JPH0242948B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing polyolefin fiber materials. Polyolefin fiber materials, especially crystalline polypropylene fibers, have many features such as being light, strong, and warm, and although they were expected to be ``dream fibers'' when they were first developed, they are hydrophobic and chemically unstable. Because it is inert, it is difficult to apply normal dyeing methods, and it has the disadvantage that it cannot be dyed. The reality is that it is only used in certain fields.
Therefore, there has been a strong desire to improve the dyeability of polyolefin fiber materials, and many methods have been proposed to date. For example, the method of adding and mixing a substance that can serve as a dyeing seat for anionic dyes to polyolefin is realistic and attracts attention because it does not impair the properties of polyolefin in terms of easy spinnability and yarn strength. . Among them, the dyeable polyolefin compound obtained by kneading a copolymer of ethylene and an aminoacrylate compound with polyolefin, which is described in Japanese Patent Publication No. 42-22523, is industrially applicable. This method can also be expected to be inexpensive. Also, JP-A-52-
Publication No. 16133 discloses the effect of improving dyeability by further adding various metal salts of organic carboxylic acids to the above composition. However, according to the practical tests conducted by the present inventors, such polyolefin compositions also impair the physical properties of the polyolefin fibers by increasing the amount of the basic polymer or even the organic carboxylic acid metal salt. Not only is there a contradiction that reducing the amount added reduces the dyeability of anionic dyes, but even if the amount added is adjusted to an appropriate range, dyeing methods using ordinary acid dye baths only dye the surface of the yarn. Therefore, it was found that the dyeing was extremely insufficient in terms of various fastnesses such as washing resistance, light resistance, and abrasion resistance. Generally speaking, a method of improving dyeability is to treat it with a carrier during or before dyeing.
Publication No. 23910 describes a method using one or more of aromatic halogen-substituted products, derivatives of aromatic carboxylic acids, and alkyl-substituted naphthalenes, and
-30028 and Japanese Patent Publication No. 45-5065 mention the use of dispersed and emulsified higher aliphatic alcohols, but the odor becomes a problem when using carriers, and the use of higher alcohols It had many drawbacks, including an insufficient dyeing rate. In order to solve this problem, the present inventors conducted intensive research on dyeing aids and found that alkyl phosphate-based aids are significantly more effective than these known aids. They discovered this and arrived at the present invention. That is, the present invention provides crystalline polyolefin 99-
80 parts by weight, ethylene and general formula () (In the formula, R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is 1
1 to 20 parts by weight of a copolymer with one or more aminoalkyl acrylate compounds represented by The present invention provides a method for dyeing polyolefin fiber materials, which is characterized in that at least one alkyl phosphate or its salt is added to the dye bath when dyeing with a dye. The first feature of the present invention is the dip dyeing method, continuous dyeing method, which is widely used for fibers or processed products thereof.
It can be applied to various dyeing methods such as textile printing, and in any dyeing method, the dye penetrates deep into the yarn, resulting in not only high dyeability but also excellent washing fastness and light fastness. It is possible to obtain dyed yarn or dyed fiber products with excellent durability and abrasion fastness. A second feature of the present invention is that the dyed yarn or dyed fiber product thus obtained is also endowed with antistatic properties. The contents of the present invention will be explained in detail below. Examples of the crystalline polyolefin in the present invention include crystalline polypropylene, polyethylene, propylene-ethylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, saponified product of ethylene-vinyl acetate copolymer, etc. Although polypropylene is included, polypropylene is of particular industrial significance. As the amyl alkyl acrylate comonomer for the ethylene copolymer used in the present invention, various compounds are effective as described in Japanese Patent Publication No. 42-22523, but a particularly preferred one is dimethylaminoethyl Examples include methacrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl acrylate. The aminoalkyl acrylate comonomer unit in the ethylene copolymer is 1 to 50% by weight, preferably 10 to 35% by weight, and the melt index is in the range of 1 to 1000, preferably 50% by weight.
~500 things. In addition to the aminoalkyl acrylate comonomer, a ternary or more comonomer containing unsaturated ester comonomer units such as vinyl acetate, vinyl propionate, methyl acrylate, and methyl methacrylate within a range of 20% by weight or less may also be used. It may also be a polymer. The ethylene copolymer is usually produced under the following conditions: ethylene pressure of 500 to 4000 Kg/cm ² and temperature of 100 to 300°C.
