JPS5926713B2 - Auxiliary agent for printing and dyeing - Google Patents

Description

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

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

Conventionally, in textile printing, a printing paste containing a water-soluble paste, a disperse dye, and other chemicals is printed on a fabric (for example, polyester), and after drying, it is heated using high-pressure saturated steam to a temperature of 110 to 14
The mainstream has been the so-called high-pressure steaming method, which fixes by steaming at a temperature of 0° C. for 20 to 40 minutes.

Recently, due to rationalization of the process, methods such as the high temperature steaming method or the thermosol method, which allow continuous fixing, have 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, surfactants are used, such as polyoxyalkylene type nonionic surfactants, such as polyoxyalkylene terminal ether type compounds, phenol-type polyoxyalkylene ether compounds, etc. There is.

However, when a printing paste containing these nonionic surfactants is used, the permeability is good, resulting in insufficient sharpness of the dyed product and insufficient deep dyeing properties.

The present inventors have arrived at the present invention as a result of studies aimed at solving the problem of curling during textile printing and dyeing.

That is, the present invention provides a water-soluble compound having an oxyalkylene chain consisting of at least 20% by weight of an oxyethylene chain or an oxyethylene chain and a tooxypropylene chain in the molecule, and an aromatic nucleus consisting of one or two benzene rings. This is a printing and dyeing aid used for polyester fiber materials made of water-dispersible or water-dispersible polyester.

In the present invention, the water-soluble or water-dispersible polyester has at least 20% by weight of a polyoxyethylene chain or a polyoxyalkylene chain consisting of a polyoxyethylene chain and a polyoxypropylene chain in the molecule, and has an aromatic Examples include polyester having a core.

Such a polyester is a polyester of a polycarboxylic acid and a polyol, in which a compound having an aromatic nucleus is used as at least one of the polycarboxylic acid and the polyol, and a compound having an aromatic nucleus as at least one of the polyols is used. Polyoxyalkylene polyol [Polyoxyalkylene refers to polyoxyethylene or poly(oxyethylene-oxypropylene).

The same applies below].

Specific examples include (I) polyesters of aromatic polycarboxylic acid-containing polycarboxylic acids and polyoxyalkylene polyol-containing polyols, and polyesters of world aliphatic polycarboxylic acids and polyoxyalkylene-containing polyols having an aromatic nucleus. .

Among these, preferred is polyester (I).

Among the polycarboxylic acids, the aromatic polycarboxylic acids include phthalic acids (phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc.), diphenyl dicarboxylic acid, diphenyl ether carboxylic acid, naphthalene dicarboxylic acid, etc.; Examples include maleic acid, maleic anhydride, 7-malic acid, itaconic acid, adipic acid, cepatic acid, and thiodiglycolic acid.

Polycarboxylic acids other than those listed above include aliphatic oxypolycarboxylic acids (malic acid, oxyglutaric acid, tartaric acid, etc.)
can be given.

The above-mentioned polycarboxylic acids may also be lower (C1-C4) esters thereof.

Among the polycarboxylic acids, aromatic polycarboxylic acids are preferred, and phthalic acids (especially terephthalic acid) are particularly preferred.

Among polyols, examples of the polyoxyalkylene polyol include the following compounds.

(1) Aliphatic polyoxyalkylene polyol (1) Polyoxyalkylene polyol from polyhydric alcohol Polyhydric alcohols include glycols (ethylene glycol, phlopylene glycol, neohentyl glycol,
C2-C1 such as hexanediol and dodecanediol
8 glycol), glycerin, pentaerythritol,
Sorbitan, sucrose, etc. (11) Polyoxyalkylene polyols from partial or complete esters of polyhydric alcohols and aliphatic oxymonocarboxylic acids. Examples of such esters include di- or triesters of ricinoleic acid and glycerin. (m) Contains amino groups. Polyoxyalkylenepolyol from aliphatic compoundsAmino group-containing aliphatic compounds include ammonia, C6-
(2) Aromatic polyoxyalkylene polyol (1) Polyoxyalkylene polyol derived from polyhydric phenol and bisphenol Polyhydric phenols include hydroquinone, catechol,
Resorcinol, pyrogallol, etc.; bisphenol such as bisphenol A (11) aromatic polycarboxylic acid or aromatic oxy(
Polyoxyalkylene polyols from mono- and polycarboxylic acids Examples of aromatic polycarboxylic acids include the aromatic polycarboxylic acids described in the section on polycarboxylic acids, and examples of aromatic oxycarboxylic acids include salicylic acid, m-oxybenzoic acid, and Frenchin. Among the polyoxyalkylene polyols mentioned above, preferred are aliphatic polyoxyalkylene polyols, and particularly preferred are polyoxyalkylene polyols such as aromatic oxymonocarboxylic acids such as 2,3-dioxybenzoic acid, resorcinic acid, and gallic acid. Polyoxyalkylene polyols made from partial or complete esters of alcohols and aliphatic oxymonocarboxylic acids.

