JPH06299474A - Method for dyeing or printing fibrous material using reactive dye - Google Patents

Abstract

PURPOSE:To carry out the uniform dyeing or printing without any change in hue using water containing a large amount of metallic ions as opposite to a conventional concept by using a specific reactive dye in dyeing a cellulosic fibrous material with the reactive dye. CONSTITUTION:Cellulosic fiber is dyed or printed with a dioxazine-based reactive dye having a parent substance for a coloring matter in the form of a free acid expressed by the formula (X1 and X2 are H or halogen atom; at least one of A1 to A6 denotes bond to a reactive group or a component containing the reactive group; others are mutually independently hydrogen atom, lower alkyl, lower alkoxy, sulfo group or amino group) by using water containing one metallic ion at >=5ppm concentration as water used for the dyeing or printing step according to a well-known exhaustion method or batch method or one-phase printing method. Thereby, the dyed or printed material without a change in concentration or hue is obtained. Copper, iron, calcium, magnesium ions, etc., can be exemplified as the metallic ion.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for dyeing or printing a cellulosic fiber material or a cellulosic fiber-containing fiber material using a reactive dye.

[0002]

2. Description of the Related Art Reactive dyes have been widely used for dyeing and printing fiber materials such as cellulosic fibers.
As a method for dyeing or printing those fiber materials, various methods such as an exhaust dyeing method, a one-bath padding method, a cold batch-up method and a one-phase printing method are used. In order to achieve uniform dyeing and printing without a change in hue in these methods, it is necessary that the concentration of metal ions in the dyeing water is low. For example, on September 15, 1972, Kyoritsu Shuppan Co., Ltd., “New Dyeing and Processing Course,” Volume 2, page 199, the concentration of metal ions in dyeing water that is normally used is 0.05 ppm for iron and manganese, respectively. Below is 3.0 pp of calcium
There is a description that it is necessary that m is less than 0.5, magnesium is 0.5 to 1.0 ppm or less, and aluminum is 0.5 to 1.0 ppm or less. Therefore, in industrial dyeing and printing, the metal ion concentration in the water used should be adjusted within the above-mentioned concentration, or by adding a sequestering agent, the concentration and hue of the dyed and printed products can be improved. Avoiding troubles such as changes and uneven dyeing.

[0003]

However, the concentration and type of metal ions in the water are not constant, and therefore,
A great deal of effort is required to adjust the metal ion concentration, and even when adding a metal ion sequestering agent, a preliminary test is performed to adjust the amount of the sequestering agent in advance, or an optimum metal ion sequestering agent suitable for the conditions is added. A complicated operation for selecting the agent is required. In addition, some sequestering agents inhibit the dyeing of reactive dyes, so a sufficient preliminary test is required in advance for industrial dyeing and printing. There is a strong demand for the development of uniform and non-discoloring dyeing technology.

[0004]

SUMMARY OF THE INVENTION In the method of dyeing or printing a cellulosic fiber material or a fiber material containing a cellulosic fiber with a reactive dye, the inventors of the present invention avoid the above problems and provide a uniform method. As a result of diligent studies on a more industrially advantageous method of obtaining a dyed or printed material that can be dyed and printed and has no change in density or hue,
The present invention has been completed.

That is, the present invention is characterized in that a dioxazine-based reactive dye is used as a reactive dye, and water having a concentration of at least 5 ppm of at least one metal ion is used as water for dyeing or printing process. Provided is a method for dyeing or printing a material or a fiber material containing a cellulosic fiber.

The dioxazine-based reactive dye used in the present invention is not particularly limited, but preferably the dye base of the dioxazine-based reactive dye is represented by the formula (I) in the form of a free acid.

[0007]

[Chemical 3]

[Where X is₁And X₂Water independent of each other
Elemental atom or halogen atom, A₁, A ₂, A₃, A_Four,
A_FiveAnd A₆At least one of the reactive groups or
Represents a bond to a moiety having a responsive group, the others independently of each other.
Hydrogen atom, lower alkyl, lower alkoxy, sulfo group
Or represents an amino group. ] The dye is preferably used,
More preferably, the dye base of the dioxazine-based reactive dye is
Formula (II) in the form of the free acid

[0009]

[Chemical 4]

[Wherein X ₁ , X ₂ , A ₁ , A ₂ and A
₃ has the meaning given above. ] Is a dye.

