JPS5825796B2 - Discharge aid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel discharge printing aid, and more particularly to a discharge printing aid containing a lower alkylene oxide adduct of a benzenesulfonamide derivative as an active ingredient.

Conventionally, thiodiethylene glycol (and other glycol)-based discharge aids have been widely used in order to enhance the discharge printing effect of ground-dyed fabrics, but the discharge printing effect is still not fully satisfactory, and there is also a tendency to There were drawbacks such as the inability to completely prevent the phenomenon.

This time, according to the present invention, a lower alkylene oxide adduct of a certain benzenesulfonamide derivative significantly improves the flow permeability of the discharge printing paste into the hanging fabric, and significantly improves the discharge printing effect of ground dyeing using the discharge printing agent. It has been found that it can effectively prevent the tearing phenomenon and provide discharge prints with clear edges.

Thus, according to the present invention, the general formula [wherein R1 and R2 each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkyl group]; R3 is a hydrogen atom, There is provided a discharge printing aid comprising at least one adduct of 1 to 50 moles of lower alkylene oxide of a benzenesulfonamide derivative represented by a lower alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

The characteristics and advantages of the discharge printing aid provided by the present invention can be summarized as follows: (1) The aid of the present invention can be used in place of glycol-based aids such as thiodiethylene glycol commonly used in discharge printing pastes. When used, the properties of the discharge printing paste, such as flowability and permeability into the fabric, are improved, and the penetration of the discharge printing paste into the interior of the fibers is significantly improved compared to the conventional discharge printing paste, and as a result, the inclusions in the discharge printing paste are improved. The discharge printing effect by the discharging agent is greatly improved.

the result. Excellent white discharge printing effect can be obtained.

(2) On the other hand, the compound of the above formula (I) also has an extremely excellent ability to dissolve dyes (this ability as a dye solubilizer was previously proposed in Japanese Patent Application No. 51-92754). Therefore, when the auxiliary agent of the present invention is used in a colored discharge printing paste, it is possible to increase the dye density of the colored discharge printing area, and at the same time, it is possible to obtain a pure and clear discharge print.

(3) Furthermore, since the auxiliary agent of the present invention has the effect of increasing the penetration power of the discharge printing paste into the fabric, when the discharge printing paste containing the auxiliary agent of the present invention is applied to the fabric, it will adhere to the surface of the fabric. The discharge printing glue layer can be made thinner.

In this way, especially when discharging is carried out using an automatic screen printing machine, the phenomenon of close contact between printed parts due to stamping is reduced, and accidents caused by the printing process can be reduced.

(4) As mentioned above, the auxiliary agent of the present invention can significantly improve the discharge printing effect of the discharge printing agent, so it can achieve the same level of discharge printing effect as when using the conventionally used glycol-based auxiliary agent. The amount of discharge agent required to achieve this can be significantly reduced (reductions by about 20% or more possible).

As a result, there is less reduction in the strength of the discharge printing paste coating in the printed area due to recrystallization of the discharge printing agent after printing and drying, and therefore, the rubbing of the fabric before printing and steaming the dried printed fabric, etc. The rate of pollution accidents caused by this can be greatly reduced.

(5) As described in the detailed description of the present invention, the edges of the printed and discharged parts are significantly clearer than those using conventional glycol-based auxiliary agents, improving the quality of discharge prints. became possible.

Furthermore, it has become possible to easily print fine dot patterns, which were conventionally considered difficult especially when using automatic screen printing machines.

In the above general formula (I), examples of halogen atoms include chlorine, bromine, iodine and fluorine, particularly chlorine and bromine, and lower alkyl groups include linear or branched carbon atoms having 1 to 4 carbon atoms. Chain alkyl group 1 such as methyl, ethyl,
n or iso propyl, n, iso
, sec or tert butyl, etc., and lower alkoxy groups include those in which the alkyl moiety is linear or branched with 1 to 4 carbon atoms, such as methoxy, ethoxy, n- or 1so-propoxy, n
-1so- or tert-butoxy, etc.,
As the lower haloalkyl group, trifluoromethyl is particularly preferred.