As the polyol, the above-mentioned low-molecular polyhydric alcohols (ethylene glycol, propylene gellicol, glycerin, pentaerythritol, etc.) can be used in part if necessary.

A monocarboxylic acid can also be used as part of the polycarboxylic acid if necessary.

Such monocarboxylic acids include aliphatic monocarboxylic acids (propionic acid, palmitic acid, oleic acid, etc.), aromatic monocarboxylic acids (benzoic acid, aromatic acid, etc.), the above-mentioned aromatic oxymonocarboxylic acids, aliphatic oxymonocarboxylic acids, etc. Examples include carboxylic acids (glycolic acid, ricinoleic acid, 9-oxy-12-octadecenoic acid, etc.) and amino acids (glycine, alanine, serine, etc.).

The water-soluble or water-dispersible polyester in the present invention has a molecular weight of at least 20%, preferably 20 to 98% by weight.
% by weight, particularly preferably from 50 to 95% by weight of polyoxyalkylene chains.

The content of polyoxyethylene chains in the polyoxyalkylene chains is usually 50% by weight or more, preferably 70 to 10% by weight.
It is 0% by weight.

20 polyoxyalkylene chains in the polyester compound
If the amount is less than 0.5% by weight, or if the polyoxyethylene chain is less than 0.50% by weight in the polyoxyalkylene chain, the solubility or dispersibility in water will decrease, resulting in poor level dyeing of the finished print.

When the polyoxyalkylene chain in the polyester is composed of an oxyethylene chain and an oxypropylene chain, these two types of oxyalkylene chains may be present in either random or block form.

When producing polyester in the present invention, the molar ratio of polycarboxylic acid and polyol is usually 1:0.2 to
2.0, preferably 1:0.1-1.2.

Manufacturing can be carried out in a conventional manner.

For example, a polyester compound may be obtained by reacting a polycarboxylic acid and a polyol (or a polyester may be obtained by reacting a polycarboxylic acid with a polyhydric alcohol having no polyoxyalkylene group, and then a polyester compound may be obtained by reacting a polycarboxylic acid with a polyhydric alcohol that does not have a polyoxyalkylene group, An oxide may be added.

The molecular weight of polyester compounds is usually 1500 to 5000
0, preferably 1,500 to 30,000.

When the molecular weight exceeds 50,000, water solubility or water dispersibility decreases.

Moreover, if it is less than 1500, the sharpness decreases.

□The auxiliary agent of the present invention can be applied to polyester fiber materials.

Examples of the polyester fibers include polyester fibers (for example, polyethylene terephthalate fibers) and mixed fibers of these fibers and other fibers (for example, cotton, wool, rayon, acrylic, nylon, acetate).

Materials for polyester fibers include cotton, thread,
Examples include tow, top, skein, and knitted fabric.

Dyes used for printing and dyeing these fiber materials include disperse dyes and blended dyes of disperse dyes and acid dyes, reactive dyes, and direct dyes.

The above dyes can also be used in combination. As the disperse dye, both azo and anthraquinone dyes can be used.

When printing is carried out using the auxiliary agent of the present invention, it is carried out by containing or adding it to a commonly used printing paste solution.

1. Prescription of printing paste containing or adding the auxiliary agent of the present invention
An example is as follows.

Original glue or sizing agent water Usually 50 to 70% by weight solution (usually 5 to 15% by weight aqueous solution of sizing agent) Dye // 0.05 to 10 Auxiliary agent of the present invention 0.05 to 10 Other agents Fine In the above, the content or addition amount of the auxiliary agent of the present invention in the printing paste solution is preferably 0.1 to 5% by weight.

Examples of the sizing component used in the base glue include locust pea gum, guabean gum, etherified starch, CMC, and sodium alginate, and semi-emulsion glues prepared by adding mineral spirits and the like to these sizing agents.

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 and sodium chlorate;
Examples include PH adjusters such as tartaric acid and citric acid.

When printing is performed using the above-mentioned printing paste, a conventional method is used.

For example, printing is carried out by printing a printing paste liquid onto a polyester fiber material, drying it, and then fixing it.

The printing method may be any conventional printing method, and typical examples include screen printing, rotary screen printing, roll printing, and the like.