The dioxazine-based reactive dye used in the present invention has, as a reactive group, -SO ₂ L ₁ (wherein, L ₁ represents -CH = CH ₂ or -CH ₂ CH ₂ L ₂ , and L ₂
Represents a group capable of leaving by the action of an alkali. ), A monochlorotriazine group, a monofluorotriazine group, a mononicotiniotriazine group, a dichlorotriazine group, a difluoromonochloropyrimidine group, a reactive dye having at least one or more of at least one of trichloropyrimidine groups, but a dioxazine-based reactive dye The reactive group of is not limited to these.

The dioxazine-based reactive dyes used in the present invention are, for example, JP-A-60-184567 and JP-A-1-18.
No. 5,370, JP-A-3-770, etc., but the dioxazine-based reactive dye of the present invention is not limited thereto.

In the dioxazine-based reactive dye used in the present invention, the atoms represented by X ₁ and X ₂ are each independently a hydrogen atom or a halogen atom such as fluorine, chlorine, bromine or iodine, and particularly preferably a hydrogen atom. Alternatively, it is a chlorine atom.

Further, in the dioxazine-based reactive dye used in the present invention, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ and A
_At least one of ₆ represents a bond to a reactive group or a component having a reactive group, and the other independently of one another is a hydrogen atom, C
_{1 to} C ₄ lower alkyl group, C _{1 to} C ₄ lower alkoxy group, sulfo group or optionally substituted amino group, particularly preferably hydrogen atom, sulfo group, methyl group,
Examples include an ethyl group, a methoxy group, an ethoxy group, an amino group, and a substituted amino group.

In the dioxazine-based reactive dye used in the present invention, examples of the group represented by L ₂ which is eliminated by the action of an alkali include a sulfate ester group, a thiosulfate ester group, a phosphate ester group and an acetate ester group. , Halogen atoms, etc. are exemplified, but the present invention is not limited thereto.

The dioxazine-based reactive dye in the present invention is present in the form of a free acid or a salt thereof, and in particular, an alkali metal salt and an alkaline earth metal salt, and further, a sodium salt, a potassium salt and a lithium salt are preferable. .

The metal ion in the present invention is usually contained in water used in the dyeing or printing process,
For example, copper ions, iron ions, calcium ions, magnesium ions and the like can be mentioned.

Further, as the amount of metal ions in the water,
The concentration of at least one metal ion is 5 ppm or more, and particularly preferably in the range of 5 to 50 ppm,
More preferably, the dyeing or printing property is good in the range of 5 to 20 ppm.

The concentration of these metal ions is at least 1.
The metal ion of the seed is 5 ppm or more, and the concentration of other metal ions that can coexist may be 5 ppm or more or 5 ppm or less. When the metal ion concentration of the water for use is out of a predetermined range, a compound which generates a desired metal ion is added to the water for use or the dioxazine-based reactive dye to be used,
Alternatively, the concentration can be adjusted by a conventionally known mechanical separation or mass transfer operation.

In order to obtain a desired hue by the dyeing or printing method of the present invention, it can be used by mixing with other dyes, if necessary. The dye used as a mixture is not particularly limited as long as the effect of the present invention is not impaired, and a known reactive dye can be used, but preferably a sulfatoethyl sulfone group, a vinyl sulfone group, or a monochloro group as a reactive group. A dye having at least one or more of a triazine group, a monofluorotriazine group, a mononicotiniotriazine group, a dichlorotriazine group, a difluoromonochloropyrimidine group, or a trichloropyrimidine group, and Sumifix, Sumifix Supra, Re
mazol, Levafix, Procion, Cibacron, Basilen, Dr
Illustrative examples include dyes that are commercially available under the generic names such as imarene, Kayacion, and Kayacelon React.

In the present invention, if desired, an inorganic salt such as anhydrous mirabilite or sodium chloride, a dispersant such as an optionally alkylated formalin condensate of naphthalene sulfonic acid, a dissolution enhancer such as a naphthalene derivative, and a dust scattering inhibitor. , A pH stabilizer, an antifoaming agent, water, and other known dyeing aids may be added to the dye, and at the time of dyeing or printing, these dyeing aids may be added to the dye bath or printing dye paste. May be.

The cellulosic fiber material in the present invention is not particularly limited, but cotton, linen,
Examples include natural or regenerated cellulose fibers such as hemp, jute, ramie fibers, viscose human silk, and bemberg. Examples of fiber materials containing cellulosic fibers include cotton / polyester blended products, cotton / nylon blended products, and cotton / wool blended products.

