KR102108694B1 - Dyed polypropylene fiber structures and medical products using the same - Google Patents

Abstract

(식중, R₁은 각각 독립적으로, 탄소수 4 ~ 8의 분기 알킬기, 및 탄소수 9 ~ 19의 아릴알킬기로 이루어지는 군으로부터 선택되는 1종이고, n은 1 ~ 3이다. 상기 분기 알킬기는 제4급 탄소원자를 포함하고, 상기 아릴알킬기의 알킬 부분은 제4급 탄소원자를 포함한다.)으로 나타내는 적색 염료로 염색되어 있는 것을 특징으로 한다.The dyed polypropylene fiber structure of the present invention has the following general formula (1):
[Tue 1]

(Wherein, R ₁ are each 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 branched alkyl group is a fourth class It contains a carbon atom, and the alkyl portion of the arylalkyl group includes a quaternary carbon atom.) It is characterized by being dyed with a red dye.

Description

Dyed polypropylene fiber structures and medical products using the same

The present invention relates to a dyed polypropylene fiber structure and a medical article using the same.

The polypropylene resin is a crystalline thermoplastic resin obtained by addition polymerization of propylene. This polypropylene resin is inexpensive because it uses propylene, a waste gas for petroleum refining, as a raw material, and has low density (0.90 to 0.92 g / cm 3) that floats in water, so it is lightweight, and has little water absorption and hygroscopic properties (process (公定) ) Moisture content is 0.0%). In addition, the polypropylene resin has many excellent characteristics and properties, such as chemical resistance, abrasion resistance, bending resistance, and antistatic properties (see Non-Patent Documents 1 and 2).

Polypropylene is a simple branched hydrocarbon polymer, and may be a methyl group as a pendant group, but does not have a functional group effective for chemical reaction with a dye. In addition, polypropylene has relatively dense crystals, is highly hydrophobic, and hardly swells in water. For this reason, coloring of polypropylene using conventional dyeing techniques has been found to be very difficult.

Most of the colored polypropylene fiber structures currently in the market are adhered yarns according to a stock solution coloring method (priming method) in which a pigment is added during the production of a polymer tip. The original method has a discomfort that the color must be determined at the earliest stage in the production of the fiber product, that is, during melt spinning, and a timely color cannot be selected. In addition, since the original yarn adds a pigment, which is a foreign substance, the yarn production is poor compared to a regular yarn that is not colored, and a fine thread having a single yarn fineness of 1 dtex or less cannot be stably produced. . In addition, when changing the color of the yarn to be produced, the resin of the previous color in the melt spinning apparatus must be extruded and replaced with the resin of the next color, so a large amount of waste resin and a lot of time are required. Considering the profitability and market price, the original yarn has to produce more than a certain amount of one color, and the number of colors is limited by itself.

Polypropylene as a synthetic resin can be mentioned as one of the four general-purpose synthetic resins such as polyethylene, polyvinyl chloride, and polystyrene, and is used in a very wide range of fields with a background of inexpensive raw material ratio and excellent properties (Non-Patent Document 3). In contrast to this, the use of polypropylene as a synthetic fiber is very limited (Non-Patent Document 4). This is considered to be mainly due to the small number of color indexes due to the inability to dye the polypropylene regular yarn, and the monofilament fineness of the original method, which is the only effective coloring method, to increase.

When the method of dyeing a polypropylene fiber into a material has been put into practical use, the number of color branches is not limited, and it becomes possible to color a regular yarn with a small (fine) single yarn fineness and inexpensive. Therefore, in order to increase the required designability, it is expected to develop a new application that exhibits its properties in fields where polypropylene fibers have not been applied, for example, in vehicle interior materials and medical fields.

In the 1960s, it has been attempted to dye polypropylene fibers with an aqueous system according to a change in the molecular structure of the dye, and patent documents 1 to 5 and non-patent documents 5 include several dyes for polypropylene dyeing. In addition, according to a study of water-based dyeing of polypropylene fibers described in Non-Patent Documents 6 to 11, dyes for very hydrophobic fibers such as polypropylene have much higher hydrophobicity than dyes commonly used for polyester fibers. Need something However, dyes capable of performing dyed polypropylene fibers with good color fastness such as light resistance, washing, friction, and sublimation all by water-based dyeing have not been found so far.