As the cycloalkyl group, those having 10 carbon atoms, particularly those having 5 to 6 carbon atoms are preferable, such as cyclopentyl,
Examples of the aryl group include substituted or unsubstituted phenyl, especially phenyl, tolyl, xylyl, or substituted or unsubstituted naphthyl, especially naphthyl. Representative examples of the aralkyl group include: Includes benzyl, phenethyl and the like.

Furthermore, as the lower alkylene oxide to be added to the benzenesulfonamide derivative of the above formula (I), those having 5 carbon atoms, particularly 2 to 4 carbon atoms, are suitable, such as ethylene oxide, propylene oxide, 2, 3
-dimethylethylene oxide, among others, ethylene oxide and propylene oxide are preferred.

These lower alkylene oxides can be added individually, or in the form of a composite adduct of two or more types.

The number of moles of the lower alkylene oxide added is determined by the formula (I
) 1 to 1 mole of benzenesulfonamide derivative
It can be 50 mol, preferably 1 to 30 mol, especially 1 to 25 mol, and when two or more lower alkylene oxides are added, the total amount can be in the above range.

Thus, adducts that can be suitably used in the present invention include:
Formula [wherein R11 and R21 are each independently a hydrogen atom,
represents a halogen atom or a lower alkyl group, and R31 represents a hydrogen atom, a lower alkyl group, or a phenyl group. [In the formula, R1□ represents a hydrogen atom, a chlorine atom, a methyl group, or an ethyl group, and R3□ represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ~
It is a 30 molar adduct.

The above formula (I) or (■-a) that can be used in the present invention
Or, representative examples (adducts) of the compound (I-b) are as follows.

2 to 15 moles of ethylene oxide adduct of benzenesulfonamide; 2 to 20 moles of ethylene oxide adduct of 〇- or p-chlorobenzenesulfonamide.

2 to 20 mole ethylene oxide adduct of o- or p-toluenesulfonamide.

o, p-Dimethylbenzenesulfonamide adduct with 4 to 30 moles of ethylene oxide.

〇- or p-ethylbenzenesulfonamide adduct with 2 to 30 moles of ethylene oxide, o, p-diethylbenzenesulfonamide with 6 to 40 mole ethylene oxide adduct.

Ethylene oxy7 of o- or p-toluenesulfonamide
12-20 mol and propylene oxy 12-10 mol mixed adduct, 2-10 mol propylene oxide adduct of o- or hap-)luenesulfonamide, 4-30 mol N-ethyl-p-toluenesulfonamitonoethylene oxide Adduct, ethylene oxide of benzenesulfonanilide 4-50
molar adduct, 0 sp-dichlorobenzenesulfonamide with 4 to 30 moles of ethylene oxide, 〇- or p-butylbenzenesulfonamide with 6 to 40 moles of ethylene oxide, 〇- or p-methoxybenzenesulfonamide with 3 to 40 moles of ethylene oxide. 25 mole adduct of o,p-dimethoxybenzenesulfonamide with 4 to 30 moles of ethylene oxide, o-or 1t'r-p-ethoxybenzenesulfonamide with 4 to 30 mole of ethylene oxide adduct, Osp'/ethoxy7benzene 6 to 35 mole ethylene oxide adduct of sulfonamide, 6 to 35 mole ethylene oxide adduct of o- or p-butoxybenzenesulfonamide, 6 to 40 mole ethylene oxide adduct of osp-dibutoxybenzenesulfonamide, o- or p- 4-30 mole ethylene oxide adduct of 4-trifluoromethylbenzenesulfonamide.

3 to 30 moles of ethylene oxide adduct of N-methylbenzenesulfonamide, 4 to 35 moles of N-ethylbenzenesulfonamide ethylene oxide adduct, 6 to 50 moles of ethylene oxide adduct of N-butylbenzenesulfonamide, N-cyclohexylbenzenesulfonamide 716 to 50 moles of ethylene oxide adduct of □, 4 to 50 moles of ethylene oxide adduct of o- or p-toluenesulfonanilide, 6 to 50 moles of ethylene oxide adduct of N-phenylethylbenzenesulfonamide, N-hensyl-o- or 5-50 mole ethylene oxide adduct of hap-)luenesulfonamide.