The method for dyeing and printing a reactive dye in the method of the present invention may be a known method. In the exhaust dyeing method, a known inorganic neutral salt such as anhydrous sodium sulfate and salt, and
Examples of the dyeing aid include a method of dyeing known acid binders such as sodium carbonate, sodium bicarbonate, caustic soda, caustic potash, sodium phosphate tribasic or commercially available synthetic alkali agents alone or in combination. It is not limited to these. The amount of the inorganic neutral salt or acid binder used at this time is not limited, but at least 1 g / L or more is preferable, and 200 g / L or more may be used. Further, the inorganic neutral salt and the acid binder may be added to the dyeing bath all at once, or may be divided and added by a conventional method. In addition, dyeing assistants such as leveling agents, slow-dyeing agents, and bath softeners may be used in combination by known methods, but the dyeing assistants are not particularly limited to these. Also,
The dyeing temperature is usually 30 to 95 ° C. In the cold batch-up dyeing method, a known inorganic neutral salt such as anhydrous Glauber's salt and salt, and a known acid binder such as caustic soda and sodium silicate are used for padding, and then allowed to stand in a closed packaging material at a constant temperature. A method of dyeing is exemplified. In the continuous dyeing method, a known acid binder such as sodium carbonate and sodium bicarbonate is mixed with a dye padding solution, and after padding by a known method, a one-bath padding method of dyeing by dry heat or steam, and after dye padding, anhydrous sodium sulfate Examples include a two-bath padding method in which a known inorganic neutral salt such as sodium chloride and salt and a known acid binder such as caustic soda and sodium silicate are padded and dyed by dry heat or steam by a known method. In the printing method, after printing a printing paste containing a known acid binder such as sodium bicarbonate, a one-phase printing method of printing by dry heat or steam by a known method, and after printing the printing paste, an inorganic medium such as salt is used. Examples of the two-phase printing method include printing in a high temperature solution of 80 ° C or higher containing a known salt and a known acid binder such as caustic soda or sodium silicate, and the like, but the dyeing and printing methods are not limited to these. Not done.

According to the present invention, in dyeing or printing a cellulosic fiber material or a fiber material containing a cellulosic fiber with a reactive dye, even when water containing a large amount of metal ions is used, the concentration is uniform. It is possible to provide a dyed or printed product having no change in hue or hue.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, parts and% mean parts by weight and% by weight.

Example 1 100 kg of a fiber material composed of unmercured cotton knit was set in a jet dyeing apparatus, and a bath ratio of 1:15 and a water temperature of 50 ° C. were obtained by using water having a concentration of 10 ppm of calcium ions.
Formula (1) in the form of predissolved free acid

[0027]

[Chemical 5]

1 kg of the dye of formula (1) was added to the bath by a known method. Further, 50 kg of anhydrous Glauber's salt was put into the bath by a known method, and then the cotton knit was treated at this temperature for 20 minutes, and 30 kg of sodium carbonate was put into the bath in two divided steps by the known method. Then treat the cotton knit at this temperature for 60 minutes,
The dyeing was completed. The obtained dyed product was washed and finished by a conventional method. The resulting dyed product was a clear, deep and uniform reddish blue color. For comparison, dyeing was carried out under the same conditions as above using water containing no metal ions, but the resulting dyed product had the same density and hue as the dyed product obtained above, and was a deep reddish blue color. Met.

Example 2 100 kg of a fiber material made of mercerized cotton knit was set in a jet dyeing device, and magnesium ion 20 pp
The bath ratio was 1:15 using water having a concentration of m, and the water temperature was 60 ° C. Formula (2) in the form of predissolved free acid

[0030]

[Chemical 6]

1.5 kg of the dye of formula (1) was added to the bath by a known method. Further, 75 kg of anhydrous Glauber's salt was put into the bath by a known method, the cotton knit was treated at this temperature for 20 minutes, and 15 kg of sodium tertiary phosphate was put into the bath by a known method. The cotton knit was then treated at this temperature for 60 minutes to complete the dyeing. The obtained dyed product was washed and finished by a conventional method. The resulting dyed product was a clear, deep and uniform reddish blue color. For comparison, dyeing was carried out under the same conditions as above using water containing no metal ions, but the resulting dyed product had the same density and hue as the dyed product obtained above, and was a deep reddish blue color. Met.

