JPS628556B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a discharge printing product exclusively for dyeing a fabric mixed with cationic dye-dyeable polyester fiber and cellulose fiber, and a discharge printing method thereof. Conventionally, discharge printing using dyes exclusively for polyester/cellulose blend fabrics has not yet reached the market due to the delay in establishing the technology, despite the high demand for such printing. The reason for this is that the disperse dyes and cationic dyes used in polyester dyeing are generally acidic, whereas the reactive dyes and vat dyes used in cellulose dyeing are alkaline. 100% polyester is dyed with a removable disperse dye, and cationic dyeable 100% polyester is dyed with a removable cation dye or a removable disperse dye after ground dyeing. White discharge printing (hereinafter referred to as white discharge) using the acidic and active discharge printing agents dechlorin, dechlorin soluble conc, and stannous chloride, and a combination of the discharging agent and the reducing agent disperse dye to create the ground color. Coloring discharge printing (hereinafter referred to as "kunuki"), which applies different colors at the same time as decolorization and decolorization, has been established, and the discharge printing method for cellulose, especially 100% cotton, uses an alkaline and active discharge printing agent after background dyeing with a removable reactive dye. It has been established that white-out printing is performed using a dye, and a pick-up method is used in which a reduction-resistant reactive dye or vat dye is mixed and used at the same time as a discharge dye. In particular, when vat dyes are used as differential color dyes, a discharge dye containing Rongarit C as a discharge dye and potassium carbonate as an alkali agent is printed and heated to decolorize the removable reactive dyes and vat dyes. The Potasshu-Rongarit method is famous, in which the vat dye is oxidized and colored after the reduction and dyeing of the dye are completed at the same time. Many of these are on the market as high-quality prints, but in the case of polyester/cellulose blend fabrics, the dyeing properties of the dyes used for each material are different as mentioned above, making it technically extremely difficult, and the technology has not been established until now. has not been done. Therefore, at present, we have to rely on application fees for differential colors, and due to its hard texture and poor color fastness, especially poor abrasion fastness, it gives an impression of being lower quality than dye-specific prints, and the quantity is low. Currently, there is no expansion, and only a small number of low-grade products are available on the market. On the other hand, when looking at the characteristics required for clothing, 100% cotton has inferior durability and shape stability (W&W properties), and 100% polyester has defects in sweat absorption and electrostatic properties.
In general, polyester/cotton blend fabrics, which compensate for the shortcomings of both materials, are the mainstream for clothing, especially for inner and outer wear, and it is now possible to establish a discharge printing method exclusively for dyeing polyester/cellulose blend fabrics, which have these excellent properties. It was long awaited. The present inventor discovered that due to the remarkable development of disperse dyes in recent years, many products that can be dyed even in alkaline conditions have been developed and are now on the market, and by combining the application of these dyes with the Potasshu-Rongarit method, which is a discharge printing method for 100% cotton, polyester・We focused on the possibility of a discharge printing method for cellulose-mixed fabrics, and as a result of extensive research, we arrived at the present invention. That is, the present invention firstly provides a fabric made of a mixture of polyester fibers and cellulose fibers dyeable with cationic dyes, in which the polyester side in the ground part is dyed with a cationic dye or a cationic dye and a disperse dye, and the cellulose side is dyed with a reactive dye, and the pattern part is dyed with a reactive dye. This article relates to a discharge printing product of a cationically dyeable polyester/cellulose mixed fabric in which the polyester side is dyed with a disperse dye and the cellulose side is dyed with a vat dye in another color.Secondly, it concerns the discharge printing method. be. The discharge printed product of the polyester/cellulose mixed fabric of the present invention is free from pattern misalignment or color doubling at the boundary between the base and pattern, which is unavoidable due to the manufacturing method of conventional overprinted products made of the same type of mixed fabric. This point is fundamentally different, and it is an excellent discharge print product that is extremely satisfactory in terms of dyeing of all dyes. The manufacturing method will be described in detail below, but in order to facilitate understanding, a preferred embodiment of this method will be shown first. That is, in this discharge printing method, when dyeing a mixed fabric of cationic dye-dyable polyester fiber and cellulose fiber, the cellulose side is fixed with a removable reactive dye, and then the polyester side is dyed with a removable cationic dye or the removable cationic dye. Temporary dyeing using a pad method or printing method using a combination of dye and removable disperse dye. After drying, print a discharge printing paste with the following composition, and after drying, heat treatment with saturated steam at 95 to 110°C for 5 to 10 minutes. The first stage steaming treatment is carried out to complete the decomposition and decolorization of the ground dye in the printing area and the reduction and dyeing of the vat dye for the cellulose side difference color at the same time, followed by saturated steam at 120 to 130℃ for 5 minutes. The second stage high-temperature steaming treatment is carried out to complete the coloring of the cationic dye for polyester side ground dyeing or the cationic dye and disperse dye and the disperse dye for differential color by the above steaming treatment, and then the final vat dye for coloring the cellulose side is carried out. This is a discharge printing method for cationically dyeable polyester/cellulose mixed fabric, which is characterized by carrying out oxidation for color development. (Discharge paste) Discharge agent: Alkaline active sulfinic reducing agent represented by Longalint C (sodium sulfoxylate formaldehyde)...2 to 10 parts by weight Alkaline agent: Potassium carbonate, caustic soda,
Soda ash, etc...2 to 10 parts by weight Cellulose side color dye: vat dye...