8-50 mole ethylene oxide adduct of N-naphthyl-benzenesulfonamide, etc.

The compound represented by the above formula (I) is, for example, [wherein R1
, R2 and R3 are as defined above], one or more lower alkylene oxy7
or ν [wherein, X represents a rogen atom, especially a chlorine atom,
R1 and R2 are 9 as defined above] The compound is reacted with a mono- or di(lower alkanol) amine, and the resulting product is optionally added with one or more lower alkylene oxides. Do you want me to do it?
Alternatively, it can be easily produced by condensing the compound [wherein R1, R2 and R3 are as defined above] with poly(lower alkylene) glycol monohalohydrin.

The reactions described in the above methods (a), (b) and (c) can be carried out by methods known per se, for example as described in British Patent No. 678,004, US Pat. No. 2,649,478, Chemical Abstracts No. 53. Volume No. 9114
This can be carried out by the method described in known documents such as column h and German Patent No. 938728.

When the lower alkylene oxide adduct of the benzenesulfonamide derivative of formula (I) is used as a discharge printing aid, it can be used alone or in combination of two or more to form a base paste, a discharge printing agent, and, if necessary, a colored discharge printing agent. A discharge printing paste can be prepared by a method known per se, together with the dyestuff and, if appropriate, other customary additives.

The amount of the benzenesulfonamide derivative of formula (I) to be used is not critical and can vary widely depending on the type of discharge printing agent used, the type of the amide derivative, etc., but in general, it is added to 100 parts by weight of the discharge printing paste. to at least 2 parts by weight, preferably 2.5 to 10 parts by weight, more preferably 3 to 10 parts by weight.
It can be in the range of 5 parts by weight.

The discharge aid of the present invention can be used in exactly the same way as conventional glycol-based discharge aids.

For example, the discharge dyeing aid of the present invention may be mixed with a colored discharge dye if necessary, and if necessary, a conventional discharge dye such as Rongalit C [component* NaH3O2CH20: manufactured by BASF], Decrolin Soluble Conc [component: Zn(H8O
2CH20)2 ; manufactured by BASF], stannous chloride, thiourea dioxide, etc. are added, and then poured into cold or hot water, followed by locust bean gum, guar gum, calhodic methyl cellulose (CMC) and its modified products, galactoman. A discharge printing paste can be prepared by adding a sizing agent such as non-glue, British gum, or a modified product thereof.

This discharge paste can then be used for printing textile products in exactly the same way as discharge pastes for conventional discharge printing operations.

Next, the present invention will be further explained by examples.

Example A Commercially available cotton broadcloth 1.2% wt
) and 20% owt of anhydrous sodium sulfate at a bath ratio of 1:20 at 30°C, the temperature was gradually raised to SO'C, dyed at this temperature for 60 minutes, and then dyed in the usual manner. Washed with water and dried.

The dyed cotton broadcloth is printed using a printing paste with the following white and colored discharge printing formulations.

White discharge printing formula 150g Rongalit C powder (manufactured by BASF) 500g
Thickening agent (Locust bean gum 10%) 309p-) 4 moles of ethylene oxide adduct of luenesulfonamide 150g Zinc white (1:1) 2g Branco white BBU 200% 168g Water coloring discharge dyeing recipe: 1 (Bi' Silas Spray Roll RR200 % (CI Direct Yellow 28) 50 g p-4 4 mole adduct of ethylene oxide of luenesulfonamide 820 g Boiling water 500 g Thickening material (Locust bean gum lO%) 120 g
After printing Rongarit C powder (manufactured by BASF), 100℃
The sample was dried with water, then steamed with saturated steam at 102° C. for 10 minutes, and then thoroughly washed with water and then subjected to a dry heat treatment.

As a result, compared to the conventional use of thiodiethylene glycol or other glycol-based auxiliary agents, the white discoloration of the white discharge print area is excellent, and the hue clarity and picture edge of the colored discharge print area are excellent. Excellent results in clarity and level dyeing were obtained.