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

In addition, non-patent documents 18 and 19 disclose specific blue and yellow dyes capable of dying polypropylene cloth with scCO ₂ , and dyed polypropylene fibers having excellent color fastness by dyeing with these dyes are disclosed. What can be provided is disclosed.

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 Specifications Patent Document 5: US Patent No. 3, 536, 735 specification Patent Document 6: Japanese Patent No. 3253649

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: HIROSHI YAMAMOTO, The Society of fiber science and technology, Japan, 61 (2005), 319-321. Non-Patent Document 5: NAGAI Yoshio, MATSUO Masatoshi, J. Synth. Org. Chem. Jpn., 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 Operpermann, 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 Schollmeyer, 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 were found as dyes for providing a dyed polypropylene fiber structure having excellent color fastness (see Non-Patent Documents 18 and 19). However, in order to obtain the color of the material, at least one type of dye (yellow, red, blue) close to the subtractive mixed three primary colors (yellow, magenta, cyan) is required, and the red dyes constituting the three primary colors are still Not found For this reason, tint dyeing of materials by dye formulation has not yet been realized with polypropylene fiber structures.

In addition, Patent Document 6 only discloses neutral dyes such as disperse dyes and oil-soluble dyes, and only synthetic synthetic fibers to be subjected to dyeing are comprehensively listed. In practice, even if the polypropylene fiber structure is dyed using the dye described in Patent Document 6, even if most of the dye is not dyed or dyed, the color fastness of the dyed polypropylene fiber structure is remarkably poor. .

The present invention has been made in view of such a problem, and its object is to provide a polypropylene fiber structure dyed with a dye having a good color fastness and a red color capable of forming a subtractive color mixture.

The present invention has the following general formula (1):

[Tue 1]

(Wherein, R ₁ are each 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, n is an integer of 1 to 3. The branched alkyl group is It is a dyed polypropylene fiber structure characterized by being dyed with a red dye represented by a quaternary carbon atom, and the alkyl portion of the arylalkyl group includes a quaternary carbon atom.). Here, the "quaternary carbon atom" as used herein means a carbon atom bonded to four different carbon atoms.

In the general formula (1), n may be 2.

In the general formula (1), n is 2, and each of the R ₁ groups may independently be the branched alkyl group. Moreover, in said General formula (1), n is 1, and R ₁ group may be the said branched alkyl group.

Further, the dyed polypropylene fiber structure may be a cloth.

Another aspect of the present invention is a medical article characterized by using the dyed polypropylene fiber structure.

According to the present invention, it is possible to provide a dyed polypropylene fiber structure that can be dyed with a red dye having excellent color fastness and dyeability to show a red color of a subtractive color mixture.

1 is a schematic view showing an apparatus used in a dyeability test in Examples.
2 is a schematic view showing an apparatus for a supercritical fluid dyeing process in an example.

The dyed polypropylene (PP) fiber structure according to the embodiment has the following general formula (1):

[Tue 2]

(Wherein, R ₁ are each 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, n is an integer of 1 to 3. The branched alkyl group is Contains a quaternary carbon atom, and the alkyl portion of the arylalkyl group includes a quaternary carbon atom.)

It is characterized by being dyed with a red dye represented by.

The polypropylene fiber structure dyed with the dye may exhibit a red color of a subtractive color mixture. In addition, the dyed polypropylene fiber structure is excellent in wash fastness, light fastness, and sublimation fastness.

(dyes)

The red dye constituting the dyed polypropylene fiber structure of the present invention is a compound represented by the general formula (1). In order to satisfactorily dye the polypropylene fiber structure in a red color capable of forming a subtractive mixed color and to have good wash fastness, light fastness, and sublimation fastness, R ₁ in the general formula (1) is each independently, A branched alkyl group having 4 to 8 carbon atoms and an arylalkyl group having 9 to 19 carbon atoms, n is an integer of 1 to 3, and the branched alkyl group includes a quaternary carbon atom, and the arylalkyl group The alkyl part in the thing needs to contain a quaternary carbon atom.

The alkyl portion of R ₁ and the alkyl portion of the arylalkyl group are branched and contain a quaternary carbon atom, whereby a dye having better color fastness is obtained. In addition, since the dye represented by the general formula (1) is a solid, it is easy to handle, it is possible to finely adjust the degree of dyeing (lightness of color), and it is advantageous for industrial production.