...X parts by weight Polyester side 〃 : Reduction-resistant alkaline dyeable disperse dye...Y parts by weight (however, the total blended paste is 100 parts) Mixed with cationic dye dyeable polyester fibers and cellulose fibers, which are the materials of the present invention Fabrics include blended knitted fabrics, mixed knits, and mixed fabrics of the polyester fibers and cellulose fibers.
Cationic dye-dyeable polyester is a product copolymerized with a modifier that has an acidic group, or a copolymer with the addition of another modifier to the modifier.In short, it is dyed with a cationic dye. All possible polyesters are meant. Especially as a modification material
Fibers made of cationic dyeable polyester copolymerized with SIP (5-sodium sulfoisophthalic acid) are the most suitable material because of their good color development. Cellulose includes natural or recycled cellulose fibers such as cotton, linen and rayon. In addition, the mixing ratio of cationic dyeable polyester and cellulose is usually 65/65/cellulose in textiles.
35, 50/50 knitted fabric is common for clothing, but the present invention is not limited to this mixing ratio. For ground dyeing on the cellulose side, we use removable reactive dyes, such as vinyl sulfone, which are often used in cotton discharge printing, using the dip dyeing method, chemical patch method,
Alternatively, complete fixation may be performed using a cold batch method or the like. For polyester side dyeing, a removable disperse dye or removable cationic dye such as azo dyes, which are often used in cationic dyeable polyester discharge printing, may be used, but this will be fixed by high-temperature dyeing, carrier dyeing, etc., as described later. As a result, discharge printing becomes extremely difficult. Therefore, in the present invention, the anti-discharge printing method generally used in polyester discharge printing, that is, the pat-dry method (first pat method) or print-
It is done in the form of a temporary dyeing method using the dry method (first ironing method), with the dye still unfixed. Cationically dyeable polyester has the ability to dye with cationic dyes as well as the ability to dye deeply with disperse dyes conventionally used in polyester. Therefore, all of them are useful as dyes for ground dyeing, and the present inventors disclosed a dye using 100% disperse dye for ground dyeing in the previous application, but the present application uses a removable cationic dye for ground dyeing. It is something to do. However, removable cationic dyes are currently unsatisfactory in yellow color, and it is possible to partially replace them with removable disperse dyes. The use in combination as a dye for ground dyeing does not impede the gist of the present invention. In this case, when a cationic dye and a disperse dye coexist in a patch bath of ground dye, the former shows cationic property and the latter dispersant shows anionic property, so in the deep color bath, the two combine and form a precipitate. However, recently developed dispersed cationic dyes have cationic groups blocked by organic anionic compounds, so they are highly compatible with dispersed dyes and can be used in combination without any problems. became possible. Next, printing with a discharge printing paste is carried out, and as a discharge printing agent, an alkaline active sulfinic reducing agent such as Rongarit C (sodium sulfoxylate formaldehyde) is used as a representative example.
