TWI742316B - Dyed polypropylene fiber structure, clothing materials using it, and anthraquinone compounds - Google Patents

Abstract

One aspect of the present invention is a dyed polypropylene fiber structure, which is dyed with a blue dye represented by the following general formula (1),

In the formula, R ₁ is a linear or branched alkyl group having 4 to 14 carbon atoms.

Description

Dyed polypropylene fiber structure, clothing materials using it, and anthraquinone compounds

The present invention relates to dyed polypropylene fiber structures, clothing materials using the same, and anthraquinone compounds.

Polypropylene resin is a crystalline thermoplastic resin obtained by addition polymerization of propylene. This polypropylene resin is made of propylene, which is the waste gas of petroleum refining, and is therefore inexpensive; it has a low density (0.90~0.92g/cm ³ ) that can float on water and is therefore lightweight; almost no water absorption. Wetness (0.0% of the nominal moisture content) therefore has quick-drying properties. Furthermore, polypropylene resins have many excellent features and characteristics such as chemical resistance, abrasion resistance, bending resistance, and antistatic properties (refer to Non-Patent Documents 1 and 2).

Polypropylene is a simple branched chain hydrocarbon polymer. Although it has a methyl group as a side group, it does not have a functional group that is effective for the chemical reaction with the dye. In addition, the crystals of polypropylene are relatively dense and highly hydrophobic, and hardly swell due to water. For these reasons, it is extremely difficult to color polypropylene using traditional dyeing techniques.

The dyeing method of polypropylene fiber, which is difficult to color, is known as supercritical (fluid) dyeing, which uses supercritical carbon dioxide (scCO ₂ ) as the dyeing medium. For example, Patent Document 1 discloses the use of scCO ₂ to dye hydrophobic fiber materials such as polyester fiber materials and polypropylene fiber materials with various dyes.

In addition, Non-Patent Documents 3 and 4 disclose _{specific blue and yellow dyes that can dye polypropylene cloth with scCO 2. By} dyeing with such dyes, dyeing with excellent dye fastness can be provided. Polypropylene fibers.

【Prior Technical Literature】 【Patent Literature】

[Patent Document 1] Japanese Patent No. 3253649

【Non-Patent Literature】

[Non-Patent Document 1] M Ahmed, Polypropylene fibers, science and technology (Amsterdam; New York: Elsevier Scientific Pub. Co., 1982).

[Non-Patent Document 2] J Akrman and J Prikryl, J. Appl. Polym. Sci., 62 (1996) 235.

[Non-Patent Document 3] K. Miyazaki et al., Color. Technol., 128 (2012), 51-59.

[Non-Patent Document 4] K. Miyazaki et al., Color. Technol., 128 (2012), 60-67.

Patent Document 1 discloses only neutral pigments such as disperse dyes and oil-soluble dyes in general, and hydrophobic synthetic fibers that are dyed objects are also listed in general terms. In fact, even if the polypropylene fiber structure is dyed with the dye described in Patent Document 1, the dye can hardly be dyed, and even if it is dyed, the dye fastness of the dyed polypropylene fiber structure is remarkably inferior.

It is known that in general, the dye fastness of fiber structures dyed with dyes of different hues tends to deteriorate compared with the case of single-dye dyeing. Usually, this phenomenon is obvious when the degree of color fading of the compounded dye is inconsistent, or when the hue change caused by discoloration and fading is not offset. For example, in the case of using a yellow dye with extremely excellent light resistance and a blue dye with a slightly inferior light resistance to obtain a green fiber structure, or using a yellow dye that discolors and fades slowly through browning and discoloration and fading are In the case of a light-colored blue dye toning to obtain a green fiber structure, when evaluating the light fastness of the fiber structure, not only the color fade (lightening) to the same color, but the color will change toward the yellow direction. (Hue change). Compared with lightening, the hue change has a greater influence on the evaluation of discoloration and fading. Therefore, if the hue change is large, the discoloration and fading are significant, and the light fastness is deteriorated. Therefore, in any case, the blue dye used as the three primary colors in the dyeing of the fiber structure requires very high light resistance.

The light resistance of the blue dye described in Non-Patent Document 4 is higher than that of the yellow dye described in Non-Patent Document 3. However, the light fastness of the green polypropylene fiber structure obtained by dyeing the two together is deteriorated. Therefore, the blue dye used as the three primary colors in the compound dyeing of polypropylene fiber structures is expected to have higher light resistance.

The present invention is made in view of these issues, and its purpose is to provide a dyed polypropylene fiber structure, which has excellent light fastness and is dyed with a dye that can form the three primary colors of subtractive mixed color blue; The invention also provides a blue dye capable of producing the dyed polypropylene fiber structure.