Examples of the branched alkyl group containing a quaternary carbon atom include 2-methylpropan-2-yl (tert-butyl) group, 2-methylbutan-2-yl (tert-amyl) group, 2, 4, and 4-trimethyl. And a pentane-2-yl (tert-octyl) group and a 2-methylheptan-2-yl group. Among these, since there are fewer residual dyes at the time of dyeing and dyeing fastness is better, 2-methylpropan-2-yl group, 2-methylbutan-2-yl group, 2, 4, 4-trimethylpentane-2-yl group Is preferred.

Examples of the arylalkyl group containing a quaternary carbon atom include a 2-phenylpropan-2-yl (cumyl) group, a 2-phenylbutan-2-yl group, and a 2- (o-toluyl) propan-2-yl group, 1 , 1-diphenyl propyl group, 1, 1, 1-triphenylmethyl group (trityl group). In addition, the number of carbon atoms of the arylalkyl group is preferably 9 or 10.

When n is 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).

[Tue 3]

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 arylalkyl group.

Since the color fastness can be further improved, the number of substituents on the phenoxy group is two, that is, it is preferable that n is 2 in the general formula (1). Further, for the same reason, in the general formula (2), two of R _{2 to} R ₄ are each independently the branched alkyl group or the arylalkyl group, and the other is preferably a hydrogen atom.

It is preferable that R ₁ is the branched alkyl group and n is 1 or 2, since there are fewer residual dyes when dyed and the degree of dyeing can be adjusted with good reproducibility. Further, for the same reason, in the general formula (2), it is preferable that R _{2 to} R ₄ are each independently a hydrogen atom or the branched alkyl group, and that one or two of R _{2 to} R ₄ is the branched alkyl group. Particularly, it is more preferable that R ₁ is the branched alkyl group and n is 2 in the general formula (1), because the color fastness becomes more excellent and the residual dye at the time of dyeing becomes less. For the same reason, in the general formula (2), two of R _{2 to} R ₄ are each independently the branched alkyl group, and the other is more preferably a hydrogen atom.

In a particularly preferred embodiment of the present invention, in the dye, R _{1 in} the general formula (1) is 2, 4, 4-trimethylpentan-2-yl group, n is 1, and R ₁ at 4 position of the phenoxy group. This compound, or R _{1 in} the general formula (1) is a 2-methylpropan-2-yl group or a 2-methylbutan-2-yl group, n is 2, and R at 2 and 4 positions of the phenoxy group ₁ is a compound present. Such a compound has excellent color fastness and dyeability, in particular, no dye remains during dyeing, and it is possible to control the color of dyeing with good reproducibility.

The red dye represented by the general formula (1), by using a blue dye and a yellow dye capable of dyeing a polypropylene fiber structure, in particular, the blue dye and yellow dye described in non-patent documents 3, 4, respectively, The polypropylene fiber structure can be dyed to the color of the material.

The dye represented by the general formula (1) is known and can be prepared according to methods already known to those skilled in the art. Commercially available 1-amino-2-bromo-4-hydroxyanthracene 9, 10-dione and commercial branched alkyl groups under known conditions described, for example, in Dyes Dand Pigments, 95, 2012, 201-205 Or it can be prepared by reacting a phenol substituted with an arylalkyl group.

(Polypropylene fiber structure)

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

From the polypropylene fibers, various types of polypropylene fiber structures can be produced according to existing methods in the art. As the form of the polypropylene fiber structure, for example, yarn-like structures (filament yarns, spun yarns, slit yarns, split yarns), cotton (cotton) shape structures, string-like structures, fabric-like structures (fabrics, knitted fabrics, non-woven fabrics, felts) , Tufts, etc.) and combinations thereof, but are not limited to these. In addition, commercially available polypropylene fiber structures can also be used. Further, a fiber structure may be produced by blending and / or blending other fibers such as polyester with polypropylene fibers.

(Method for manufacturing dyed polypropylene fiber structures)

The dyed polypropylene fiber structure of the present invention can be produced by using a supercritical carbon dioxide fluid and dyeing the polypropylene fiber structure with a dye represented by the general formula (1). Methods of dyeing polypropylene fiber structures with supercritical carbon dioxide fluid as a medium are already known to those skilled in the art. 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 general formula (1) may exhibit a subtractive color of three primary colors. In addition, the range of the "red color of the subtractive mixed three primary colors" is well known in the art, and refers to all of the ranges allowed as red in the color (H value) among the three attributes (color, brightness, and saturation) of the color. Among the attributes of color perception, the color scaled color H (JIS: Z8721: 1993) ranges from 10 P to 10 R centering on 10 RP. In addition, the dye represented by the general formula (1) and, for example, a blue dye and a yellow dye described in non-patent documents 3 and 4, respectively, are combined to dye a polypropylene fiber structure, and the dyed polypropylene fiber structure You may manufacture. In this case, the polypropylene fiber structure can be dyed with the color of the material.