When Rongarit C is used, it may be partially or completely replaced with Rongarit DS, H, FD, Rongarit HT, etc. whose reduction effect has improved over time. This discharge printing agent, an alkaline agent, and a color difference dye are mixed into a paste to obtain a discharge printing paste. As the differential color dye, a vat dye is used on the cellulose side, and a reduction-resistant alkali-dyable disperse dye is used on the polyester side. With the recent remarkable development of disperse dyes, many products with reduction resistance, such as anthraquinone and quinophthalone dyes, have been put on the market, and some of these dyes can be dyed even in alkaline conditions. is used. Although it is possible to remove white areas in the ground dyed area without any problem using medium/acidic active discharge dyes such as dechlorin, dechlorin soluble conc, and stannous chloride, reactive dyes and vat dyes that are considered for cellulose side coloring Since the PH range in which it can be dyed is alkaline, it cannot be dyed and cannot be used for dyeing. The content of the above-mentioned discharging agent such as Rongarit C in the blended paste is sufficient to be 2 to 10 parts by weight per 100 parts of the blended paste. The higher the content of the discharging agent (reducing agent), the more effective it is for the decolorization of both ground dyes and the reduction dyeing of vat dyes for cellulose side difference colors, but if it is 10 parts by weight or more, it is less effective for polyester difference colors. Problems include decreased color development of disperse dyes, poor long-term stability of vat dyes (gelation), problems such as halation and bleeding, decreased strength of constituent materials, and decreased color fastness due to residual discharge dye in the final product. wake up As will be described later, it was found that by using saturated steam at around 100°C with a large amount of condensed water as the steaming condition, the discharging agent was effective in an extremely small amount.
On the other hand, under steaming conditions with little condensed water, the reduction and dyeing of vat dyes is insufficient no matter how much the amount of discharge printing agent is increased. If the amount is less than 2 parts, the decolorization of ground dye and the reduction of vat dye will be insufficient. The alkaline agent may be potassium carbonate, caustic soda, or soda ash, and it is sufficient to add it in an amount of 2 to 10 parts by weight per 100 parts of the mixed paste. That is, under the above-mentioned specific discharge printing agent and steaming conditions, decomposition decolorization of both ground dyes and reduction dyeing of vat dyes are sufficiently carried out, and reductive decolorization of disperse dyes for polyester side color does not occur, and subsequent high-temperature steaming does not occur. Normal color development is possible with heat treatment. Roughly ordering the ease of reduction of each dye on each material under the above-mentioned discharging agent and steaming conditions, ((easy)) white of removable reactive dye (fixed cellulose) > reduction-resistant reactive dye Start of discoloration/bleaching of cellulose (fixed) > White removal of removable cationic dyes (on polyester, unfixed), white removal of removable disperse dyes (on polyester, unfixed) > Completion of reduction dyeing of vat dyes ( Unfixed on cellulose → fixed, but not oxidized) > White spots on removable cationic dyes (fixed on polyester), white spots on removable disperse dyes (fixed on polyester) > Reduction-resistant alkaline dyeable disperse dyes (on polyester, unfixed) ) Start of discoloration/bleaching> Start of discoloration/bleaching of vat dye (fixed cellulose, but unoxidized). ((difficult)) Based on the reducing power required for reduction dyeing of vat dyes, it is possible to use removable reactive dyes (cellulose fixation) and removable cationic dyes (fixed on polyester) in the ground dyeing area. , unfixed) and removable disperse dyes (on polyester, unfixed) can both be used for blanking, and it is also possible to use removable cationic dyes and removable disperse dyes together for background dyeing on the polyester side. On the other hand, as a disperse dye for polyester side color, an alkali dyeable type that can withstand the reducing power necessary for reduction dyeing of vat dyes may be selected. As mentioned above, the more discharge dyes there are, the more advantageous it is for reducing and dyeing vat dyes, but as disperse dyes for polyester side color, the lower the reducing power, the wider the dye selection range, so discharge printing is more effective. It is important to keep the content of the agent to the minimum necessary for reducing and dyeing the vat dye. Furthermore, as shown in the above diagram, when a removable cationic dye is completely fixed for polyester ground dyeing, under the minimum conditions that allow reduction dyeing of vat dyes, the color remains light and does not become white. A similar tendency is shown in the case of removable disperse dyes. It is also possible to use reactive dyes instead of vat dyes for cellulose side coloring, but monochlorotriazine, which has a substitutional structure, has a stronger reduction resistance than the vinyl sulfone type, which has an addition structure, which is used for background dyeing. , trichloropyrimidine, sulfopyrimidine, and other reactive dyes were also investigated, but all of them were unusable due to discoloration or decolorization under white-out conditions of unfixed removable disperse dyes on polyester. Other dyes for cellulose include direct dyes and naphthol dyes, but they cannot be used because their resistance to reduction is lower than that of reactive dyes. That is, the point of the present invention is that a vat dye is taken up as a cellulose side color dye, and an alkali dyeable disperse dye that can withstand the minimum reducing power required for reduction dyeing of the dye is applied for polyester side color. 1st
This is a characteristic point. After printing, dry as usual, but to prevent decomposition of the discharge printing agent, it is best to dry it at 110℃ or less as quickly as possible.It is also desirable to keep the printed fabric as short as possible, and if possible, dry it immediately. It should be moved to the next steaming treatment. When formulating the colored paste, other auxiliary agents such as a hydrotope agent, deep dyeing agent, anti-recoloring agent, anti-migration agent, leveling agent, etc. may be added as necessary.