It is obtained by bringing ethylene into contact with an aminoalkyl acrylate compound having the above general formula in the presence of a free radical catalyst such as oxygen, an organic peroxide, or a diazo compound. Usually, industrially, it is obtained by polymerizing in a continuous method at an addition rate of 20% or less based on the total amount of ethylene and comonomer, but it may be obtained by a batch method. The amount of the ethylene copolymer added is crystalline polyolefin 99
1 to 20 parts by weight, preferably 5 to 80 parts by weight
~10 parts by weight is suitable. If the amount added is less than this range, the dyeability will be insufficient, and if the amount added is more than this, the spinnability and yarn properties will be impaired. In the present invention, organic carboxylic acid metal salts such as aromatic carboxylic acids or higher aliphatic carboxylic acids such as benzoic acid, pt-butylbenzoic acid, phenylacetic acid, 1,8-naphthylic acid, stearic acid, lauric acid, oleic acid, etc. Sodium or potassium salts of acids such as palmitic acid, nicotinic acid, etc. may be added. Among these, addition of higher fatty acid sodium salts such as sodium stearate is preferred. The amount of these organic carboxylic acid metal salts added is in the range of 0 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 99 to 80 parts by weight of the crystalline polyolefin. Even if the amount added is larger than this, not only will the deep dyeing effect not increase accordingly, but the spinnability and physical properties of the yarn will be impaired. In the present invention, the objects to be dyed are usually fibers obtained by melt-spinning the above-mentioned crystalline polyolefin composition and further stretching or crimping as necessary, or processed products thereof. It may also be a blended yarn, intertwisted yarn, or interwoven product with different types of fibers such as nylon and wool. The polyolefin fiber material usually contains various additives such as heat stabilizers, antioxidants, UV deterioration inhibitors, antistatic agents, and flame retardants, and in some cases, small amounts of inorganic fillers or pigments. may be included. Examples of the alkyl phosphates or salts thereof used in the present invention include those represented by the following general formulas () and (). (In the formula, R is an alkyl group having 81 to 22 carbon atoms or an aryl group substituted with an alkyl group having 8 to 18 carbon atoms, m is 0 to 30, M ₁ and M ₂ , M ₃ are each H,
Represents Na, K, Li, NH ₄ , alkylamine or alkanolamine. ) More specifically, various higher aliphatic alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and cetyl alcohol, or alkyl phenols such as nonylphenol and octylphenol, and phosphoric acid. or the monoester or diester of Na, K,
Alkali metal salts such as Li, ammonium salts, alkylamine salts, alkanolamine salts, polyoxyethylene alkyl phosphoric acid mono- or diesters obtained from the above-mentioned various higher aliphatic alcohols or alkyl phenols, ethylene oxide and phosphoric acid; Examples thereof include alkali metal salts, ammonium salts, alkylamine salts, and alkanolamine salts. Examples of these alkyl phosphates or their salts include Electrostripper K, N or F (all manufactured by Kao Atlas Co., Ltd.), Xerex
IOK (manufactured by Miyon Oil Co., Ltd.), Fcol 301 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), Sunstat 230D (manufactured by Sanyo Chemical Industries)
Commercially available products such as these can be used. The amount of these alkyl phosphates or their salts added is usually 0.1 to 15% by weight, preferably 0.5 to 5% by weight, based on the target polyolefin fiber material.
It is. When dyeing the polyolefin fiber material according to the present invention, the following dyeing means can be used. That is, the above-mentioned modified polyolefin fiber material is placed in an exhaust dyeing bath prepared by adding an anionic dye, an acid that maintains acidic conditions, and an alkyl phosphate or its salt, and heated to perform exhaust dyeing. In addition to exhaust dyeing, a dye padding bath containing an anionic dye, an acid, and an alkyl phosphate or its salt is prepared, and the modification imparts a padding liquid to the polyolefin fiber material, followed by a fixing treatment (generally steaming). ) Continuous dyeing method involves continuous dyeing. In addition, in the textile printing method, an acid and an alkyl phosphate or a salt thereof are added to a textile dyeing paste containing an anionic dye, and printing can be carried out by printing and fixing treatment (generally steaming). Here, acids for preparing acidic conditions include acetic acid, formic acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid,
Inorganic or organic acids such as oxalic acid, benzoic acid, salicylic acid and mixtures thereof are used. In the present invention, examples of anionic dyes include acid dyes, metal-containing dyes, direct dyes, and acid mordant dyes. The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The dyeability, color fastness, and electrostatic voltage were measured by the following methods. (1) Dye exhaustion rate: Based on colorimetric method. That is, where a is the absorbance of the dye solution before dyeing at the absorption wavelength of the dye and b is the absorbance of the residual dye solution after dyeing, it is given by a-b/a×100. (2) Final dyed area: The colorimetric method was used in the same way as the dye exhaustion rate. That is, if the absorbance of the residual liquid after soaping with the same amount of liquid as during dyeing at the absorption wavelength of the dye concerned is C, then the final dyeing rate=dye exhaustion rate-c/a×100 is given. (3) Light fastness...Compliant with JIS L-0842. The light source is a carbon arc. After irradiation at 63°C for 80 hours, the fastness is graded 1-8. (4) Fastness to friction...Compliant with JIS L-0849. The load is 200g using wet cotton (JIS L0803).