(Use of dyed polypropylene fiber structures)

Although the use of the dyed polypropylene fiber structure of the present invention is not particularly limited, for example, clothing, underwear, hats, socks, gloves, medical products such as sportswear, vehicle interior materials such as seat seats, carpets, curtains, mats , Interior products such as sofa covers and cushion covers. Since the dyed fiber structure of the present invention can express the color tone of materials, it can be suitably used for medical products.

Hereinafter, the present invention will be described in more detail according to examples, but these examples are not intended to limit the invention.

Example

(material)

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

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

[Table 1-5]

[Table 1-6]

Dyestuffs 1 to 5, 7, 8, 12, 14, 15, 24, 25, and 26 are ARIMOTO CHEMICAL CO., LTD. Was obtained from. Dye 9 is a product name KP Plast Blue G, dye 21 is a product name KP Plast Yellow HR, dye 22 is a product name KP Plast Yellow 2 HR, dye 23 is a product name KP Plast Brilliant Red MG, KIWA Chemical Industry Co., Ltd. Was obtained from. Dye 6 was a product name KayasetakuRed B, dye 10 was a product name Kayaset Blue FR, and dye 11 was a product name Kayaset Red 168, which was obtained from Nippon Kayaku Co., Ltd. Dye 13, dye 16, and dye 20 were extracted and isolated from TeratopaPink 3G, Terasil Pink 2GLA, and Terasil Blue BGE manufactured by Huntsman Japan Co., Ltd., respectively. Dye 17 is Nippon Kayaku Co., Ltd. It was extracted from Kayalon Polyester Blue EBL-E. Dye 18 and Dye 19 were extracted and isolated from Dianix Blue GL-FS and Dianix Blue AM-77, respectively, manufactured by Dystar Japan.

Two types of polypropylene fabric, Mitsubishi Rayon Co., Ltd. Was obtained from. One is made of 110 dtex / 36 filaments of polypropylene fiber yarn and woven into a circular knitting tester (polypropylene fabric No. 1). The loop density of this knitted fabric was loose (wale 20 / 2.54 cm; course 32 / 2.54 cm), and therefore, the magnetic stirrer could be easily leveled with a weak stirring force. The other one is a dense two-layer knit for measuring color fastness (polypropylene fabric No.2; 250 g / m2; 190 dtex / 48 yarn of firaments; wale 2 x 33 / 2.54 cm; course 2 x 34 / 2.54 cm It was). This two-stage knit, soda ash (industrial grade, 2 g / dm ³ ), 1 g / dm ³ surfactant (Daisurf MOL-315; DKS Co. Ltd.), 0.5 g / dm ³ chelating agent (Sizol FX-20 ; DKS Co. Ltd.), and refined at 80 ° C in a water system using a liquid dyeing machine. Subsequently, polypropylene fabric No. 2 was centrifugally dehydrated, and the incised one was heat set at 130 ° C as a pretreatment.

,HASEGAWA MENKO CO., LTD. 으로부터 구입했다.Cotton yarn (30 / cotton number), Clover Mfg Co., Ltd. Purchased from. In the dyeing process, three types of cotton cloth were used to diffuse the supercritical fluid and wrap the polypropylene cloth. One type had a gauze structure (cotton No. 1: 30 warp yarns / 2.54 cm, 30 yarns / 2.54 cm), and the second one had a single-sided flannel structure (cotton yarn No. 2). These fabrics were purchased from PIP CO., LTD.). The third one has a plain weave structure (cotton fabric No. 3: 45 warp yarns / 2.54 cm, 45 yarns / 2.54 cm; product name ``

, HASEGAWA MENKO CO., LTD. Purchased from.

Liquid carbon dioxide (> 99.5%) was added to Uno Sanso Co., Ltd. Was obtained from. Acetone of reagent grade was purchased from NACALAI TESQUE, INC.