In addition, as the sizing agent, an alkali-resistant sizing agent is used, and since halation and bleeding are likely to occur due to steaming in the presence of excess condensed water, vat dyes such as modified starch, British gum, and locust bean gum are used to prevent halation and bleeding. It is best to use only those listed on the signboard. For steaming, we use the HPS method using saturated steam (closed high-pressure cooker, batch type), and the HTS method using superheated steam (open to atmosphere, 1-pass method = continuous method).
However, condensed water is required in the initial stage of steaming for reduction dyeing of vat dyes, and for this purpose steaming is carried out with saturated steam at 95 to 110°C for 5 to 15 minutes. There is no particular problem with HPS, but when using HTS, if the overheating mechanism can be suppressed as much as possible, it can be cut to create essentially saturated steam. At temperatures above this temperature, reduction dyeing of vat dyes is insufficient, and therefore no matter how much the amount of discharge printing agent is increased, the result will be the same due to insufficient condensed water. Although reduction occurs even at temperatures below this temperature, water droplets falling onto the ground-dyed area cause density unevenness of the unfixed dye on the polyester side, causing dyeing spots. Furthermore, if the steaming time is more than 15 minutes, the condensed water will be excessive, causing problems such as halation, bleeding, discoloration of the ground color, and decreased whiteness of white areas.If the steaming time is less than 5 minutes, the reduction of vat dyes will be insufficient. be. This steam heat treatment removes the white color of both base dyes and completes the reduction dyeing of the established dyes. The cationic dyes, disperse dyes, and disperse dyes for differential colors in the ground-dyed areas on the polyester side other than the printed areas are hardly dyed in this steaming treatment and are in an unfixed state. Saturated steam of 110°C or higher is advantageous for dyeing cationic dyes and disperse dyes, but is disadvantageous for vat dyes as described above. Therefore, it is impossible to dye all types of dyes only by steaming at a constant temperature;
Following the previous and subsequent saturated steam treatments, a second heat treatment is required to dye the cationic dye and disperse dye. Dyeing with disperse dyes requires temperature rather than moisture, and it is possible to use saturated steam, superheated steam, or dry heat (thermosol), but for dyeing with cationic dyes, a moderate amount of moisture is required. and temperature, and saturated steam treatment is better. Superheated steam at 170 to 190℃, which is commonly used for polyester,
High temperature alone, such as dry heat at 180-220°C, does not result in satisfactory dyeing. Therefore, the second heat treatment condition is to heat the dye at 120 to 130 DEG C. for 5 minutes or more using saturated steam capable of dyeing both cationic and disperse dyes. Considering operational processing, the same steamer can be used for the first
Following the steam treatment at around 100℃ on the stage, the temperature is increased under pressure.