Drying is performed, for example, at 100° C. for 1 to 5 minutes.

Specific treatment methods include normal pressure high temperature steaming method and thermosol method.

A high pressure steaming method can also be applied.

After fixing, wash with water, de-glue, soap, wash with water,
Perform drying.

The auxiliary agent of the present invention is usually contained or added to the printing paste solution, but it may also be blended in advance into a dye such as a disperse dye.

The auxiliary agent of the present invention exhibits excellent effects as a deep dyeing and leveling dye,
Prints printed with the printing paste containing the auxiliary agent of the present invention are thick, clear, and have excellent sharpness.

The auxiliaries of the invention can also be used as auxiliaries for pad dyeing of polyester fiber materials.

Dyeings that are pad-dyed in a pad bath containing the auxiliary agent of the present invention are rich, vivid, and have excellent level dyeing properties.

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

In the production examples and examples, parts indicate parts by weight, % indicates weight %, EO indicates ethylene oxide, and PO indicates propylene oxide.

Production Example 1 (1) Auxiliary agent (a) of the present invention (polyester compound of terephthalic acid and ricinoleic acid diglyceride EO adduct) 652 parts of ricinoleic acid diglyceride and 4 parts of caustic potassium were charged into an autoclave reaction vessel, and dehydrated under reduced pressure. After purging with nitrogen, 1232 parts of EO was added at 170 to 190° C. and 5 kg/c for neutralization by aging.

1886 parts of an EO adduct of ricinoleic acid diglyceride in the form of a pale yellow paste was obtained at 25°C.

1,884 parts of this adduct were placed in a flask with a plate, 213 parts of dimethyl terephthalate and 6 parts of bistributyltin oxide were added thereto, and the temperature was raised to 160°C over 2 hours. The esterification reaction was carried out by demethanol reaction for about 2 hours, then the temperature was raised to 210°C, the pressure was reduced to 10 to 20ml/LHg1, and the ester polymerization reaction was carried out for 2 hours.
2023 parts of a pale yellowish brown viscous paste polyester compound vAa) of 0.00 cps was obtained.

The content of polyoxyethylene chains in the molecule of this polyester compound (a) was about 60%, and it was dissolved in water.

The polyester (a) is used as assistant Ra) of the present invention.

(2) Auxiliary agent (b) of the present invention (Polyester compound of terephthalic acid and polyethylene glycol) 194 parts of dimethyl terephthalate and 1500 parts of polyethylene glycol having a molecular weight of 1500 are mixed with 0.5 part of zinc acetate and 0.2 part of antimony oxide. It was then placed in an autoclave and heated while passing nitrogen through it, which took 2 hours to complete.
The temperature was raised to 0°C, and methanol was distilled off.

After methanol distillation, the temperature was raised to 230° C., and the pressure was gradually reduced to 5 mmHg over 1 hour, and the reaction was continued in this state for 2 hours.

The obtained polyester (b) was a pale brown solid at 25°C, the content of polyoxyethylene chains in the molecule was about 80%, and it was dispersed in water.

The polyester compound (b) is used as the auxiliary agent (b) of the present invention.

(3) Auxiliary agent (C) of the present invention (polyester compound of adipic acid and EO adduct of 2,3-dioxybenzoic acid) Add 1 of 2,3-dioxybenzoic acid to an autoclave reaction pot.
54 parts of caustic potassium and 5 parts of caustic potash were charged, dehydrated under reduced pressure, and then replaced with nitrogen.
2420 parts were added and neutralized by aging.

At 25°C, 2,575 parts of a pale yellowish brown solid adduct was obtained.

2,574 parts of this adduct were placed in a flask with a plate, and 175 parts of adipic acid and 5 parts of bistributyltin oxide were added thereto as a catalyst.Then, the temperature was raised to 180°C over 2 hours, and then at 180°C for 3 hours. An esterification reaction is carried out by dehydration network, then the temperature is raised to 220°C, the pressure is reduced to 2 mmHg, and an ester polymerization reaction is carried out for 2 hours to form a polyester compound (
c) 2725 parts were obtained.

The content of polyoxyethylene chains in the molecule of this polyester compound was about 90%, and it was dissolved in water.

The polyester compound (e) is used as the auxiliary agent (e) of the present invention.

(4) Auxiliary agent (d) of the present invention and its derivative me) (EO adduct of polyester compound of terephthalic acid and glycerin) 582 parts of dimethyl terephthalate, 248 parts of glycerin, and 4 parts of lead oxide were charged in a flask with a plate. ℃ to 3
Esterification was carried out by a demethanol reaction at 160° C. for 5 hours, which took some time, and after cooling, the mixture was neutralized with 12 parts of a 30% aqueous solution of caustic soda.

840 parts of brown viscous polyester was obtained at 25°C.

830 parts of this polyester compound was charged into an autoclave reaction pot along with 5 parts of caustic potash at 110°C and 10 mm.
170-190 after dehydration under reduced pressure with Hg and then replacing with nitrogen
℃, 396 parts of EO was added at s kg/c4 or less to neutralize by aging.

Polyester compound (d) in brown viscous paste at 25°C
1225 copies were obtained.

The content of polyoxyethylene chains in the molecule of this polyester compound kd) was about 31%, and it was dissolved in water.

The polyester compound (d) was used as the auxiliary agent (d) of the present invention.

(5) Auxiliary agent (e) of the present invention (Polyester compound of phthalic anhydride and stearylamine E O/P O random adduct) 538 parts of stearylamine and 6 parts of caustic potassium were charged into an autoclave reaction vessel and dehydrated under reduced pressure. Next, after nitrogen substitution, 160-180'
4400 parts of EO and PO58 below C15kg/crA
0 parts were uniformly mixed in a liquefied state and the entire amount was added to obtain 5520 parts of stearylamine EO/PO random adduct which was a pale yellow solid at room temperature.

Next, 4140 parts of this adduct was placed in a flask, 148 parts of phthalic anhydride and 8 parts of tin chloride were added as a catalyst, and the temperature was raised to 180°C over 4 hours.
The pressure was reduced to mHg and ester polymerization reaction was carried out for 4 hours to obtain 4296 parts of polyester compound (e).

The content of polyoxyethylene chains in the molecule of this polyester compound [e) was about 56%, and it was dissolved in water.

The polyester compound vlXe) is referred to as assistant Re) of the present invention.

(6) Auxiliary agent of the present invention) (Polyester compound of adipic acid and EO adduct of bisphenol A) 456 parts of bisphenol A and 2 parts of caustic potassium were charged into an autoclave reaction vessel, dehydrated under reduced pressure, then replaced with nitrogen, and then 2,640 parts of EO was added at 170 to 190°C to form a pale yellowish brown paste-like bisphenol AEO adduct 3.
A 9° portion was obtained.

Take 300 parts of this adduct into a branch flask, add 262 parts of adipic acid and 6 parts of tin chloride as a catalyst, and heat to 180°C.
The mixture was further reacted at 200° C. for 3 hours under a reduced pressure of 10 mmHg to obtain 3,120 parts of polyester compound (f).

The content of polyoxyethylene chains in the molecule of this polyester compound vAf) was about 84%, and it was dissolved in water.

The polyester compound (g) is used as the auxiliary agent (f) of the present invention.

(Auxiliary layer g of the present invention) (Polyester compound of 1.5 naphthalene dicarboxylic acid and polyethylene glycol) 1.5 naphthalene dicarboxylic acid dimethyl ester 216
polyethylene glycol 20 parts and molecular weight 2000
00 parts was placed in an autoclave with 0.5 parts of zinc acetate and 0.2 parts of antimony oxide and heated while passing nitrogen.
It took some time to raise the temperature to 180°C, and methanol was distilled off.

After methanol distillation, the temperature was raised to 230° C., and the pressure was gradually reduced to 5 mmHg over 1 hour, and the reaction was allowed to proceed for 2 hours under these conditions.

The obtained polyester (g) was a pale brown solid at 25°C, the content of polyoxyethylene chains in the molecule was about 90%, and it was dispersed in water.

The polyester compound g) is referred to as assistant Rg) of the present invention.

(8) Sublayer h) of the present invention (polyester compound of terephthalic acid and EO adduct of bisphenol A)
A 050 molar adduct was made.

2,428 parts of this adduct, 194 parts of dimethyl terephthalate, and 10 parts of bistributyltin oxide as a catalyst were charged into an autoclave, and heated while passing nitrogen.
The temperature was raised to 0° C. for 2 hours, and methanol was distilled off.

After methanol distillation, the temperature was raised to 230° C., and the pressure was gradually reduced for 1 hour, and the reaction was made to 5 parts mHg for 2 hours under these conditions.

The obtained polyester A(h) was a light yellow solid at 25°C, the content of polyoxyethylene chains in the molecule was about 85%, and it was dispersed in water.

The polyester compound h) is the auxiliary layer h) of the invention.

(9) Sub-R1 of the present invention) (Polyester compound of adipic acid and EO adduct of 1,3 naphthalene diol) A 45 mol adduct of EOo of 1,3 naphthalene diol was prepared in the same manner as Sub-Rf) of the present invention. Created.

2,148 parts of this adduct, 146 parts of adipic acid, and 5 parts of bis) IJ butyltin oxide as a catalyst were charged into an autoclave, heated while passing nitrogen, heated to 180°C for 2 hours, and dehydrated at 180°C for 3 hours. Esterification reaction is carried out by network, then the temperature is raised to 220℃ and 3 m
The pressure was reduced to mHg, and the ester polymerization reaction was carried out for 3 hours.

The obtained polyester (i) was light brown and viscous at 25°C, the content of polyoxyethylene chains in the molecule was 87%, and it was dispersed in water.

The polyester compound starch i) is referred to as the aid Mi) of the present invention.

Example 1 Printing of polyester fiber material Using a printing paste having the following composition, printing, drying, fixing and soaping were carried out under the following printing conditions.

(1) Printing paste composition; Original paste (*1) 70 parts dye
1 part citric acid 0.3 part sodium chlorate 0.3 part Auxiliary agent of the present invention
1 part water Total remaining 100 parts Motogori;
Sorbitose C-5 (modified starch paste, manufactured by Skolten) 2.5% Fine Gum MCMC-2 (C paste, manufactured by Dai-Kogyo Seiyaku) 2.5% Printex ZETA (guar-based gum paste, Lamperti) Aqueous solution containing 2.5% (2) Printing conditions (1) Wiping cloth; polyester processed yarn fabric Amundsen (2)
Dye: Dianic Sprue KBFS (manufactured by Mitsubishi Kasei) (3) Printing and drying: Using a test auto screen printing machine (manufactured by Tsujii Senko Kogyo), print a solid pattern and a pattern that shows sharpness, It was dried at 100°C for 3 minutes.

(4) Fixation: High temperature steaming at normal pressure was performed at 170° C. for 7 minutes using an HTS steamer tester (manufactured by Showa Kikai Tsusho).

(5) Soaping: After fixing, the product was washed with water to remove the size, and then treated with the following aqueous bath (*2) at 80°C for 5 minutes, and further washed with water and dried.

*2 Aqueous bath; Ionetsu) RK-15 (Seisei Kasei) Is'/l Caustic soda 1 g/l Sodium hydrosulfide 1 ? Performance of the printed product obtained from the aqueous bath containing /l (deep dyeing property, sharpness and desizing property)
The results of the evaluation are shown in Table 1.

Note that nonylphenol EO(1,0) is a nonylphenol EOIO molar adduct.

The same description will be used below.

Evaluation method (same as Examples 1 and 2) (1) Deep dyeing property The color development rate of the obtained solid pattern print is measured by the surface optical density /S value, and the case where no auxiliary agent is added is set as 100. Expressed as specific concentration.

(11) Sharpness The resulting printed pattern showing sharpness was visually evaluated.

Evaluation criteria: ◯; Good △; Fair ×; Poor. Desizing property The texture of the obtained solid pattern print was evaluated by the touch of the hand.

Evaluation criteria: ○; Good △; Fair
2.5% Fine Gum MCMC-2 (C-based glue, manufactured by Dai-Kogyo Seiyaku) 2.5% Duck Algin NSPM (sodium alginate manufactured by Kamogawa Kasei) 2.5% Polyester Georgette (50 denier) with a wiping cloth Next, printing was carried out in the same manner as in Example 1 except that the dye was changed to Diamond X Brown G-8E (manufactured by Mitsubishi Kasei), and the obtained printed material was evaluated.

Claims (1)

[Claims] 1. A polyester of an aromatic polycarboxylic acid-containing polycarboxylic acid having one or two benzene rings and a polyoxyalkylene-containing polyol, and an aromatic compound consisting of an aliphatic polycarboxylic acid and one or two benzene rings. polyoxyalkylene polyol having a group nucleus, containing at least 20% by weight of an oxyalkylene chain or an oxyalkylene chain consisting of an oxyethylene chain and an oxypropylene chain in the molecule. A printing and dyeing aid used for polyester fiber materials made of water-soluble or water-dispersible polyester. 2. The auxiliary agent according to claim 1, wherein the polyester has a molecular weight of 1,500 to 50,000. 3 The content of polyoxyalkylene chains is 20 in one molecule.
98% by weight of the auxiliary agent according to any one of claims 1 to 2. 4. The auxiliary agent according to any one of claims 1 to 3, wherein the content of polyoxyethylene chains is 50% by weight or more in the polyoxyalkylene chains.