TW201823366A - Dyed polypropylene fiber structure and garment using same - Google Patents

Abstract

This dyed polypropylene fiber structure is characterized by being dyed with a red dye that is represented by general formula (1). (In the formula, each R1 independently represents a group selected from the group consisting of branched alkyl groups having 4-8 carbon atoms and aryl alkyl groups having 9-19 carbon atoms; and n represents a number of 1-3. The branched alkyl groups contain a quaternary carbon atom; and alkyl moieties of the aryl alkyl groups contain a quaternary carbon atom).

Description

   Dyed polypropylene fiber structure and clothing product using the same   

The present invention relates to a dyed polypropylene fiber structure and a clothing product using the same.

Polypropylene resin is a crystalline thermoplastic resin obtained by addition polymerization of propylene. This polypropylene resin uses propylene as the raw material for exhaust gas during petroleum refining and is therefore cheap; it is light-weight due to its low density (0.90 ~ 0.92g / cm ³ ) that can float in water; almost no water absorption‧ Hygroscopicity (0.0% of nominal moisture content) is therefore quick-drying. Furthermore, polypropylene resins have many excellent features and characteristics such as chemical resistance, abrasion resistance, bending resistance, and antistatic properties (see Non-Patent Documents 1 and 2).

Polypropylene is a polymer of pure branched hydrocarbons. Although it has a branched methyl group, it has no functional groups effective for chemical reactions with dyes. In addition, the crystals of polypropylene are relatively dense and extremely hydrophobic, and hardly swell with water. For these reasons, the coloring system of polypropylene using conventional dyeing techniques is extremely difficult.

Currently, the colored polypropylene fiber structures on the market are almost original lines made by the dope coloring method (original method) where pigments are added during the manufacturing stage of polymer pelletizing. The original method must be at the initial stage of the production of the fiber product, that is, there is an inconvenience that the color must be determined at the time of melt spinning, and the color cannot be selected in a timely manner. In addition, since the original thread was added with a pigment that is a foreign substance, the linearity is poorer than that of an uncolored conventional thread, and it is not possible to stably produce a thin thread with a single-line fineness of 1 dtex or less. Furthermore, when changing the color of the thread to be manufactured, it is necessary to push out and replace the resin of the previous color in the melt spinning device with the resin of the next color, and therefore it is necessary to discard a large amount of resin and a lot of time. If the profitability and market price are considered, the original work is bound to produce more than a certain amount in one color, and the number of colors is naturally limited.

As a synthetic resin, polyethylene, polyvinyl chloride, and polystyrene are listed as one of the four general-purpose synthetic resins. It is used in a wide range of fields with low raw material costs and excellent characteristics (non-patented) Reference 3). In contrast, the use of polypropylene as a synthetic fiber is quite limited (Non-Patent Document 4). This is mainly due to the scarce number of colors due to the inability to dye conventional polypropylene threads, and the fact that the original effective method of the only effective coloring method has to make the single thread fineness larger.

If the method of freely dyeing polypropylene fibers is put into practical use, there is no restriction on the number of colors, and inexpensive conventional threads with small (fine) single thread fineness can be colored. As a result, the pursuit of design has become more advanced, and new applications that utilize this feature can be expected in areas where polypropylene fibers have not yet been applied, such as in the field of vehicle interior materials or clothing.

In the 1960s, there were attempts to dye polypropylene fibers in water by changing the molecular structure of the dye. Patent Documents 1 to 5 and Non-Patent Document 5 listed several dyes for polypropylene dyeing. Furthermore, according to the aqueous dyeing studies of polypropylene fibers described in Non-Patent Documents 6 to 11, dyes used for fibers with very high hydrophobicity, such as polypropylene, must have a dyestuff that is much higher than conventional dyes for polyester fibers. Hydrophobic. However, dyes which can be dyed in water and which have good fastness to light, washing, rubbing, sublimation, etc. of the dyed polypropylene fibers have not yet been discovered.

A method for dyeing polypropylene fibers instead of water-based dyeing is known as supercritical (fluid) dyeing, and a method using supercritical carbon dioxide (scCO ₂ ) as a dyeing medium. For example, Patent Document 6 discloses that, using scCO ₂ , hydrophobic fiber materials such as polyester fibers and polypropylene fibers can be dyed with various dyes. Non-patent documents 12 to 17 describe that supercritical dyeing can be used to dye polypropylene fibers with polyester dyes currently on the market.

In addition, Non-Patent Documents 18 and 19 disclose specific blue and yellow dyes capable of dyeing polypropylene cloth with scCO _2. Dyeing with these dyes can provide dyeing with excellent fastness to dyeing. Polypropylene fibers.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 38-10741

[Patent Document 2] Japanese Patent Publication No. 40-1277

[Patent Document 3] Japanese Patent Publication No. 41-3515

[Patent Document 4] British Patent No. 872,882

[Patent Document 5] US Patent No. 3,536,735

[Patent Document 6] 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] P. Galli, S. Danesi and T. Simonazzi, Polym. Eng. Sci, 24 (1984), 544.

[Non-Patent Document 4] Yamamoto Yang, Journal of the Fiber Society, 61 (2005), 319-321.

[Non-Patent Document 5] Yoshio Nagai, Masaki Matsuo, Journal of the Organic Synthetic Chemistry Association, 23 (1) (1965), 2-11.

[Non-Patent Document 6] Z H Cui, S F Zhang and J Z Yang, Chin. Chem. Lett., 18 (2007) 1145.

[Non-Patent Document 7] T Kim, J Jung, K Jang, S Yoon and M Kim, Fibers Polym., 10 (2009) 148.

[Non-Patent Document 8] T Kim, J Jung, S Son, S Yoon, M Kim and J S Bae, Fibers Polym., 9 (2008) 538.

[Non-Patent Document 9] T Kim, J Jung, S Yoon, M Kim and Y-A Son, J. Korean Soc. Dye. Finish., 19 (2007) 28.

[Non-Patent Document 10] T Kim, S Yoon, J Hong, H Kim and J Bae, J. Korean Soc. Dye. Finish., 18 (2006) 30.

[Non-Patent Document 11] S J Mangan, J Crouse and F Calogero, Text. Chem. Color., 21 (1989) 38.

[Non-Patent Document 12] W Oppermann, H Herlinger, D Fiebig and O Staudenmayer, Melliand Textilberichte-Int. Text.Rep., 77 (1996) 588.

[Non-Patent Document 13] E Bach, E Cleve and E Schollmeyer, J. Text. Inst. Part 1 Fiber Sci. Text. Tecnol., 89 (1998) 647.

[Non-Patent Document 14] E Bach, E Cleve and E Sehollmeyer, J. Text. Inst. Part 1 Fiber Sci. Text. Tecnol., 89 (1998) 657.

[Non-Patent Document 15] D Knittel, W Saus and E Schollmeyer, Tech. Text., 38 (1995) 184.

[Non-Patent Document 16] S-K Liao, P-S Chang and Y-C Lin, J. Text. Eng., 46 (2000) 123.

[Non-Patent Document 17] S-K Liao, P-S Chang and Y-C Lin, J. Polym. Res., 7 (2000) 155.

[Non-Patent Document 18] K. Miyazaki et al., Color. Technol., 128 (2012), 51-59.

[Non-Patent Document 19] K. Miyazaki et al., Color. Technol., 128 (2012), 60-67.

As described above, blue and yellow dyes have been found as dyes for providing dyed polypropylene fiber structures having excellent dyeing fastness (see Non-Patent Documents 18 and 19). However, in order to obtain colors freely, at least one of each dye having a hue (yellow, red, and blue) similar to the three primary colors of subtraction (yellow, magenta, and cyan) must be provided. The red dyes that make up the three primary colors have not been found. Therefore, in polypropylene fiber structures, dyeing with a free hue by dye blending has not yet been achieved.

Furthermore, Patent Document 6 discloses neutral pigments such as disperse dyes and oil-soluble dyes, but the hydrophobic synthetic fibers to be dyed are only listed in general. In fact, even if the polypropylene fiber structure is dyed using the dye described in Patent Document 6, the dye is hardly dyed, and even if dyed, the dyeing fastness of the dyed polypropylene fiber structure is significantly poor.

The present invention has been made in view of these problems, and an object thereof is to provide a dyed polypropylene fiber structure which is dyed with a red dye which has excellent fastness to dyeing and which exhibits a subtractive mixed primary color.

In one aspect, the present invention provides a dyed polypropylene fiber structure characterized by being dyed with a red dye represented by the following general formula (1): In the formula, R1 is independently selected from the group consisting of a branched alkyl group having 4 to 8 carbon atoms and an arylalkyl group having 9 to 19 carbon atoms, and n is an integer of 1 to 3. The branched alkyl group includes a quaternary carbon atom, and the alkyl portion of the arylalkyl group includes a quaternary carbon atom.

When the term "quaternary carbon atom" is used in this specification, it means a carbon atom bonded to 4 other carbon atoms.

In the general formula (1), n may be two.

In the general formula (1), n may be 2, and each of the R ₁ groups is independently the aforementioned branched alkyl group. In the above general formula (1), n may be 1 and the R ₁ group may be the aforementioned branched alkyl group.

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

In another aspect, the present invention provides a clothing product, which is characterized in that the dyed polypropylene fiber structure is used.

According to the present invention, it is possible to provide a red dyed polypropylene fiber structure which can exhibit a subtractive color mixing of three primary colors, which is dyed with a red dye having excellent dyeing fastness and dyeability.

100‧‧‧ Device used in dyeability test

101‧‧‧Liquid CO ₂ cylinder

102‧‧‧stop valve

103‧‧‧Needle Valve

104‧‧‧Cooler

105‧‧‧High-pressure pump

106‧‧‧ Liquid Delivery Pump

107‧‧‧stop valve

108‧‧‧safety valve

109‧‧‧Pressure gauge

110‧‧‧stop valve

111‧‧‧preheater

112‧‧‧Staining tank

116‧‧‧Filter

117‧‧‧ Magnetic Stirrer

118‧‧‧ constant temperature empty bath

119‧‧‧ Magnetic stirring constant temperature empty bath

120‧‧‧ thermometer

121‧‧‧stop valve

122‧‧‧Back pressure control valve

123‧‧‧heater

124‧‧‧Semi-automatic back pressure control valve

200‧‧‧Supercritical fluid dyeing device

201‧‧‧Liquid CO ₂ cylinder

202‧‧‧Filter

203‧‧‧Cooling jacket

204‧‧‧High-pressure pump

205‧‧‧preheater

206, 207, 208‧‧‧ manometer

209‧‧‧ Magnetic Drive

210‧‧‧DC Motor

211, 212‧‧‧safety valve

213‧‧‧Cooler

214, 215, 216, 217, 218‧‧‧Stop valves

219‧‧‧Needle Valve

220‧‧‧heater

221‧‧‧ cylinder

222‧‧‧High-pressure stainless steel tank

223‧‧‧ Dye coated with dust-free paper

224‧‧‧ Impeller

FIG. 1 is a schematic diagram showing an apparatus used in a dyeability test in the examples.

Fig. 2 is a schematic diagram showing a device for dyeing supercritical fluid in the embodiment.

The polypropylene fiber (PP) structure dyed in the embodiment is characterized in that it is dyed with a red dye represented by the following general formula (1): In the formula, R ₁ is independently selected from the group consisting of a branched alkyl group having 4 to 8 carbon atoms and an arylalkyl group having 9 to 19 carbon atoms, and n is an integer of 1 to 3. The branched alkyl group includes a quaternary carbon atom, and the alkyl portion of the arylalkyl group includes a quaternary carbon atom.

The polypropylene fiber structure dyed with the above-mentioned dyes can show the red color of the subtractive mixed primary colors. Further, the dyed polypropylene fiber structure is excellent in washing fastness, light fastness, and sublimation fastness.

(Dye)

The red dye constituting the dyed polypropylene fiber structure of the present invention is a compound represented by the general formula (1). In order for the polypropylene fiber structure to be well dyed with red that constitutes the three primary colors of subtractive color mixing, and to make it good in any of washing fastness, light fastness, and sublimation fastness, it must be: R _{1 in the} formula is independently selected from the group consisting of a branched alkyl group having 4 to 8 carbon atoms and an aryl alkyl group having 9 to 19 carbon atoms; n is an integer of 1 to 3; The group contains a quaternary carbon atom; the alkyl portion of the aforementioned arylalkyl group contains a quaternary carbon atom.

By making the alkyl portion of the alkyl group and the arylalkyl group of R ₁ branched and containing a quaternary carbon atom, a dye having excellent dyeing fastness can be obtained. Further, since the dye represented by the general formula (1) is a solid, it is easy to handle, and the degree of dyeing (color intensity) can be finely adjusted, which is advantageous for industrial production.

Examples of the above-mentioned alkyl group containing a quaternary carbon atom include a 2-methylpropane-2-yl (tert-butyl) group, a 2-methylbutane-2-yl (tert-amine) group, and 2, 4,4-trimethylpentane-2-yl (tert-octyl), 2-methylheptane-2-yl. Among these, there are few residual dyes at the time of dyeing, and excellent dyeing fastness. 2-methylpropane-2-yl, 2-methylbutane-2-yl, 2,4,4-trimethyl Pentane-2-yl is preferred.

Examples of the above-mentioned aromatic alkyl group containing a quaternary carbon atom include 2-phenylpropane-2-yl (cumyl) yl, 2-phenylbutane-2-yl, and 2- (o-tolyl) yl ) Propane-2-yl, 1,1-diphenylpropyl, 1,1,1-triphenylmethyl (triphenylmethyl). The carbon number of the arylalkyl group is preferably 9 or 10.

When n = 2 or 3, two or three R ₁ may be the same or different.

The compound represented by the general formula (1) may be a compound represented by the following general formula (2).

In the formula, R ₂ to R ₄ are each independently selected from the group consisting of a hydrogen atom, a branched alkyl group having 4 to 8 carbon atoms, and an arylalkyl group having 9 to 19 carbon atoms. The branched alkyl group includes a quaternary carbon atom, the alkyl portion of the arylalkyl group includes a quaternary carbon atom, and at least one of R ₂ to R ₄ is the branched alkyl group or the aryl alkyl group.

The dyeing fastness can be further improved, and the number of substituents on the phenoxy group is preferably two, that is, in the general formula (1), n is preferably 2. For the same reason, in the general formula (2), it is preferred that two of R ₂ to R ₄ are each independently the branched alkyl group or the aryl alkyl group, and the remaining one is a hydrogen atom.

It is preferable that R ₁ is the aforementioned branched alkyl group, and n is 1 or 2 based on the fact that less residual dyes can be obtained at the time of dyeing, and the reproducibility of the degree of dyeing can be well adjusted. Further, for the same reason, the above general formula (2), preferably based R ₂ ~ R ₄ each independently a hydrogen atom or the branched alkyl group and R ₂ ~ R ₄ have one or two of the Branched alkyl. In particular, based on the fact that it can become a dyeing fastness with less residual dye during dyeing, in the general formula (1), it is further preferred that R ₁ is the aforementioned branched alkyl group and n is 2. For the same reason, in the general formula (2), it is more preferable that two of R ₂ to R ₄ are each independently the branched alkyl group, and the remaining one is a hydrogen atom.

In a particularly preferred embodiment of the present invention, the dye is as follows: R _{1 in} the general formula (1) is 2,4,4-trimethylpentane-2-yl, n is 1, and phenoxy is 4 R ₁ bit present in the compound; or R in the general formula (1) of _{2-methyl-2-1-yl} or 2-methyl-butan-2 group, n is 2, the two phenoxy And compounds in which R _{1 is} present at the 4-position. These compounds have excellent dyeing fastness and dyeing property, and in particular, no dye remains during dyeing, and the color of the dyeing can be controlled with good reproducibility.

The red dye represented by the general formula (1) is a blue dye and a yellow dye that can be used to dye a polypropylene fiber structure, and is specifically a blue dye and a non-patent document 3 and 4 respectively. Yellow dyes are used together to dye free shades on polypropylene fiber structures.

The dye represented by the above general formula (1) is known and can be produced by a method known to those skilled in the art. For example, a commercially available 1-amino-2-bromo-4-hydroxyanthracene-9,10-diamine can be prepared under known conditions as described in Dyes and Pigments, 95, 2012, 201-205. Ketones are produced by reacting commercially available branched alkyl or arylalkyl-substituted phenols.

(Polypropylene fiber structure)

The polypropylene fiber structure of the present invention includes polypropylene fibers. Here, the polypropylene fiber is not particularly limited as long as it contains a polypropylene resin. The polypropylene fiber structure may be formed by using a fiber composed of a polypropylene resin alone, or the polypropylene fiber may be formed by blending and / or joining other polymer components in the polypropylene fiber.

Based on the above-mentioned polypropylene fibers, polypropylene fiber structures of various forms can be produced by methods known in the art. The types of polypropylene fiber structures include, for example, linear structures (long fiber, short fiber, slit, split, etc.), cotton (cotton) structures, and button shapes Structures, cloth-like structures (textiles, knits, non-wovens, felts, plush tufts, etc.) and combinations thereof, but are not limited to these. Alternatively, a commercially available polypropylene fiber structure may be used. Further, other fibers such as polyester may be blended and / or mixed with polypropylene fibers to produce a fiber structure.

(Manufacturing method of dyed polypropylene fiber structure)

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

The polypropylene fiber dyed with the dye represented by the above general formula (1) can exhibit a red color of subtractive color mixing. In addition, the range of "the red of the three primary colors of subtractive color mixing" is known in the field, and refers to those in which all the hue (H value) among the three attributes of color (hue, lightness, and chroma) are regarded as the red range. That is, among the attributes of color perception, the hue H (JIS Z8721: 1993) after the hue scale is tabulated ranges from 10P to 10R. In addition, the dye represented by the general formula (1) may be combined with, for example, the blue dye and the yellow dye described in Non-Patent Documents 3 and 4, respectively, to dye a polypropylene fiber structure to produce a dyed polypropylene fiber structure. Thing. In this case, the polypropylene fiber structure can be dyed to a free hue.

(Use of dyed polypropylene fiber structure)

Although the application of the dyed polypropylene fiber structure of the present invention is not particularly limited, examples thereof include clothing products such as clothing, underwear, hats, socks, gloves, sports clothing, vehicle interior materials such as seat sheets, carpets, Curtains, floor mats, sofa covers, pillow cases, etc. Since the dyed fiber structure of the present invention can express a free color tone, it can be suitably used for clothing.

Examples are described below to explain the present invention in detail, but the present invention is not limited to these examples.

[Example]

(Material)

The chemical structures of the dyes 1 to 26 used in the test are shown in Table 1 below. In addition, regarding the dyes 1 to 23, 25, and 26, the following table shows the structural formulas and substituents described in Patent Document 6 corresponding to these.

Dyes 1 ~ 5, 7, 8, 12, 14, 15, 24, 25, 26 are trial products made by Yumoto Chemical Industry Co., Ltd. The following are obtained by Jihe Chemical Industry Co., Ltd .: the product of dye 9 is KP Plast Blue G; the product of dye 21 is KP Plast Yellow HR; the product of dye 22 is KP Plast Yellow 2HR; The product name is KP Plast Brilliant Red MG. The following are obtained by Nippon Kayaku Co., Ltd .: The product of dye 6 is named Kayaset Red B; the product of dye 10 is named Kayaset Blue FR; and the product of dye 11 is named Kayaset Red 168. Dye 13, Dye 16, and Dye 20 were respectively extracted and separated from Teratop Pink 3G, Terasil Pink 2GLA, and Terasil Blue BGE manufactured by Huntsman Japan Co., Ltd., respectively. Dye 17, was extracted from Kayalon Polyester Blue EBL-E manufactured by Nippon Kayaku Co., Ltd. Dye 18 and dye 19 were obtained by extraction and separation from Dianix Blue GL-FS and Dianix Blue AM-77, respectively, manufactured by DyStar Japan.

Two types of polypropylene cloth were obtained from Mitsubishi Rayon Co., Ltd. (Mitsubishi Rayon). One of them is made of polypropylene fiber thread of 110dtex / 36 filaments and knitted by a circular knitting tester (polypropylene cloth No. 1). The yarn loop density of this fabric is thick (warp loop 20 / 2.54cm; weft loop 32 / 2.54cm). Therefore, the weak stirring force of the magnetic stirrer can be easily leveled. The remaining one is a two-stage knitting (polypropylene cloth No. 2; 250g / m ² ; 190dtex / 48 filaments thread; warp loop 2 × 33 / 2.54cm; weft loop 2 × 34 / 2.54cm). These two knits are made of soda ash (industrial grade, 2g / dm ³ ), 1g / dm ³ surfactant (Daisurf MOL-315; First Industrial Pharmaceutical Co., Ltd.), and 0.5g / dm ³ admixture ( Sizol FX-20; Daiichi Pharmaceutical Co., Ltd.), refined in a liquid dyeing machine at 80 ° C in a water system. Thereafter, the dewatered polypropylene cloth No. 2 was centrifuged, and the cut was thermoset at 130 ° C as a pretreatment.

The cotton thread (30 / cotton count) was purchased from Clover Mfg Co., Ltd. In the dyeing procedure, three kinds of cotton cloths were used to cover the polypropylene cloth to diffuse the supercritical fluid. The first type has a wire mesh structure (cotton cloth No. 1: 30 vertical lines / 2.54cm, the horizontal line 30 / 2.54cm), and the second type has a single-sided flannel structure (cotton cloth No. 2). These cloths were purchased from Pip Fujimoto Co., Ltd. The third type has a flat weave structure (cotton cloth No. 3: 45 vertical lines / 2.54cm, 45 horizontal lines / 2.54cm; the product name is "Shandong Sun"), and was purchased from Hasegawa Mianxing Co., Ltd.

Liquid carbon dioxide (> 99.5%) was obtained by Uno Oxygen Co., Ltd. Test drug grade acetone was purchased from Nacalai Tesque, INC.

Using the above dyes 1 to 26, a dyeing test of polypropylene cloth was performed according to the following method.

(Dyeability test)

The apparatus used for the dyeability test is shown in FIG. 1. The dyeability test device 100 is composed of a liquid CO ₂ cylinder 101, stop valves 102, 107, 110, 121, a needle valve 103, a liquid sending pump 106 (consisting of a cooler 104 and a high pressure pump 105), and a safety valve 108. , Pressure gauge 109, magnetic stirring constant temperature empty bath 119 (composed of preheater 111, dyeing tank 112, filter 116, magnetic stirrer 117, constant temperature air bath 118), thermometer 120, semi-automatic back pressure control valve 124 (made by Back pressure control valve 123 and heater 123). The magnetic stirring constant temperature empty bath 119 is a set (SCF-Sro type) of a 50 cm ³ stainless steel tank in a temperature control furnace manufactured by JASCO Corporation. The liquid supply pump 106 is a carbon dioxide liquid supply pump (SCF-Sro type) manufactured by JASCO Corporation. The semi-automatic back pressure control valve 124 is a semi-automatic back pressure control valve (SCF-Bpg / M type) manufactured by JASCO Corporation.

Using glass fiber filter paper (2 × 2cm; ADVANTEC GA-55; manufactured by Advantec Toyo Co., Ltd. (ADVANTEC Toyo)), each dye (approximately 3 mg) was maintained as follows: First, a sheet of filter paper was dipped in acetone, Place the dye on the remaining filter paper and cover it with the impregnated filter paper. Acetone is used to make it easy to laminate two filter papers. Next, this is equal to room temperature drying to remove acetone. The stirrer 115, polypropylene cloth No. 1 (approximately 10 g) 114, and the dye 113 sandwiched between two filter papers were sequentially placed in the dyeing tank 112, and then the dyeing tank 112 was sealed. The air in the dyeing tank 112 is replaced with carbon dioxide under atmospheric pressure.

After the temperature in the constant temperature empty bath 118 reaches a predetermined temperature (120 ° C), the dyeing tank 112 is pressurized to a carbon dioxide pressure of 25 MPa through a carbon dioxide liquid pump 106, and then heated to a dyeing temperature (120 ° C). The back pressure control valve 122 was used to control the pressure of carbon dioxide in the dyeability test system to 25 MPa, and the dye bath was stirred with a magnetic stirrer. After 60 minutes, the backing pressure control valve 122 was used to gradually reduce the dyeing tank 112 to atmospheric pressure while maintaining stirring.

The treated polypropylene fiber cloth was taken out of the dyeing tank 112. Next, if the dye does not diffuse inside the fiber and precipitate on the fiber surface, the dyed cloth is immersed in acetone at room temperature for 30 seconds to remove the dye deposited on the surface of the dyed cloth. The impregnated cloth was taken out and dried at room temperature to remove acetone. Regarding dyeing energy, the results are classified as follows.

○: Good dyeing

△: light dyeing

×: All were unstained or only slightly stained.

Furthermore, it was confirmed whether there was any residual dye between the two filter papers. In addition, it was also confirmed whether there was a dye deposited on the inner wall of the dyeing tank 112. Those remaining in the filter paper and those precipitated on the inner wall are totaled as residual dye in the tank, and the results are classified as follows.

◎: No residue

○: trace residue (powder can be visually confirmed)

△: Many residues

×: almost all remain

(Supercritical fluid dyeing procedure)

A dyeing cloth having excellent dyeability (that is, good dyeability and less residual dye in the tank) was prepared to evaluate the fastness of dyeing. Polypropylene cloth No. 2 was cut into 20 × 150 cm, and the weight was measured (about 75 g). 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 sequentially wound around a stainless steel cylinder (width 220 mm; outer diameter 30 mm, inner diameter 26 mm) with perforations (3 mm diameter, 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, these cloths are used as the base cloth. The base cloth prevents the fluid from passing straight through the perforations, so that it can flow uniformly on the dyed object. Next, polypropylene cloth No. 2 and cotton cloth No. 3 were wound up. Cotton cloth No. 3 is to prevent the polypropylene cloth from shrinking due to the radiant heat from the groove. The wound roll is loosely tied to the tip with a cotton thread and fixed.

The device used for supercritical fluid dyeing is shown in Figure 2. Supercritical fluid dyeing device 200 is composed of liquid CO ₂ cylinder 201, filter 202, cooling jacket 203, high pressure pump 204, preheater 205, pressure gauge 206 ~ 208, magnetic drive unit 209, DC motor 210, safety valve 211, 212, cooler 213, stop valves 214-218, needle valve 219, and heater 220. The air cylinder 221 wound with the cloth sample was placed in a high-pressure stainless steel tank 222 (volume 2230 cm ³ ). Dye 223 (0.3% by mass of polypropylene dyed substance; that is, 0.3% omf) coated with dust-free paper (KimWipes S-200, made by Japan-based Crecia Co., Ltd.) was placed in the groove 222 The fluid passage above the cylinder 221.

The valve of tank 222 was closed and heated at 120 ° C. After reaching the dyeing temperature, the liquid carbon dioxide (1.3 kg) was passed through the cooling jacket 203 to the tank 222 through the pump 204. The carbon dioxide fluid is circulated by a stainless steel impeller 224 and a magnetic driving unit 209 installed at the bottom of the groove 222. The rotation speed of the magnetic drive cloth 209 is 750 rpm. The direction of fluid flow is from the inside to the outside of the cylinder 221.

After the temperature and pressure cycle speed reached a certain value (that is, 120 ° C., 25 MPa, 750 rpm), the polypropylene cloth was dyed by maintaining the conditions for 60 minutes. Control the release speed to reduce the pressure from 25 MPa to atmospheric pressure in 15 minutes. The circulation system continues until the internal pressure of the tank is almost reduced to the critical pressure (8.0 to 7.4 MPa). Thereafter, the dyed polypropylene cloth was taken out of the groove 222. When polypropylene cloth No. 2 was used, the dyeing energy and residual dye in the tank were the same as the results of the dyeability test using polypropylene cloth No. 1.

The dye deposited on the surface of the polypropylene cloth was removed by slowly releasing pressure under a continuous cycle. Therefore, as long as it does not cause a large excess of dye concentration, subsequent washing procedures should not be required. When the dye is precipitated from the surface, the rubbing fastness (JIS L0849, type II, added white cloth: cotton) tends to exhibit an abnormally low performance, which is normalized by the pressure release operation. In the embodiment of the present invention, both dry friction and wet friction are shown as 4-5 to 5 grades. In the case of using polypropylene cloth No. 2, the dyeing ability and the residual dye in the tank are equivalent to the results of the dyeability test using polypropylene cloth No. 1.

(Washing fastness)

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

(Light fastness)

The light fastness of the dyed polypropylene fiber cloth was evaluated based on JIS L0842 (third exposure method). The light fastness test is performed by using a UV carbon arc light and performing a 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, and nylon was added to the white cloth (single fiber cloth (I) No. 7: JIS L0803: 2005).

(Color measurement)

For color measurement of the dyed polypropylene cloth, a spectrophotometer (CM-600d: manufactured by Konica Minolta, Japan) was used. The measurement conditions of the spectral reflectance are as follows: 4 samples are overlapped on non-fluorescent white paper, the measurement diameter is φ8mm, the observation condition is 2 ° field of view, the light source D65 is observed, the measurement wavelength range is 400 ~ 700nm, and the measurement wavelength interval is 10nm, and the regular reflection light is removed (SCE: Specular Component Exclude). Based on the spectral reflectance, the values of L *, a *, and b * were calculated using CIE1976L * a * b * as a reference. Further, based on JIS Z8721: 1993, the hue H in the D65 light source was obtained.

(Examples 1 to 6, Comparative Examples 1 to 20)

The individual test results of Examples 1 to 6 and Comparative Examples 1 to 20 using dyes 1 to 26 are shown in Table 2. In Examples 1 to 6, Comparative Examples 1 to 3, and Comparative Examples 6, 7, 19, and 20, which confirmed that the dyeing of the polypropylene cloth was good, the fastness to dyeing was also evaluated. In Comparative Example 3, since the dye 5 used for dyeing was tar-like and difficult to measure, the fastness to washing and the fastness to sublimation were not evaluated. In addition, the color measurement of the dyed polypropylene fabrics of Examples 1 to 6 and Comparative Examples 1, 2, and 20 was performed. The results are shown in Table 3.

As shown in Table 2, the dyed polypropylene fabrics of Examples 1 to 6 exhibited excellent dyeability and excellent fastness to dyeing at the same time. In contrast, in Comparative Examples 1, 2, and 20, although the dyeing ability is good, there are many dyes remaining in the tank, and the contamination of washing fastness and sublimation fastness is bad; Comparative Examples 4, 5, 8 to 18, polypropylene cloth is not dyed. Good staining. Although Comparative Examples 6, 7, and 19 exhibited good dyeability, both the washing fastness and the light fastness in Comparative Example 6 were poor, the washing fastness in Comparative Example 7 was poor, and the light fastness in Comparative Example 19 was poor. .

Based on the results of the above-mentioned dyeing test, among dyes 1 to 23 equivalent to the representative dyes described in Patent Document 6, those who can dye polypropylene cloth well are only dyes 1 to 8, 11, 12, and 25 (Example 1). ~ 5, Comparative Examples 1 ~ 3, 6, 7, and Example 6). It is understood that there are many dyes that cannot dye polypropylene cloth even with supercritical carbon dioxide. On the other hand, the dye 24 (Comparative Example 19) corresponding to a positional isomer of a representative dye (1,4-bis (octylamine) -anthraquinone) described in Non-Patent Document 19 has good dyeability, However, light fastness is poor. It can be understood that the dyes obtained by changing the substitution position to obtain the target hue cannot be those with good dyeability and fastness. In addition, according to the comparison of Examples 1 to 6 and Comparative Examples 1 to 3, 6, 7, 8 to 11, 19, and 20, in order to obtain dyeability (dyeing energy, residual dye in the tank), dyeing fastness (washing) If the fastness, light fastness, and sublimation fastness are all good, the chemical structure of the dye, as shown in the general formula (1) above, needs to be: the substituent at the 1 position of the anthraquinone ring is an amine group; the substitution at the 2 position The group is phenoxy, and is substituted with a branched alkyl group or an arylalkyl group containing a quaternary carbon atom; the substituent at the 4-position is a hydroxyl group.

In addition, all dyes used in Examples 1 to 6 are solid, and dye 8 is equivalent to those in which R ₂ in the general formula (1) is a linear alkyl group having 9 carbon atoms and is tar-like, and the degree of dyeing cannot be controlled ( The shade of color) is not suitable for industrial production.

As shown in Table 3, the dyed polypropylene fabrics of Examples 1 to 6 all exhibited a red color of subtractive color mixing and three primary colors. In Examples 1, 2, 4, and 6, dyes 1, 2, 4, and 20 in which the substituent on the phenoxy group in the general formula (1) is a branched alkyl group are used. In particular, Example 4 uses dye 4, which is that R ₁ of the general formula (1) is 2-methylbutane-2-yl, n = 2, and R is present at the 2 and 4 positions of the phenoxy group. ₁ ; Example 6 uses dye 25, which is that R ₁ of the above general formula (1) is 2-methylpropane-2-yl, n = 2, and R ₁ exists at the 2 and 4 positions of the phenoxy group, These two dyes have only a trace amount of dye remaining in the groove as a stain on the clean paper, which means that the dye used is almost completely absorbed by the fiber. In addition, Examples 4 and 6 are excellent in washing fastness, light fastness, and sublimation fastness.

As mentioned above, although the present invention is described with reference to the above-mentioned embodiments, the present invention is not limited to the above-mentioned embodiments. Those who appropriately combine or replace the structures of the embodiments also belong to the present invention. In addition, based on the knowledge of those who have ordinary knowledge in the field, the implementation form can be combined and replaced in the order of the implementation form or the order of the steps, or various design changes can be changed. It is included in the scope of the present invention.

[Industrial availability]

The present invention can be used in clothing, underwear, hats, socks, gloves, sportswear and other clothing materials, vehicle interior materials such as seat sheets, carpets, curtains, floor mats, sofa covers, pillow cases, etc. Interior supplies, etc.

Claims (8)

A dyed polypropylene fiber structure characterized by being dyed with a red dye represented by the following general formula (1): In the general formula (1), R ₁ is independently selected from the group consisting of a branched alkyl group having 4 to 8 carbon atoms and an arylalkyl group having 9 to 19 carbon atoms, and n is 1 to 3 The aforementioned branched alkyl group includes a quaternary carbon atom, and the alkyl portion of the aforementioned arylalkyl group includes a quaternary carbon atom.     The dyed polypropylene fiber structure described in item 1 of the patent application scope, wherein n is 2.     The dyed polypropylene fiber structure according to item 1 or 2 of the scope of the patent application, wherein n is 2 and the R ₁ group is the aforementioned branched alkyl group. The dyed polypropylene fiber structure described in item 1 of the scope of the patent application, wherein n is 1 and the R ₁ group is the aforementioned branched alkyl group.     The dyed polypropylene fiber structure described in item 1 of the scope of the patent application, wherein the red dye is 1-amino-4-hydroxy-2- [2,4-bis (2-methylpropane-2- Phenyl) phenoxy] anthracene-9,10-diketone.         The dyed polypropylene fiber structure according to item 1 of the patent application scope, wherein the red dye is 1-amino-4-hydroxy-2- [4- (2,4,4-trimethylpentane 2-yl) phenoxy] anthracene-9,10-dione.         The dyed polypropylene fiber structure as described in any one of claims 1 to 6 of the scope of patent application, and it is a cloth.         A clothing product using the dyed polypropylene fiber structure described in any one of claims 1 to 7 of the scope of patent application.