Steaming at 120-130°C for 5 minutes or more is most economical. That is, as a heat treatment for dyeing each dye used, the first stage is a saturated steam treatment at around 100°C, which provides enough condensed water for vat dye reduction and dyeing, and then the second stage is a cationic steam treatment. A second feature of the invention is the combination of high temperature steaming with saturated steam for dye and disperse dye dyeing. Then, after washing with water, the vat dye is oxidized for final color development. The oxidation may be carried out in the same manner as in the case of ordinary vat dye dyeing, and may be carried out using hydrogen peroxide, sodium perborate, sodium dichromate, or the like. Subsequently, soaping with an activator and drying may be performed in the same manner as in the conventional overprinting method for polyester/cotton blend fabrics. Reduction washing, which is commonly carried out in disperse dye dyeing, is not carried out because it causes decomposition of the reactive dye. The contents of the present invention have been described in detail above, and will be explained in more detail below with reference to Examples. Note that "parts" in the examples are parts by weight per 100 parts of blended paste unless otherwise specified. Example 1 Three materials: 100% cotton, 100% cationically dyeable polyester copolymerized with 2.5 mol% SIP, and a blend of cotton and cationically dyeable polyester copolymerized with SIP (50/50), with a weight of 36G and a basis weight of approximately 150g/m ² Tenjiku was knitted and pretreated using conventional methods such as scouring and underbleaching. Next, after ground dyeing under the ground dyeing conditions shown below, white-out glue or pick-up paste was printed, and the white-out and pick-up conditions after steaming were examined.

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[Table] Based on the above, for ground dyeing, use a removable reactive dye on the cotton side, and use removable cationic dyes or partially removable disperse dyes on the polyester side.
- White lines can be removed by drying, and for differential colors, products using vat dyes on the cotton side and reduction-resistant alkali-dyable disperse dyes on the polyester side showed good attachment and removal properties. . Example 2 The other dyed ester/cotton jersey material used in Example 1 (the removable cationic dye on the polyester side was
(up to Dry), and using the blended paste of Example 1 as a white paste and a color removal paste (the color removal paste is a (D) processed paste) with different discharge agent conditions, the steaming conditions after printing were changed. We investigated the discharge status. The results are shown below.

[Table] From the above results, we cannot find a condition that satisfies the dyeing of all dyes (differential colors on the cotton side and ground dyeing and different color dyes on the cationic dyeable polyester side) at the same time with only one stage of steaming treatment, and A second heat treatment is required to develop color from cationic dyes and disperse dyes. The test No. 3 sample was subjected to second-stage steaming treatment, in which the steam pressure was increased and the temperature was increased in the same HPS.
After steaming at 125°C for 20 minutes, the product is oxidized and soaped as shown below, washed with water, and dried. There is no change in texture, and the color fastness and strength and elongation are significantly different from normal dyed products. It was in good condition.

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Claims (1)

[Scope of Claims] 1 A fabric made of a mixture of cationic dye-dyeable polyester fibers and cellulose fibers, in which the polyester side of the base part is dyed with a cationic dye or a cationic dye and a disperse dye, and the cellulose side is dyed with a reactive dye, and the pattern part is dyed with a cationic dye or a cationic dye and a disperse dye. A discharge print product of a cationically dyeable polyester/cellulose mixed fabric, characterized in that the polyester side is dyed with a disperse dye and the cellulose side is dyed with a vat dye to a different color. 2. When dyeing a mixed fabric of cationic dye-dyeable polyester fiber and cellulose fiber, the cellulose side is fixed with a removable reactive dye, and then the polyester side is dyed with a removable cationic dye or the cationic dye and a removable disperse dye. After drying, an alkaline activated sulfinic reducing agent is used as a discharge printing agent.
A discharge paste using an alkaline agent, a vat dye as a cellulose side difference color dye, and a reduction-resistant alkali dyeable disperse dye as a polyester side difference color dye is printed, and after drying, the background dye in the printed area is At the same time as decomposition and decolorization, the first stage steaming treatment is carried out to complete the reduction dyeing of the vat dye for the cellulose side difference color, and then the cationic dye for the polyester side ground dyeing or the cationic dye and disperse dye, and the disperse dye for the difference color. A discharge printing method for a cationically dyeable polyester/cellulose blend fabric, which is characterized by carrying out a second stage high-temperature steaming treatment to complete color development, and then oxidizing a vat dye for cellulose side difference color for final color development. 3. Discharge printing of a cationically dyeable polyester/cellulose mixed fabric according to claim 2, characterized in that the discharge printing agent is 2 to 10 parts by weight and the alkali agent is 2 to 10 parts by weight out of 100 parts of discharge printing paste in total. Law. 4. The first stage steaming treatment is steaming treatment with saturated steam at 95 to 110°C for 5 to 10 minutes, and the second stage high temperature steaming treatment is steaming treatment with saturated steam at 120 to 130°C for 5 minutes or more. A method for discharging a cationically dyeable polyester/cellulose blend fabric according to claim 2 or 3, which is characterized by: