtained, similar to the case using the high-pressure steaming method.

The present invention will be further explained below with reference to Production Examples and Examples.

In the examples, EO represents ethylene oxide and PO represents propylene oxide. Parts in the examples are parts by weight.

Example 1゜Acrylic acid polymer aqueous solution (solid content 41%) (Note 1) 50
0 g (!: Sorbitan monooleate EO (a) 50
0g was blended to obtain the auxiliary agent LOOOg of the present invention.

(Note 1.) 1 / Pour hot water aoog into 4 locolbens, add 850 g of 8096 acrylic acid aqueous solution, 8.
50 g of an aqueous catalyst solution containing 4 g of sodium persulfate was added dropwise from a separate dropping funnel over 2 hours while keeping the temperature in the Kolben at 80°C with stirring, and aged for 1 hour to obtain an average molecular weight of 8.
700 g of an aqueous acrylic acid polymer solution was obtained.

Example 2 Aqueous solution of acrylic acid and methacrylic acid copolymer (solid content 41
%; molar ratio of acrylic acid: methacrylic acid 1: 0.8B
) (Note 2) 500 g and nonylphenol EO
Q5500g was blended to obtain 1,000g of the auxiliary agent of the present invention.

(Note 2.) Pour 800 g of hot water into IZ four locolben, add 200 g of acrylic acid, and 80 g of methacrylic acid.
850 g of a monomer aqueous solution containing 8.4 g of sodium persulfate and 50 g of a catalyst aqueous solution containing 8.4 g of sodium persulfate were added dropwise from separate dropping funnels over 1 hour with stirring while maintaining the temperature in the Kolben at 80°C, and aged for 1 hour. , 700 g of an aqueous copolymer solution of acrylic acid and methacrylic acid having an average molecular weight of 110,000 was obtained.

Example 3 Emulsion copolymer of acrylic acid-methacrylic acid-ethyl acrylate (molar ratio 1:4.2:6.5) (solid content 48%) (Note 8) 500 g Tosorbitan monolaurate E 500 g of 0(5)P 0(3) was blended to obtain 1000 g of the auxiliary agent of the present invention.

(Note 8.) 240 g of water, 800 g of monomers (20 g of acrylic acid, 100 g of methacrylic acid, 180 g of ethyl acrylate), 1.2 g of potassium persulfate, 1.2 g of potassium persulfate, and 1.2 g of potassium persulfate. 0.5 g of acid soda and nonylphenol K O (445.5 g, total 6 g were prepared at room temperature,
A homogeneous monomer emulsion was obtained by stirring thoroughly.

60 g of the above monomer emulsion was left in the full pen, and 60 g of water was added thereto, and the temperature was raised to 80°C. The remaining monomer emulsion was added dropwise over a period of 2 hours using a dropper, and emulsion polymerization was carried out with stirring. Furthermore, 3 og of catalyst aqueous solution containing 0.8 g of potassium persulfate was added, and the mixture was aged at 85° C. for 2 hours to obtain 687.2 g of an emulsion copolymer having an average molecular weight of 850,000.

Example 4, methacrylic acid-vinyl acetate-butyl acrylate (molar ratio: 1:0.88:0.46) emulsion polymer (
Auxiliary agent 10 of the present invention was prepared by blending 500 g of sorbitan monooleate (solid content 48%) and 500 g of sorbitan monooleate E O (5).
00g was obtained.

(Note 4.) In 11 locolbens, add 240 g of water, 800 g of monomers (150 g of methacrylic acid, 50 g of vinyl acetate, 100 g of butyl acrylate), 1.2 g of potassium persulfate, emulsifier, and sodium alkyl diphenyl ether disulfonate (Sanded BL Sanyo). A total of 8 g of polyoxyethylene nonyl phenyl ether (Nonipol 400 (nonionic activator manufactured by Sanyo Chemical Industries)) was charged at room temperature and thoroughly stirred to form a uniform emulsion. 60 g of the monomer emulsion was left in the Kolben, 60 g of water was added thereto, and the temperature was raised to 80°C.The remaining monomer emulsion was added dropwise using a dropping funnel over 2 hours, and emulsion polymerization was carried out with stirring. 80 g of an aqueous catalyst solution containing 10 g of potassium persulfate was added, and the mixture was aged at 85° C. for 2 hours to produce an emulsion polymer with an average molecular weight of 280,000. Printing was performed on a polyester fiber material using the printing paste having the following printing conditions under the following printing conditions.