One aspect of the present invention is a dyed polypropylene fiber structure, which is characterized by It is dyed with a blue dye represented by the following general formula (1).

(式中，R₁係碳數4~14的直鏈或支鏈烷基。)

(In the formula, R ₁ is a straight or branched chain alkyl group having 4 to 14 carbon atoms.)

In the above general formula (1), R ₁ may be tertiary butyl, n-octyl, n-dodecyl or n-tetradecyl. In addition, R ₁ may be n-octyl or n-dodecyl.

In addition, the above-mentioned dyed polypropylene fiber structure may be cloth.

Another aspect of the present invention is a clothing product using the above-mentioned dyed polypropylene fiber structure.

(式中，R_1-1為碳數10、12或14的直鏈烷基，或碳數為4的支鏈烷基。)通式(1-1)中，R_1-1可為正十二基。 Yet another aspect of the present invention is an anthraquinone-based compound characterized in that it is represented by the following general formula (1-1):

(In the formula, R _1-1 is a linear alkyl group having 10, 12 or 14 carbons, or a branched alkyl group having 4 carbons.) In the general formula (1-1), R _1-1 may be normal Twelve bases.

By means of the present invention, it is possible to provide a dyed polypropylene fiber structure that has excellent light fastness and can constitute the subtractive mixed color of the three primary colors of blue; and can provide a blue dye that can produce the dyed polypropylene fiber structure .

200‧‧‧Supercritical fluid dyeing device

201‧‧‧Liquid CO ₂ Cylinder

202‧‧‧Filter

203‧‧‧Cooling Jacket

204‧‧‧High pressure pump

205‧‧‧Preheater

206、207、208‧‧‧Pressure gauge

209‧‧‧Magnetic Drive

210‧‧‧DC motor

211, 212‧‧‧Safety valve

213‧‧‧Cooler

214, 215, 216, 217, 218‧‧‧Stop valve

219‧‧‧Needle valve

220‧‧‧Heater

221‧‧‧roller

222‧‧‧High pressure stainless steel tank

223‧‧‧Dyes covered by dust-free paper

224‧‧‧Impeller

[Fig. 1] A schematic diagram showing the apparatus used for supercritical fluid dyeing in the embodiment.

(式中，R₁係碳數4~14的直鏈或支鏈烷基。)該染色之聚丙烯纖維構造物，可表現減法混色三原色之藍色。進一步地，該染色之聚丙烯纖維構造物，係洗滌堅牢度、耐光堅牢度、昇華堅牢度中任一者皆優異。特別係，該染色之聚丙烯纖維構造物，與非專利文獻4所記載之藍色染料所染色的聚丙烯纖維構造物相比，耐光堅牢度為優異。因此，將通式(1)所表示之藍色染料與其他顏色之染料配合染色所得的聚丙 烯纖維構造物中，配合染色導致的耐光堅牢度之劣化較少。 The polypropylene fiber (PP) structure dyed in the implementation mode is dyed with the blue dye represented by the following general formula (1):

(In the formula, R ₁ is a straight or branched chain alkyl group with 4 to 14 carbon atoms.) The dyed polypropylene fiber structure can express blue of the three primary colors of subtractive mixed color. Furthermore, the dyed polypropylene fiber structure is excellent in any of washing fastness, light fastness, and sublimation fastness. In particular, the dyed polypropylene fiber structure has superior light fastness compared to the polypropylene fiber structure dyed with the blue dye described in Non-Patent Document 4. Therefore, in the polypropylene fiber structure obtained by dyeing the blue dye represented by the general formula (1) with dyes of other colors, the deterioration of the light fastness caused by the dyeing is less.

(Blue dye)

The blue dye constituting the dyed polypropylene fiber structure of the present invention is a compound represented by the above general formula (1). This compound can well dye the polypropylene fiber structure with blue, which can constitute the three primary colors of subtractive color mixing. In addition, the polypropylene fiber structure dyed with the compound is excellent in any of washing fastness, light fastness, and sublimation fastness. In particular, this compound has better light resistance than the blue dye described in Non-Patent Document 4. Therefore, even when the compound is combined with dyes of other colors to dye polypropylene fiber structures, the resulting polypropylene The deterioration of the light fastness of the fiber structure is still small. Furthermore, since the dye represented by the above general formula (1) is a solid, it is easy to handle, and the degree of dyeing (color intensity) can be adjusted slightly, which is beneficial to industrial production.

In order to make the washing fastness and sublimation fastness of the dyed polypropylene fiber structure better, R ₁ is preferably tertiary butyl, n-octyl, n-dodecyl or n-tetradecyl. _{Among these, it is more preferable that R 1} is n-octyl or n-dodecyl from the viewpoint of achieving both color strength and dye fastness.

The dye represented by the above general formula (1) can be based on well-known methods. For example, as an example, a general prescription represented by Japanese Patent No. 2024094, etc., can be obtained by making commercially available 1-methylamine-4-bromoanthracene It is produced by reacting quinone with commercially available alkyl-substituted aniline. There are many similar reports, so it is not limited to the reference patent document prescriptions listed as examples.

(Anthraquinone compounds)

Another embodiment of the present invention is an anthraquinone compound represented by the following general formula (1-1).

式中，R_1-1為碳數10、12或14的直鏈烷基，或碳數為4的支鏈烷基。該化合物，具有新穎性，可作為藍色染料使用，且前述藍色染料係可良好地將可構成減法混色三原色之藍色染於聚丙烯纖維構造物。進一步地，同上述通式(1)所表示之化合物，以通式(1-1)所表示之化合物染色的聚丙烯纖維構造物，係洗滌堅牢度、耐光堅牢度、昇華堅牢度中任一者皆優異。此外，即使是以通式(1-1)所表示之化合物與其他染料配合將聚丙烯纖維構造物染色之情形下，所得聚丙烯纖維構造物的耐光堅牢度的劣化仍少。 【化4】

In the formula, R _1-1 is a linear alkyl group having 10, 12, or 14 carbons, or a branched alkyl group having 4 carbons. This compound is novel and can be used as a blue dye, and the aforementioned blue dye system can well dye blue, which can constitute the three primary colors of subtractive color mixing, on polypropylene fiber structures. Further, the same as the compound represented by the above general formula (1), the polypropylene fiber structure dyed with the compound represented by the general formula (1-1) is any one of washing fastness, light fastness, and sublimation fastness Both are excellent. In addition, even when the polypropylene fiber structure is dyed with the compound represented by the general formula (1-1) in combination with other dyes, the resulting polypropylene fiber structure has little deterioration in light fastness.

In order to make the washing fastness and sublimation fastness of the dyed polypropylene fiber structure better, R _1-1 is preferably tertiary butyl, n-dodecyl, or n-tetradecyl. Among these, from the viewpoint of achieving both color strength and color fastness, R _1-1 is more preferably twelve bases.

The anthraquinone compound in this embodiment can be produced in the same manner as the method for producing the compound of the general formula (1), for example.

(Polypropylene fiber structure)

The polypropylene fiber structure of the present invention contains polypropylene fibers. Among them, the polypropylene fiber system is not particularly limited as long as it contains a polypropylene resin. A polypropylene fiber structure can be formed using fibers composed of polypropylene resin alone, or a polypropylene fiber structure can be formed using fibers prepared by mixing and/or joining other polymer components to polypropylene fibers.

Based on the above-mentioned polypropylene fiber, according to the methods known in the field, various kinds of Type of polypropylene fiber structure. The types of polypropylene fiber structures include, for example, linear structures (long fiber spun yarn, short fiber spun yarn, slit thread, split thread, etc.), cotton (cotton) structure, Button-shaped structures, cloth-shaped structures (textiles, knitted products, non-woven fabrics, felts, terry fabrics, etc.) and combinations thereof, but are not limited to these. In addition, commercially available polypropylene fiber structures can also be used. In addition, other fibers such as polyester may be blended and/or blended with polypropylene fibers to produce a fiber structure.

(Method of manufacturing dyed polypropylene fiber structure)

The dyed polypropylene fiber structure of the present invention can be produced by dyeing the polypropylene fiber structure with the dye represented by the above general formula (1) or the above general formula (1-1) using supercritical carbon dioxide fluid. The method of dyeing polypropylene fiber structures with supercritical carbon dioxide fluid as a medium is well known to those with ordinary knowledge in this field. For example, the polypropylene fiber structure can be dyed according to the dyeing method with supercritical carbon dioxide fluid described in Non-Patent Documents 3 and 4.

The polypropylene fiber structure dyed with the dye represented by the above general formula (1) or the above general formula (1-1) can exhibit a blue of the three primary colors of subtractive mixed color. In addition, the range of "blue of the three primary colors of subtractive mixed color" is well-known in this field, and refers to the range of all hues (H values) of the three attributes of color (hue, lightness, and chroma) that can be regarded as blue. That is, among the attributes of color perception, the hue H (JIS Z8721: 1993) expressed as a hue quantity is centered on 10B and ranges from 10BG to 10PB.

In addition, the dye represented by the above general formula (1) or the above general formula (1-1) may also be combined with the yellow dye described in Non-Patent Document 3 to the extent that the chemical structure of the yellow dye does not affect its properties. A combination of at least one of the yellow dye and the red dye represented by the following general formula (2) is used to dye the polypropylene fiber structure to produce a dyed polypropylene fiber structure Things. In this case, the polypropylene fiber structure can be dyed in free colors.

式中，R₂係分別獨立選自碳數4~8的支鏈烷基、及碳數9~19的芳基烷基所成群中的1種，n為1~3。前述支鏈烷基係包含四級碳原子，前述芳基烷基之烷基部分係包含四級碳原子。其中，在本說明書中使用「四級碳原子」時，係指與4個其他碳原子結合的碳原子。

In the formula, R ₂ is one independently selected from the group of branched alkyl groups having 4 to 8 carbons and arylalkyl groups having 9 to 19 carbons, and n is 1 to 3. The aforementioned branched alkyl group contains quaternary carbon atoms, and the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms. However, when the "quaternary carbon atom" is used in this specification, it refers to a carbon atom bonded to 4 other carbon atoms.

Among them, the red dye represented by the above general formula (2) can dye the polypropylene fiber structure well with the red color that can constitute the three primary colors of subtractive color mixing, and any one of fastness to washing, fastness to light, and fastness to sublimation All are good. _{Furthermore, by making the alkyl portion of the alkyl group of R 2} and the alkyl group of the aryl alkyl group in the above general formula (2) branched and contains quaternary carbon atoms, it is possible to obtain a further excellent color fastness dye. Furthermore, since the dye represented by the above general formula (2) is a solid, it is easy to handle, and the degree of dyeing (color density) can be adjusted slightly, which is beneficial to industrial production.

The above-mentioned branched alkyl groups containing quaternary carbon atoms include, for example, 2-methylprop-2-yl (tertiary butyl), 2-methylbut-2-yl (tertiary pentyl), 2, 4,4-Trimethylpent-2-yl (tertiary octyl), 2-methylheptan-2-yl. Among these, based on the fact that there are fewer residual dyes during dyeing and better dye fastness, the use of 2-methylprop-2-yl, 2-methylbut-2-yl, 2,4,4-trimethylpentan -2-yl is preferred.

The above-mentioned arylalkyl groups containing quaternary carbon atoms include, for example, 2-phenylprop-2-yl (cumyl), 2-phenylbut-2-yl, 2-(o-tolyl)propanyl- 2-base, 1,1-diphenylpropyl, 1,1,1- Trityl (trityl). In addition, the carbon number of the above-mentioned arylalkyl group is preferably 9 or 10.

In the case of n=2 or 3, the 2 or 3 R ₂ may be the same or different.

The compound represented by the above general formula (2) may also be a compound represented by the following general formula (3).

式中，R₃~R₅係分別獨立選自氫原子、碳數4~8的支鏈烷基、及碳數9~19的芳基烷基所成群中的1種。前述支鏈烷基包含四級碳原子，前述芳基烷基之烷基部分包含四級碳原子，R₃~R₅中至少1個為前述支鏈烷基或前述芳基烷基。

In the formula, R ₃ to R ₅ are each independently selected from the group consisting of a hydrogen atom, a branched alkyl group having 4 to 8 carbons, and an arylalkyl group having 9 to 19 carbons. The aforementioned branched alkyl group contains quaternary carbon atoms, the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms, _{and at least one of R 3} to R ₅ is the aforementioned branched alkyl group or the aforementioned aryl alkyl group.

In order to further improve the fastness to dyeing, the number of substituents on the phenoxy group is preferably two, that is, in the above general formula (2), n is preferably 2. In addition, for the same reason, in the above general formula (3), it is preferable that two of R ₃ to R ₅ are each independently the aforementioned branched alkyl group or the aforementioned aryl alkyl group, and the remaining one is a hydrogen atom.

_{It is preferable that R 2} is the aforementioned branched alkyl group and n is 1 or 2 in order to reduce the residual dye during dyeing and adjust the degree of dyeing with good reproducibility. In addition, for the same reason, in the above general formula (3), it is preferable that R ₃ to R ₅ are each independently a hydrogen atom or the aforementioned branched alkyl group, and one or two of _{R 3} to R _{5 are the aforementioned} Branched alkyl. Particularly, based on the fact that the dyeing fastness is better, the residual dye during dyeing is less. In the above general formula (2), it is more preferable that R ₂ is the aforementioned branched alkyl group, and n is 2. For the same reason, in the above general formula (3), it is more preferable that two of R ₃ to R ₅ are each independently the aforementioned branched alkyl group, and the remaining one is a hydrogen atom.

Especially preferred, the above-mentioned red dye is a compound in which R ₂ of the above general formula (2) is 2,4,4-trimethylpent-2-yl, n is 1, and R ₂ exists in the 4-position of the phenoxy group _{; Or R 2} of the above general formula (2) is 2-methylprop-2-yl or 2-methylbut-2-yl, n is 2, and R ₂ exists in the 2-position and 4-position of the phenoxy group Compound. These compounds have excellent fastness to dyeing and dyeability, in particular, no dye remains during dyeing, and the color of dyeing can be controlled with good reproducibility.

The red dye represented by the above general formula (2) is well known and can be produced by a method known to those with ordinary knowledge in the field. For example, the commercially available 1-amine-2-bromo-4-hydroxyanthraquinone-9,10-dione can be made under known conditions as described in Dyes and Pigments, 95, 2012, 201-205 It is produced by reacting with commercially available branched alkyl or aryl alkyl substituted phenol.

(Use of dyed polypropylene fiber structure)

Although the use of the dyed polypropylene fiber structure of the present invention is not particularly limited, examples include clothing, underwear, hats, socks, gloves, sports clothing, etc., vehicle interior materials such as seat sheets, and carpets. , Curtains, floor mats, sofa covers, pillowcases and other indoor products. Since the dyed fiber structure of the present invention can express free colors, it can be applied to clothing products.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples.

Example

(Material)

Polypropylene cloth, obtained from Mitsubishi Rayon Co., Ltd. (now Mitsubishi Chemical Co., Ltd.). The obtained polypropylene cloth is a compact two-stage knit (polypropylene cloth No.2; 250g/m ² ; 190dtex/48 filaments; warp loop 2×33/2.54cm; weft loop 2) suitable for determining the fastness of dyeing. ×34/2.54cm). The two-stage knitting uses soda ash (industrial grade, 2g/dm ³ ), 1g/dm ³ surfactant (Daisurf MOL-315; First Industrial Pharmaceutical Co., Ltd.), 0.5g/dm ³ chelating agent ( Sizol FX-20; First Industrial Pharmaceutical Co., Ltd.), refined in a liquid flow dyeing machine with water at 80°C. After that, the polypropylene cloth No. 2 was dewatered by centrifugation, and the cut pieces were heat-set at 130°C as a pretreatment.

Wood wool thread (30/ cotton yarn count), purchased from Clover Mfg Co., Ltd. In the dyeing process, the supercritical fluid is diffused, and three types of cotton cloth are used to cover the polypropylene cloth. The first type has a wire mesh structure (cotton cloth No. 1: 30 vertical lines/2.54 cm, and 30 horizontal lines/2.54 cm), and the second type has a single-sided flannel structure (cotton cloth No. 2). These cloths were purchased from Pip Fujimoto Co., Ltd. (Pip Fujimoto). The third type has a plain weave structure (cotton cloth No. 3: vertical threads 45/2.54cm, horizontal threads 45/2.54cm; product name "Shandong Sun"), purchased from Hasegawa Cotton Co., Ltd.

Liquid carbon dioxide (>99.5%), obtained by Uno Oxygen Co., Ltd.

The chemical structures of dyes 1-9 used in the experiment are shown in Table 1 below.

【Table 1-1】

【Table 1-2】

Dyes 1, 2, 4, 7, 8, and 9 are prototype synthetic products obtained by Arimoto Chemical Industry Co., Ltd. Dyes 3, 5, and 6 were synthesized according to the following synthesis examples. Any dye is in solid form. In the synthesis example shown here, the reaction solvent used N-methylpyrrolidone (hereinafter referred to as NMP) or isobutanol, but it is not limited to this.

(Synthesis Example 1: 1-(methylamine)-4-[(4-tertiary butylbenzene)amine]anthracene-9,10-dione)

47 g of 1-methylamine-4-bromoanthraquinone, 19 g of potassium acetate, 67 g of p-tertiary butylaniline, and 48 g of NMP were heated to about 90°C while stirring. After reaching 90°C, 0.17 g of copper (I) chloride and 2 g of NMP were added. The temperature was further increased to 140°C, and the reaction was carried out at 140°C for 2 hours. After the reaction, the reaction liquid was allowed to cool naturally while stirring. When the temperature of the reaction solution was close to 65°C, 150 g of methanol was added. one While continuing to stir to cool, collect the precipitated dye by suction filtration at the temperature of the reaction solution below 35°C. Next, the obtained dye was stirred in 85 g of methanol for more than 1 hour. After that, the dye was taken out by suction filtration. Further, the taken-out dye was stirred in 300 g of hot water at about 60° C. and 8 g of concentrated hydrochloric acid for more than 1 hour, and the target dye was obtained by suction filtration. At this time, wash with hot water until the pH of the filtrate is in the neutral range. The resulting wet cake of the dye was dried at 70°C.

Yield 50.1g, yield 87.4% (HPLC purity 94.952%)

(Synthesis Example 2: 1-(methylamine)-4-[(4-dodecylphenyl)amine]anthracene-9,10-dione)

47 g of 1-methylamine-4-bromoanthraquinone, 17 g of potassium acetate, 59 g of p-n-dodecylaniline, and 48 g of isobutanol were heated to about 90°C while stirring. After reaching 90°C, 0.36 g of copper (I) chloride and 2 g of isobutanol were added. The temperature was further increased to 113°C, and the reaction was carried out at 113°C for 5 hours. After the reaction, the reaction liquid was allowed to cool naturally while stirring. When the temperature of the reaction solution was close to 65°C, 100 g of methanol was added. While continuing to stir to cool, collect the precipitated dye by suction filtration at the temperature of the reaction solution below 35°C. Next, the obtained dye was stirred in 250 g of methanol for more than 1 hour. After that, the dye was taken out by suction filtration. Furthermore, the taken-out dye was stirred in 200 g of hot water and 8 g of concentrated hydrochloric acid at about 60° C. for more than 1 hour, and the target dye was obtained by suction filtration. At this time, wash with hot water until the pH of the filtrate is in the neutral range. The resulting wet cake of the dye was dried at 70°C.

Yield 59.8g, yield 80.8% (HPLC purity 97.459%)

(Synthesis Example 3: 1-(methylamine)-4-[(4-tetradecylphenyl)amine]anthracene-9,10-dione)

Combine 10.9g of 1-methylamine-4-bromoanthraquinone, 3.93g potassium acetate, 15g p-n-tetradecylaniline and 10 g of isobutanol was heated to about 90°C while stirring. After reaching 90°C, 0.16 g of copper (I) chloride and 5 g of isobutanol were added. The temperature was further increased to 113°C, and the reaction was carried out at 113°C for 4 hours. After the reaction, the reaction liquid was allowed to cool naturally while stirring, and 35 g of methanol was added when the temperature of the reaction liquid was close to 75°C. While continuing to stir to cool, collect the precipitated dye by suction filtration at the temperature of the reaction solution below 35°C. Next, the obtained dye was stirred in 35 g of methanol for more than 1 hour. After that, the dye was taken out by suction filtration. Further, the taken-out dye was stirred in 120 g of hot water and 4 g of concentrated hydrochloric acid at about 60° C. for more than 1 hour, and the target dye was obtained by suction filtration. At this time, wash with hot water until the pH of the filtrate is in the neutral range. The resulting wet cake of the dye was dried at 70°C.

Yield 15.5g, yield 85.5% (HPLC purity 95.766%)

(Supercritical fluid dyeing procedure)

Using the above dyes 1-9, the polypropylene cloth was dyed according to the following method, and the dyeing ability of each dye to polypropylene fiber was evaluated. In addition, the presence or absence of the dye deposited on the inner wall of the dyeing tank was also confirmed. The residual dye in the tank is evaluated for the total of the residue of the wiping paper and the deposit on the inner wall. Furthermore, a dyed cloth for evaluating the fastness of dyeing was produced for each dye. Cut the polypropylene cloth No.2 to 20×150cm, and measure the weight (about 75g). Cotton cloth No. 1, 2 and 3 were cut into 20×100cm, 20×75cm, and 20×35cm, respectively. First, the cotton cloth Nos. 1 and 2 were wound in sequence on a stainless steel drum (width 220 mm; outer diameter 30 mm, inner diameter 26 mm) ^{with perforations (diameter 3 mm, number of holes/area 1.87/cm 2, effective width 190 mm).} In order to avoid the direct impact of perforation on the dyeing of polypropylene cloth No.2, use this cloth as a base cloth. The base fabric prevents the fluid from passing straight through the perforations, so that it can flow uniformly on the dyed material. Next, the polypropylene cloth No. 2 and the cotton cloth No. 3 are wound in order. Cotton cloth No.3 prevents the shrinkage of the polypropylene cloth caused by the radiant heat from the tank. The wound roll is loosely tied to the tip with cotton thread and fixed.

The device used for supercritical fluid dyeing is shown in Figure 1. The supercritical fluid dyeing device 200 is composed of a liquid CO ₂ cylinder 201, a filter 202, a cooling jacket 203, a high-pressure pump 204, a preheater 205, a pressure gauge 206~208, a magnetic drive unit 209, a DC motor 210, and a safety valve 211 to 212, cooler 213, stop valve 214 to 218, needle valve 219, heater 220. The drum 221 wound with the cloth sample is placed in a high-pressure stainless steel tank 222 (volume 2230 cm ³ ). Dye 223 (0.3% of the weight of the polypropylene dyed object; that is, 0.3% omf) covered with wiping paper (KimWipes S-200, manufactured by Nippon Paper Crecia Co., Ltd.) is placed in the tank 222 The fluid path above the roller 221.

Close the valve of tank 222 and heat to 120°C. After reaching the dyeing temperature, the pump 204 is used to flow liquid carbon dioxide (1.13 kg) through the cooling jacket 203 to the tank 222. The carbon dioxide fluid is circulated by the stainless steel impeller 224 and the magnetic drive part 209 installed at the bottom of the tank 222. The rotational speed of the magnetic drive unit 209 is 750 rpm. The flow direction of the fluid is from the inner side to the outer side of the drum 221.

After the temperature and pressure cycle speed reaches a certain value (that is, 120°C, 25MPa, 750rpm), maintain 60 minutes under these conditions to dye the polypropylene cloth. Control the release speed to reduce the pressure from 25MPa to atmospheric pressure within 15 minutes. The circulation system continues until the internal pressure of the tank is almost reduced to the critical pressure (8.0~7.4MPa). After that, the dyed polypropylene cloth is taken out from the tank 222.

The dye deposited on the surface of the polypropylene cloth is removed by the operation of slowly releasing pressure under continuous circulation. Therefore, as long as it is not a dye concentration that will cause a large surplus, subsequent cleaning procedures should not be required. The rubbing fastness (JIS L0849, Type II, lining fabric: cotton), which tends to exhibit abnormally low performance when the dye is precipitated from the surface, is normalized by this pressure-relieving operation. In the embodiment of the present invention, both dry friction and wet friction have a performance of 4-5 to 5 grades. Use dyes 1~9 to make this example The dyeing ability of the polypropylene cloth No.2 used is good. In addition, no dye remains (trace amount) in the tank.

(Washing fastness)

Washing fastness test, using multi-fiber interwoven fabric as lining fabric (Interwoven No. 1: JIS L0803: 2005; cotton, nylon, acetate fiber, wool, rayon, polyacrylonitrile fiber, silk and polyester cloth woven ), implemented in accordance with JIS L0844:2005 A-2 method (based on ISO 105-C02: 1989 Test 2). The contamination of multi-fiber interwoven fabric is an evaluation of the most contaminated nylon part. In addition, not only the pollution of the cloth, but also the evaluation of the pollution of the test solution with reference to ISO 105-D01:1994. In the evaluation of the contamination of the test solution, the test solution remaining in the container is passed through the filter paper. Use the penetrating light under the gray scale for pollution evaluation to color the pollution of the filtered test solution in the glass test tube (diameter 25mm) before the white card, and compare it with the unused test solution.

(Light fastness)

The light fastness of the dyed polypropylene cloth was evaluated based on JIS L0842 (3rd exposure method). The light fastness test uses ultraviolet carbon arc lamp to implement the third exposure method at level 3 and/or level 4.

(Sublimation fastness)

The sublimation fastness of the dyed polypropylene cloth was evaluated based on JIS L0854, using nylon as the lining fabric (single fiber cloth (I) No. 7: JIS L0803: 2005).

(Color measurement)

For the color measurement of the dyed polypropylene cloth, a spectrophotometer (CM-600d: manufactured by Konica Minolta Co., Ltd., Japan) was used. The measurement conditions of the spectral reflectance are: superimpose 4 samples on non-fluorescent white paper, measure diameter φ8mm, observe condition 2° field of view, observe light source D65, measure wavelength range 400~700nm, measure wavelength interval 10nm, remove specular reflection light (SCE: Specular Component Exclude). Based on the spectral reflectance, calculate the values of ^{L *} , a ^* , and b ^{* on} the basis of ^{CIE1976L *} a ^* b ^*. Furthermore, based on JIS Z8721: 1993, the hue H of the D65 light source is determined.

(Examples 1 to 11, Comparative Examples 1 to 4, Reference Examples 1 to 4)

The test results of dyeing with dyes 1-9 alone are shown in Table 2. Table 3 shows the test results of dyeing by combining the blue dyes of dyes 3, 5, and 7 with the yellow dye of dye 8 or the red dye of dye 9.

As shown in Table 2, the polypropylene fabrics of Examples 1 to 5 dyed with dyes 2 to 6 separately have light fastnesses above level 4. This system means that in order to have good light fastness, the chemical structure of the dye needs to be: the substituent at position 1 of the anthraquinone ring is a methylamino group, and the substituent at position 4 is a straight or branched chain with 4 to 14 carbon atoms Alkyl substituted anilino. Among them, the dyed polypropylene cloths of Examples 2 to 5 have excellent washing fastness and sublimation fastness. In addition, the dyes 2 to 6 with different carbon numbers of the alkyl substituents on the phenyl group of formula (1) were dyed with the same quality in Examples 1 to 5, and the polypropylene cloth of Example 5 dyed with dye 6 Since the molecular weight becomes larger when the molar absorption coefficient is almost the same, the color is lighter than that of Examples 1 to 4. On the other hand, the polypropylene fabrics of Comparative Examples 2 and 3 dyed with the blue dye dye 7 described in Non-Patent Document 4 had worse light fastness than Examples 1 to 5. In particular, in Comparative Example 3 dyed at a lower concentration, the light fastness was deteriorated.

For general clothing, the washing fastness, light fastness, and sublimation fastness are required to be level 3 or higher. As shown in Table 3, examples 6 to 9 dyed with blue dye 3 or dye 5 and yellow dye 8, and examples 10 and 11 dyed with blue dye 5 and red dye 9 are left in the tank It has few dyes, and the washing fastness, light fastness, and sublimation fastness are all above level 3, which meets the standards required by general clothing. Polypropylene cloth dyed with yellow dye 8 will slowly fade through browning due to light irradiation. Therefore, the light fastness of Examples 6-9 dyed with dye 8 in combination with dyes of other colors is higher than that of dye 8. Reference examples 1 to 3 for single-product dyeing are higher. In contrast, the blue dye 7, which is inferior to the blue dye of the present invention in light fastness under single-product dyeing, and the polypropylene cloth of Comparative Example 3 dyed with the yellow dye 8, has a light fastness of less than 3. Grade, does not meet the standards required by general clothing.

Above, although the present invention has been described with reference to the above-mentioned embodiments, the present invention is not limited to the above-mentioned embodiments. Any combination or replacement of the constitution of the embodiments also belongs to the present invention. Included. In addition, based on the knowledge of a person with ordinary knowledge in the field, appropriate combinations of the implementation patterns can be used to replace the combination or the sequence of steps in the implementation patterns, or to change various designs and other deformations. Such a modified implementation pattern is also It can be included in the scope of the present invention.

【Industrial Utilization】

The present invention can be used in clothing, underwear, hats, socks, gloves, sports clothing and other clothing materials, seat sheets and other vehicle interior materials, carpets, curtains, floor mats, sofa covers, pillowcases, etc. Indoor supplies, etc.

Claims (8)

A dyed polypropylene fiber structure characterized in that it is dyed with a blue dye represented by the following general formula (1), and supercritical carbon dioxide fluid is used as the dyeing medium:

In the formula, R ₁ is a linear or branched alkyl group having 4 to 14 carbon atoms. Such as the dyed polypropylene fiber structure described in item 1 of the scope of patent application, wherein R ₁ is tertiary butyl, n-octyl, n-dodecyl or n-tetradecyl. Such as the dyed polypropylene fiber structure described in item 1 of the scope of patent application, wherein R ₁ is n-octyl or n-dodecyl. The dyed polypropylene fiber structure described in item 1 of the scope of patent application, wherein the aforementioned blue dye is 1-(methylamine)-4-[(4-dodecylphenyl)amine]anthracene-9,10 -Diketone. The dyed polypropylene fiber structure described in any one of items 1 to 4 in the scope of the patent application is cloth. A clothing product using the dyed polypropylene fiber structure described in any one of items 1 to 5 in the scope of the patent application. A dye for dyeing using supercritical carbon dioxide fluid as a dyeing medium, characterized in that it contains an anthraquinone compound represented by the following general formula (1-1):

In the formula, R _1-1 is a linear alkyl group having 10, 12, or 14 carbons, or a branched alkyl group having 4 carbons. For dyeing dyes using supercritical carbon dioxide fluid as a dyeing medium as described in item 7 of the scope of the patent application, R _1-1 is n-dodecyl.

Images