Using the dyes 1 to 26, a dyeing test of polypropylene fabric was conducted according to the following method.

(Dyeing test)

The apparatus used for the dyeability test is shown in FIG. 1. The dyeability test apparatus 100 is a liquid CO ₂ cylinder 101, a stop valve 102 107, 110, 121, a needle valve 103, a liquid feeding pump 106 (a cooler 104 and a high pressure pump 105) Configuration), safety valve 108, pressure gauge 109, magnetic stirring constant temperature air bath 119 (preheater 111, dyeing tank 112, filter 116, magnetic stirrer 117, constant temperature air bath) (118)), temperature gauge 120, semi-automatic back pressure valve 124 (consisting of back pressure valve 122, heater 123). The self-stirring constant temperature air bath 119 utilized a set of 50 cm 3 stainless steel baths (SCF-Sro type) in a temperature-controlled oven manufactured by JASCO Corporation. As the liquid feeding pump 106, a carbon dioxide liquid feeding pump (SCF-Sro type) manufactured by JASCO Corporation was used. As the semi-automatic back pressure valve 124, a semi-automatic back pressure valve (SCF-Bpg / M type) manufactured by JASCO Corporation was used.

Each dye (about 3 mg) was maintained as follows using a glass fiber filter (2 × 2 cm; ADVANTEC® GA-55; manufactured by Advantec Toyo Kaisha, Ltd.). First, one piece of the filter was immersed in acetone, then the dye was placed on the rest of the filter and covered with the immersed filter. Acetone was used to easily stack two filters. Next, these were dried at room temperature, and acetone was removed. Stirrer 115, polypropylene fabric No. 1 (approximately 1.0 g) (114), and dye (113) sandwiched between two filters are placed in a dye tank (112) in order to seal the dye tank (112). did. The air in the dyeing tank 112 was replaced with carbon dioxide at atmospheric pressure.

After the temperature in the constant temperature air bath 118 reaches a predetermined temperature (120 ° C), the dyeing tank 112 is pressurized to a carbon dioxide pressure of 25 MPa by the carbon dioxide feeding pump 106 to the dyeing temperature (120 ° C). Reheated. The pressure of carbon dioxide in the dyeability test apparatus system was controlled to 25 MPa by the back pressure valve 122, and the salt bath was stirred with a magnetic stirrer. After 60 minutes, the dyeing tank 112 was gradually depressurized to atmospheric pressure by the back pressure agent valve 122 while maintaining stirring.

The treated polypropylene fabric was taken out from the dyeing tank 112. Next, when the dye did not diffuse inside the fiber and precipitated on the fiber surface, the dyed fabric was immersed in acetone at room temperature for 30 seconds, and the dye deposited on the surface of the dyed fabric was removed. The soaked fabric was taken out and dried at room temperature to remove acetone. For dyeing ability, the results were classified as follows.

○: well dyed

△: faintly dyed

×: not dyed at all or slightly contaminated

In addition, the presence or absence of the dye remaining between the two filters was confirmed. In addition, the presence or absence of the dye deposited on the inner wall of the dyeing tank 112 was also confirmed. Residual dyes in the tank, which combined what remained on the filter and what precipitated on the inner wall, were classified as follows.

◎: No residue

○: Residual trace (the powder can be confirmed visually)

△: there are many residues

×: almost all residual

(Supercritical fluid dyeing process)

For dyes with excellent dyeability (i.e., good dyeing ability and few residual dyes in the bath), a dye cloth was prepared to evaluate the color fastness. Polypropylene fabric No. 2 was cut to 20 × 150 cm and weighed (about 75 g). Cotton fabrics No. 1, 2 and 3 were cut into 20 × 100 cm, 20 × 75 cm, and 20 × 35 cm, respectively. First, cotton cloth Nos. 1 and 2 were wound in turn into a stainless steel cylinder (220 mm wide; 30 mm outer diameter, 26 mm inner diameter) having a punch hole (diameter 3 mm, number of holes / area 1.87 / cm 2, effective width 190 mm). All. To avoid the direct effect of the punch hole on the polypropylene fabric No. 2 dyeing, this fabric was used as an undercross. The undercross prevents the fluid from passing through the punching hole linearly and flows uniformly through the dye. Then, polypropylene fabric No. 2 and cotton fabric No. 3 were wound one after another. The cotton fabric No. 3 prevented the polypropylene fabric from shrinking due to radiant heat from the bath. The roll roll was fixed by loosely binding the edges with cotton yarn.