(1) Printing paste composition Original paste (Note 5.) 70 parts Dye 1 part Citric acid 0.8 parts Sodium chlorate 0.3 parts Auxiliary agent of the present invention 1 part Total 100 parts (Note 5) Original paste; Sorbitose C-5 (Processed starch-based sizing agent, manufactured by Skorten) 2.5%, Fine Gum MCMC
-2 (O-based glue, manufactured by Dai-Kogyo Seiyaku) 25%, Duck Algin NSPM (sodium alginate-based glue, manufactured by Kamogawa Kasei)
Aqueous solution containing 2.5% (2) Printing conditions (1) Wiping cloth: Polyester pongee (50 denier) (
11) Dye: Diamond Sprue KBFS (disperse dye made by Mitsubishi Hanasei) 011) Printing and drying: Print solid patterns and patterns with sharpness using a test autoscreen printing machine (manufactured by Tsujii Senki Kogyo). It was printed and dried at 100°C for 8 minutes.

OVI fixation: HTS steamer tester (manufactured by Showa Kikai Tsusho)
Normal pressure high temperature steaming was then carried out at 170° C. for 7 minutes.

(V) Soaping: After the fixing machine was washed with water and desized, it was treated with the following aqueous bath (Note 6) at 80°C for 5 minutes, and further washed with water and dried.

(Attention) Aqueous bath; Ione? l-RK-15 (manufactured by Sanyo Kasei Kogyo) IS/e, an aqueous bath containing 1%/l of caustic soda, and sodium hydrosulfide IV. Table 1 shows the results of evaluating the deep dyeing properties and sharpness of the prints obtained. Shown below.

Table -1゜ (Note 6.) Comparison part (a): Sorbitan oleate monoester E O (10) dynamic # 3 broom property comparison product (b): Nonylphenol E O (1b% r final age a Comparison part ( C): Sorbitan lauric acid monoester Eo
(St#p o(a) inquirer comparison section Cd) "Sorbitan oleate monoester E
O(5)←≠Salmon force (Note 7.) Evaluation method (1) Dense dyeing property 1 The color development rate of the obtained solid pattern print is measured by the surface optical density KZS value, and the case where no auxiliary agent is added is measured. The specific concentration was expressed as 100.

(II) Sharpness The obtained patterned prints exhibiting sharpness were visually evaluated.

Evaluation criteria ◎: Very good ○: Good

Claims (1)

[Claims] 14A), a water-soluble or water-dispersible polyoxyalkylene nonionic surfactant, and (B), a hydrophilic group-containing ethylenically unsaturated monomer (bl) or (bl), and others. A printing aid used in polyester fiber materials consisting of a water-soluble or water-dispersible (co)polymer (molecular weight is 10,000 to 1,000,000) with an ethylenically unsaturated monomer (b2) of . 2. (A), Water-soluble or water-dispersible polyoxyalkylene nonionic surfactant and (B), Hydrophilic group-containing ethylenically unsaturated monomer (BL)
, or (bl) and other ethylenically unsaturated monomers (b2
) A printing aid consisting of a water-bathable or water-dispersible (co)polymer (with a molecular weight of 10,000 to 1,000,000) with [C] and locust hean gum type and guahine gum type. A method for printing a polyester fiber material, which comprises printing using a printing paste containing a sizing agent (D) selected from the group consisting of etherified starch-based, carboxymethyl cellulose-based and alginate sorter-based sizing agents. 8. The method according to claim 2, wherein the content of (c) in the printing paste is 0.05 to 3% by weight. 4. The blending ratio of (A) and (B) is (A) on a weight basis
: (B)-1:o, i~8. The method according to claim 2 or 3. 5. The method according to any one of claims 2 to 4, wherein (bl) is a carboxyl group-containing ethylenically unsaturated monomer. 6. The method according to claim 5, wherein the carboxyl group-containing ethylenically unsaturated monomer is acrylic acid and/or methacrylic acid.