Example B Commercially available cotton broadcloth was put into a dye bath containing 2% owt of Leverfix Gold Yellow EG (CI Reactay Yellow 27) at a bath ratio of 1:20 and dyed for a short period of time at 40°C. Anhydrous sodium sulfate (20 g/') was added in three portions, and 20 g/') ivy soda ash was added in three portions, followed by dyeing at this temperature (40 DEG C.) for 60 minutes.

After staining. After washing with water and hot water, a bath ratio of 1:50 containing 1g/I)
Boiling soaping was carried out for 15 minutes in a washing bath, followed by regular washing and drying.

The dyed cotton broadcloth is printed with a printing paste having the following white and colored printing formulations.

White discharge printing recipe: 150g Rongalit C powder (manufactured by BASF) 350
g Thickening agent [15% locust bean gum and 10% modified starch
] 80 g potassium carbonate 150 g zinc white (1:1) 30 g p-ethylbenzenesulfonamide 4 mole adduct of ethylene oxide 2 g Branco white BBU 200% 238 g water coloring discharge dyeing formula: 50 g indanthrene frilliant high olette E5
Rcol, fig C (CI Bat Violet 21
) 30 g glycerin 50 g p-ethylbenzenesulfonamitonoethylene oxide 4 mole adduct 160 g water 500 g Thickening material [3-neat mixture of 10% locust bean gum and 10% modified starch] 60 g Potassium carbonate 150 g Rongalit C powder (manufactured by BASF) After printing,
Dry at 100'C, then steam for 8 minutes at 104°C with saturated steam in a steamer with complete exclusion of air, rinse with water and add 5 cc/IJ footer 30% hydrogen oxide and 5 c
The sample was oxidized in a 40° C. bath containing c/IJ taffetaacetic acid 6Be, washed with water, boiled and soaped in a washing bath containing 197e Revapon TH (manufactured by Bayer), washed with water again, and then dried.

As a result, the white discoloration in the white discharge printed area was superior to that in the case of using thiodiethylene glycol or other glycol-based auxiliary agents, and clearer results were obtained in the colored discharge printed area.

Example C Commercially available wool muslin was mixed with 1% owf of Subracene Yellow GR 200% (CI Acid Yellow 49).

It was poured into a dye solution containing 5% OWF anhydrous sodium sulfate and 60% 3% OWF acetic acid at a bath ratio of 1:40 at 40°C, dyed for a while, then gradually raised to boiling temperature, and dyed at this temperature for 45 minutes. , Finally, wash with water as usual.

Dry.

The dyed wool muslin is printed with a printing paste having the following white and colored printing formulations.

White discharge printing recipe: 150g Rongalit C powder (manufactured by BASF) 30.9
Glycerin 50 go - 7 moles of ethylene oxide adduct of p-diethylbenzenesulfonamide 500 g Gluing material (crystal gum 33%) 20 g Rodan ammonium 100 g Zinc white (1:1) 150 g Water color discharge printing formula: 5 g Supranolube #-BL200% 30 g Glycerin 309 o- 7 moles of ethylene oxide adduct of p-diethylbenzenesulfonamide 50 g Urea 235 g Boiling water 500 g Thickening agent (guar gum 12%) 100 g Rongalite C powder (BASF) 50 g Zinc white (1:1) After printing, dry at 100°C, then saturated steam After washing with water, soaping was performed at 40° C. in a washing bath containing 39/Rittermonogen (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and finally dry heat treatment was performed.

As a result, compared to the case of using conventionally used thiodiethylene glycol or other glycol-based auxiliary agents, excellent results can be obtained in terms of white discoloration in white discharge printed areas and dye concentration clarity in colored discharge printed areas. Ta.

Example D Commercially available polyamide taffeta was mixed with 2% owf Teron Fast Yellow A2RL (CI Acid Yellow 159) and 5
The sample was placed in a dye bath containing %owf ammonium acetate at a bath ratio of 1:40 at 30°C, gradually raised to boiling, and dyed at this temperature for 30 minutes.

The dyed polyamide taffeta is printed with a printing paste having the following white and colored discharge printing formulations.

White discharge printing prescription: 500g glue (33% crystal gum) 150g Dechlorin Soluble Conch (manufactured by BASF) 5g citric acid 5g Blancohower DcBu, f.