Rub 100 times at a speed of 30 times/minute. The fastness is shown in grades 1-5. (5) Charging voltage: Rub the cloth 10 times using dry cotton using the same method as the friction fastness test, and immediately measure the charging voltage. Example 1 Noblen FL-800 (Sumitomo Chemical Co., Ltd.,
7 parts by weight of a 70/30 weight ratio copolymer of ethylene and dimethylaminoethyl methacrylate (melt index 100) and 1 part by weight of sodium stearate are mixed with 92 parts by weight of polypropylene (melt index 10). After granulation, the fibers were spun at 240°C and drawn 3 times at 110°C to obtain fibers of 16 denier/filament. Ranil Gray BGl/C (manufactured by Sumitomo Chemical Co., Ltd., metal-containing complex dye, CI No. Acid Black 58) 0.8% owf, formic acid 2% owf, Electrostripper K (manufactured by Kao Atlas Co., Ltd., alkyl phosphate potassium salt ) The above fibers were immersed in a dye bath consisting of 3% OWF and dyed for 30 minutes at a bath ratio of 1:60 and at 100°C. The dye exhaustion rate at this time is
It showed 98%. Furthermore, the dyed items are taken out, washed with water, and monogen
(manufactured by Daiichi Kogyo Seiyaku Co., Ltd., alkyl sulfate ester sodium salt) Soaping was carried out for 5 minutes at 60 ° C. in a soaping bath containing 2 g of Na salt at a bath ratio of 1:60.
It was further washed with water and dried. The final dyeing rate is 83%,
It showed a light fastness level of 6th grade and a friction fastness level of 5th grade. Furthermore, the charging voltage was -0.5KV. Comparative Example 1 The same operation as in Example 1 was carried out except that Electrostripper K was not added. As a result, the final dyeing rate was only 39%, and both light fastness and rubbing fastness were 4-5 grade. Furthermore, the charging voltage was -2.5KV. Example 2-5 The same yarn obtained in Example 1 was treated with various dyes as shown in Table 1 with acid and electrostripper.
It was dyed in a dye bath containing K. In all cases, the dyeing properties, light fastness, abrasion resistance, and antistatic properties were all good. Comparative Example 2-5 The same operation as in Examples 2 to 5 was performed except that electrostripper K was not added. As a result,
As shown in Table 1, dyeability, light resistance, abrasion resistance,
The antistatic properties were inferior to those of Examples 2-5. Examples 6-10 When dyeing the same yarn obtained in Example 1 with the acid dye Lanyl Gray BGl/C, various alkyl phosphate salts as shown in Table 1 were added to the dyebath as auxiliaries. As a result, in all cases, the dyeing properties, light fastness, abrasion resistance, and antistatic properties were all good. Example 11 Noblen FL-800 (manufactured by Sumitomo Chemical Co., Ltd., polypropylene, melt index 10) 93
After mixing and granulating 7 parts by weight of a 70/30 weight ratio copolymer of ethylene and dimethylaminoethyl methacrylate (melt index 100),
The fibers were spun at 240°C and drawn 3 times at 110°C to obtain fibers of 16 denier/filament. Ranil Gray BGl/C (manufactured by Sumitomo Chemical Co., Ltd., metal-containing complex dye, CI No. Acid Black 58) 0.8% owf, formic acid 2% owf, Electrostripper K (manufactured by Kao Atlas Co., Ltd., alkyl phosphate potassium salt ) The above fibers were immersed in a dye bath consisting of 3% OWF and dyed for 30 minutes at a bath ratio of 1:60 and at 100°C. The dye exhaustion rate at this time is
It showed 90%. Furthermore, the dyed object is taken out, water-dyed, and monogen
(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) In a soaping bath containing 2 g/ml of soap at a bath ratio of 1:60, soaping was carried out at 60° C. for 5 minutes, followed by washing with water and drying. The final dyeing rate is 73%, the light fastness is grade 5, and the rubbing fastness is grade 5.