Example 3 100 kg of a fiber material made of rayon was set in a jet dyeing apparatus, and water having a concentration of 10 ppm of calcium ion and 10 ppm of magnesium ion was used, and a bath ratio of 1: 1.
5. The water temperature was set to 60 ° C. Formula (3) in the form of the previously dissolved free acid

[0033]

[Chemical 7]

2 kg of the dye of formula (1) was added to the bath by a known method. Further, 40 kg of anhydrous Glauber's salt was put into the bath by a known method, and then the cotton knit was treated at this temperature for 20 minutes, and 10 kg of sodium carbonate was put into the bath in two times by the known method. Then treat the cotton knit at this temperature for 60 minutes,
The dyeing was completed. The obtained dyed product was washed and finished by a conventional method. The obtained dyed product was a clear and uniform deep reddish blue color. For comparison, dyeing was carried out under the same conditions as above using water containing no metal ions, but the resulting dyed product had the same density and hue as the dyed product obtained above, and was a deep reddish blue color. Met.

Example 4 Formula (4) in the form of the free acid

[0036]

[Chemical 8]

50 g of the dye represented by the formula (5) in the form of free acid

[0038]

[Chemical 9]

After dissolving 50 g of the dye represented by the formula in hot water, it was cooled to 25 ° C., and 150 g of sodium silicate of 50 ° Baume and a 32.5% aqueous solution of caustic soda 15
Immediately after adding mL, water containing divalent iron ions is added to obtain a total amount of divalent iron ions of 25 ppm at a concentration of 15 ppm.
A 1 L dye solution was prepared at ° C. Immediately thereafter, a cotton fabric was padded by a known method using this solution as a padding solution, immediately rolled up, sealed with a polyethylene film, and left in a room at 20 ° C. for 10 hours. Then, the dyed product is washed and finished by a conventional method. The obtained dyed product was a clear and uniform deep reddish blue color. For comparison, dyeing was carried out under the same conditions as above using water containing no metal ions, but the resulting dyed product had the same density and hue as the dyed product obtained above, and was a deep reddish blue color. Met.

Example 5 200 kg of a mixed knitted fabric consisting of 50 parts of cotton fiber and 50 parts of polyester fiber was set in a high-pressure jet dyeing device, and a bath ratio of 1:
10, the water temperature was adjusted to 80 ° C., and the pH was adjusted to 5 with acetic acid. Disperse dye Sumikaron Blue that is well dispersed in water
3 kg of E-FBL (Sumitomo Chemical Co., Ltd.) and 2 kg of dispersant Sumipon TF (Sumitomo Chemical Co., Ltd.) were put into the bath, and then 4
The temperature was raised to 130 ° C. in 0 minutes, and the polyester side was dyed at this temperature for 40 minutes. Next, the dyeing liquor was drained, and then water having a concentration of 3 ppm of calcium ions and 7 ppm of copper ions was supplied, and the bath ratio was 1:10 and the water temperature was 60 ° C. Formula (6) in the form of the previously dissolved free acid

[0041]

[Chemical 10]

3 kg of the dye represented by the formula (3) was added to the bath, and the water temperature was kept at 60 ° C. Thereafter, 40 kg of anhydrous Glauber's salt was put into the bath by a known method, the knitted fabric was treated at this temperature for 20 minutes, and 30 kg of sodium carbonate was put into the bath by a known method.
The knitted fabric was then treated at this temperature for 60 minutes to complete the dyeing. The obtained dyed product was washed and finished by a conventional method.
The resulting dyed product was a clear, deep and uniform reddish blue color. For comparison, dyeing was carried out under the same conditions as above using water containing no metal ions, but the resulting dyed product had the same density and hue as the dyed product obtained above, and was a deep reddish blue color. Met.

Example 6 Formula (7) in the form of predissolved free acid

[0044]

[Chemical 11]

80 g of the dye represented by: was dissolved in hot water containing calcium ions and magnesium ions, and further cooled to 25 ° C. Immediately after adding 1 g of sodium alginate, 10 g of sodium metanitrobenzenesulfonate, and 20 g of sodium bicarbonate to this dye solution, and further adding water to make a dye solution of 1 L at a concentration of 15 ppm of calcium ion and 15 ppm of magnesium ion at 25 ° C. Then, a cotton fabric was padded using this solution as a padding solution. The padded cotton fabric was dried at 120 ° C. for 2 minutes and then steamed at 100 ° C. for 5 minutes to fix the dye. The obtained dyed product was washed and finished by a conventional method. The resulting dyed product was a clear, deep and uniform reddish blue color. For comparison, dyeing was carried out under the same conditions as above using water containing no metal ions, but the resulting dyed product had the same density and hue as the dyed product obtained above, and was a deep reddish blue color. Met.