310 g water 31 pJ 4.1 mole adduct of ethylene oxide of chlorobenzenesulfonamide Coloring and discharge printing recipe: 5 g Alizarin Brilliant Violet RW (CI Acid Violet 103) 4.1 mole adduct of ethylene oxide of 31p-chlorobenzenesulfonamide After printing, heat to 100°C. and then dried with saturated steam at 102 °C.
After steaming at ℃ for 20 minutes and washing with water, 1 g/'
) Termeditol PS (manufactured by Bayer) and 0.597
It was washed in a 40°C treatment bath containing Ritter Trilon B (manufactured by BAS'), and finally washed with water and dried.

As a result, compared to the case of using conventionally used thiodiethylene glycol or other glycol-based auxiliary agents, the white printing area has excellent self-printing properties, and the color and discharge printing area has excellent clarity of hue, level dyeing property, and image border. Excellent results were obtained for the sharpness of the image.

Example E Astrazomple-GL with 2% owf acrylic fabric
(CI Basic Blue 54) 0.5% awf Astragal PAW (manufactured by Bayer), acetic acid and sodium acetate were added to adjust the pH to 4.5, and the mixture was poured into a dye bath at a bath ratio of 1:40 at 40°C. The temperature was gradually raised to boiling, and dyeing was carried out at this temperature for 30 minutes.

Finally, wash and dry as usual.

The dyed acrylic fabric is shown below.

After printing, dry at 100°C, then dry with saturated steam at 104°C.
After steaming for 20 minutes and thoroughly washing with water, it was washed at 60'C in a washing bath containing 1g/liter Revapon TH (manufactured by Bayer), 1g/liter soda ash, and 2g/liter hydrosulfide conc. After thoroughly washing with water, drying was performed.

As a result, compared to the case of using conventionally used thiodiethylene glycol or other glycol-based auxiliary agents, the white discharge print area has excellent self-staining, and the colored discharge print area has excellent level dyeing and sharpness of the edge of the image. We obtained the following results.

90 after padding a polyester processed yarn fabric with a dye solution containing 409/Ritter Resolin Lupine BL (CI Deathbirds Violet 40) and 19/Ritter sodium alginate and immediately squeezing it with a mangle at a squeezing rate of 50%. Dry with hot air at ℃.

The polyester processed yarn fabric to which the dye has been attached through padding is printed with a printing paste having the following white and colored discharge printing formulations.

After printing, dry at 100°C and then heat at 102°C with saturated steam.
Steam for 8 minutes at C, followed by 17 minutes in a high temperature steamer.
After steaming at 5°C for 8 minutes, washing with water, reduction washing at 80°C in a washing bath containing 1cc/liter of caustic soda 38°Be and 1g/liter of hydrosulfide concrete, neutralization in an acetic acid bath, and washing with water. Dry heat treatment was performed.

As a result, compared to the conventional use of thiodiethylene glycol or other glycol-based auxiliary agents, the white discoloration of the discharged part of white discharge printing, the leveling of the printed part of colored discharge printing, and the clarity of the edges of the picture are excellent. Got the results.

Reference Example 1e An autoclave was charged with 400 g (20 M) of N-ethyl-p-)luenesulfonamide and 0.8 g of caustic soda, and the pressure was reduced at 100°C according to a conventional procedure for the ethylene oxide addition reaction, and the autoclave was replaced with nitrogen.

After repeating this operation three times, ethylene oxide 7 391.
9 (3.88 mol) and heated at 140 ° C1,
The ethylene oxide addition reaction was started.

The reaction was carried out at 140±5°C and 14kg/Cr1L.

After neutralizing the alkali in the reaction mixture with phosphoric acid and filtering, a 4.4 mol ethylene oxide adduct of N-ethyl-p-toluenesulfonamide was obtained as a yellow transparent liquid.

Claims (1)

[Scope of Claims] [In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkyl group; R3 is a hydrogen atom, a lower alkyl group, a cycloalkyl group; A discharge printing aid comprising at least one adduct of a 1 to 50 mole lower alkidine oxide of a benzenesulfonamide derivative represented by a group, an aryl group or an aralkyl group.