showed the grade. The charging voltage was -0.6KV. Comparative Example 6 The same operation as in Example 11 was carried out except that Electrostripper K was not added. As a result, the final dyeing rate was only 30%, and the color fastness to light was 4th grade, and the fastness to rubbing was 3rd to 4th grade. Furthermore, the charging voltage was -3.0KV. Example 12 Aminyl Blue E-PRL (manufactured by Sumitomo Chemical Co., Ltd., acid dye, CI No. Acid Blue 129)
2.2g/, octyl phosphate potassium salt,
A dye padding bath was prepared containing 5 g of formic acid, 3 g of formic acid, and 2.5 g of Indarka 7883 (commercially available from Chugai Trading Co., Ltd., etherified locust bean gum) as a sizing agent. A loop pile carpet tufted using No. 3 single yarn spun from the same fibers as obtained in Example 1 (twisting number: 100 times/m) was immersed in the above padding bath at room temperature, and the dye liquor pick-up rate was 500.
After squeezing the liquid to %, it was steamed in a steamer at 100°C for 10 minutes. Next, it was washed with water, further soaped for 5 minutes at 60°C in a soaping bath containing 2 g of Monogen (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), washed with water, and dried to finish. The dyed object is dyed a deep blue color, and the final dyeing rate is
It was 88%. Example 13 Aminyl Red E-2BL (Sumitomo Chemical Co., Ltd., acid dye, CI No. Acid Red 266)
1.0% owp, tartaric acid 2.0% owp, octyl phosphate potassium salt 3.0% owp, and as a sizing agent, Maypro Gum NP 14% paste (Sanshosha commercial product,
A textile dyeing paste consisting of 40% owP (etherified locust bean gum) was prepared. A tufted carpet processed by the method shown in Example 12 was printed with the colored paste using a 50 mesh screen and steamed in a steamer at 100°C for 20 minutes. Next, it was washed with water, further soaped, washed with water, and dried to finish. The printed tufted carpet was printed in a deep red color, with no dye bleeding from the printed area or staining of the white area, and the final dyeing rate was 84%. Comparative Example 7 When printing was carried out in the same manner as in Example 13 except that octyl phosphate potassium salt was not added, dye bleed from the printed area occurred during steaming, and staining of the white area occurred during soaping. Remarkably, the final dyeing rate was only 40%. Example 14 The same yarn obtained in Example 1 was dyed with Aminyl Blue E-PRL (Sumitomo Chemical Co., Ltd., acid dye, C, I.No. Acid Blue 129) 1.1% owf,
potassium salt of formic acid 2% owf and nonylphenyl phosphate, When dyeing was carried out in the same manner as in Example 1 in a dye bath consisting of 3% OWF, the dye exhaustion rate was 98%, and the final dyeing rate after soaping was 92%. The dyed article showed good light fastness and abrasion fastness. Example 15 The same yarn obtained in Example 1 was made into lanille.
Gray BGl/C (CI No. Acid Black 58) 0.8
%owf, formic acid 2%owf and potassium salt _of stearyl 15 oxyethylene phosphate _C18H37- (
When dyeing was carried out in the same manner as in Example 1 in a dye bath consisting of ₃ % owf _{( OC2H4 ) -15OPO3K2} , the dye exhaustion rate was
The final dyeing rate after soaping was 80%. The dyed article also showed good light fastness and abrasion fastness.

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Claims (1)

[Claims] 1. 99 to 80 parts by weight of crystalline polyolefin, ethylene and general formula () (In the formula, R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 4.) When dyeing a polyolefin fiber material obtained by adding and mixing 1 to 20 parts by weight of a copolymer with an aminoalkyl acrylate compound and melt-spinning with an anionic dye, the following general formula () and A method for dyeing polyolefin fiber materials, which comprises dyeing by adding at least one alkyl phosphate or its salt represented by (). (In the formula, R is an alkyl group having 8 to 22 carbon atoms or an aryl group substituted with an alkyl group having 8 to 18 carbon atoms, m is 0 to 30, M ₁ and M ₂ , M ₃ are each H,
Represents Na, K, Li, NH ₄ , alkylamine or alkanolamine. )