Example 7 Formula (8) in the form of predissolved free acid

[0047]

[Chemical 12]

60 g of dye, 50 g of urea, 5%
Alginate 550g, calcium ion 30p
320 g of boiling water containing pm and 20 g of sodium bicarbonate
A printing paste consisting of After printing the obtained printing paste on 40th mercerized cotton broad cloth by the usual method, 100 ° C
Steaming treatment was performed for 5 minutes. The obtained printed material was washed and finished by a conventional method. The resulting print was a clear, deep and uniform reddish blue color. For comparison, printing was performed under the same conditions as above using water containing no metal ions, but the resulting prints were of the same density and hue as the prints obtained above, with a uniform deep reddish blue color. Met.

Example 8 100 kg of fiber material made of unmercured cotton yarn was set in a cheese dyeing apparatus, and water having a concentration of 5 ppm of calcium ion and 5 ppm of magnesium ion was used, and a bath ratio was 1: 1.
5. The water temperature was set to 60 ° C. Formula (9) in the form of the previously dissolved free acid

[0050]

[Chemical 13]

1.5 kg of the dye represented by the formula (10) in the form of free acid

[0052]

[Chemical 14]

1.0 kg of the dye represented by the formula (11) in the form of free acid

[0054]

[Chemical 15]

0.5 kg of the dye of formula (1) was added to the bath by a known method. Further, 50 kg of anhydrous Glauber's salt was put into the bath by a known method, the cotton yarn was treated at this temperature for 20 minutes, and 30 kg of sodium carbonate was put into the bath by a known method. Then, the cotton yarn was treated at this temperature for 60 minutes to finish the dyeing. The obtained dyed product was washed and finished by a conventional method. The obtained dyed product was uniform and dark brown.

Example 9 100 kg of a fiber material made of mercerized cotton knit was set in a jet dyeing device, and water having a concentration of calcium ion of 15 ppm and magnesium ion of 2 ppm was used, the bath ratio was 1:15, and the water temperature was 60 ° C. did. Formula (12) in the form of the previously dissolved free acid

[0057]

[Chemical 16]

Dye 0.5 kg, Sumifix Yellow
2GL special (Sumitomo Chemical Co., Ltd.) 2kg and Sumifi
x Supra Brilliant Red BSF (Sumitomo Chemical Co., Ltd.) 1 kg was melted by a known method, then put in a bath, and the water temperature was 60 ° C.
Kept at. After that, 75 kg of anhydrous sodium sulfate was put into the bath by a known method, a cotton knit was treated at this temperature for 30 minutes, and 30 kg of sodium carbonate was put into the bath by a known method. Then
The cotton knit was treated at this temperature for 60 minutes to finish the dyeing. The obtained dyed product was washed and finished by a conventional method. The obtained dyed product was uniform and dark brown.

Examples 9-13 A cotton knit is dyed by the same procedure as in Example 1 except that the compounds shown in Tables 1 and 2 are used in place of the dioxazine-based reactive dye of the formula (1). , Washed. The obtained dyed products had the hues shown in Tables 1 and 2 and were uniform. For comparison, dyeing was performed under the same conditions as above using water containing no metal ion, but all the obtained dyed products were uniform and had the same concentration and hue as the dyed product obtained above. .

[0060]

[Table 1]

[0061]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuhei Hashizume 3-98 Kasugadeka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (4)

[Claims] 1. A cellulosic fiber material or cellulosic material characterized in that a dioxazine-based reactive dye is used as the reactive dye, and water having a concentration of at least 5 ppm of at least one metal ion is used as water for dyeing or printing process. A method for dyeing or printing a fiber material containing fibers. 2. A dye matrix of a dioxazine-based reactive dye is released.
Formula (I) in the acid form[Where X is₁And X₂Are hydrogen atoms or
Halogen atom, A₁, A ₂, A₃, A_Four, A_FiveAnd A
₆At least one of which has a reactive group or a reactive group
Represents a bond to a component, the others independently of each other
Primary alkyl, lower alkoxy, sulfo group or amino group
Represents ] The method of claim 1, wherein 3. A dye base of a dioxazine-based reactive dye is represented by the formula (II) in the form of a free acid. [Wherein X ₁ , X ₂ , A ₁ , A ₂ and A ₃ are the compounds of the formula 2
Has the meaning described in. ] The method of Claim 2 which is this. 4. The metal ion is copper ion, iron ion, calcium ion or magnesium ion.
The method according to any one of 3 above.