The apparatus for supercritical fluid staining is shown in FIG. 2. The supercritical fluid dyeing apparatus 200 includes 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 to 208, and a magnetic drive unit It consists of 209, DC motor 210, safety valves 211 and 212, cooler 213, stop valves 214 to 218, needle valve 219, and heater 220. The cylinder 221 wound around the fabric sample was placed in a high-pressure stainless steel bath 222 (volume 2230 cm 3). The cylinder 221 in the tank 222 of dye 223 (0.3% of the mass of the polypropylene dye, i.e. 0.3% omf) wrapped with paper wipe (manufactured by KimWipes S-200, NIPPON PAPER CRECIA CO., LTD.) It was placed in the fluid passage above.

The valve of the bath 222 was closed and heated to 120 ° C. After reaching the dyeing temperature, liquid carbon dioxide (1.13 kg) was flowed into the tank 222 through the cooling jacket 203 with a pump 204. The carbon dioxide fluid was circulated to the stainless steel impeller 224 mounted on the bottom of the tank 222 and the magnetic drive unit 209. The rotation speed of the magnetic drive unit 209 was 750 rpm. The flow direction of the fluid was from the inside of the cylinder 221 to the outside.

After the temperature and the pressure circulation rate reached a certain value (ie, 120 ° C, 25 MPa, 750 rpm), these conditions were maintained for 60 minutes, and the polypropylene cloth was dyed. The release rate was controlled and the pressure was reduced from 25 MPa to atmospheric pressure over 15 minutes. Circulation continued until the tank internal pressure almost decreased to a critical pressure (8.0 to 7.4 MPa). Thereafter, the dyed polypropylene fabric was taken out from the bath 222. The dyeing ability when using polypropylene fabric No. 2 and the residual dye in the tank were the same as the results of the dyeability test using polypropylene fabric No. 1.

The dye precipitated on the surface of the polypropylene fabric is removed by the operation of continuously releasing the pressure to continue the circulation. Therefore, if the dye concentration is not excessive, a subsequent cleaning process is unnecessary. When the dye precipitates on the surface, the color fastness (JIS 백 L0849, type II, attached white cloth: cotton), which tends to exhibit an unusually low performance, is normalized by this pressure relief operation. In the examples of the present invention, both dry and wet friction showed 4-5 to 5 grade. The dyeing ability when using polypropylene fabric No. 2 and the residual dye in the tank were the same as the results of the dyeability test using polypropylene fabric No. 1.

(Wash fastness)

The laundry fastness test was performed using a multi-sum cloth fabric (Teacher No. 1: JISJL0803: 2005; cotton, nylon, acetate, wool, rayon, acrylic, silk and polyester fabric), JIS L0844 : It was carried out according to the 2005 A-2 method (based on ISO 105-C02: 1989 Test 2). In the contamination of multi-sum fabrics, the most contaminated parts were evaluated. In addition, the contamination of the test solution as well as the contamination of the foam was evaluated with reference to ISO 105-D01: 1994. As an evaluation of contamination of the test solution, the test solution remaining in the container was passed through a filter paper. The staining of the filtered test solution was compared with that of an unused test solution in a glass test tube (25 mm in diameter) placed in front of a white card using transmitted light in a gray scale for contamination evaluation.

(Light fastness)

The light fastness of the dyed polypropylene fabric was evaluated according to JIS L0842 (third exposure method). The light fastness test was performed using light such as ultraviolet carbon arc, and the third exposure method was performed for the third and / or fourth grade.

(Sublimation fastness)

The sublimation fastness of the dyed polypropylene fabric was evaluated according to JIS L0854, and nylon (single fiber fabric (I) 7: JIS L0803: 2005) was evaluated as the attached white fabric.

(Color)

A spectrophotometer (CM-600d: Konica Minolta, Japan Inc.) was used for the color measurement of the dyed polypropylene fabric. The measurement conditions of the spectral reflectance are four samples on a non-fluorescent white paper, measuring diameter φ 8 mm, observation conditions 2 ° field of view, observation light source D65, measurement wavelength range 400 to 700 nm, measurement wavelength interval 10 nm, Specular reflection light was excluded (SCE: Specular Component Exclude). From the spectral reflectance, values of L *, a *, and b * were determined based on CIE1976L * a * b *. Further, in accordance with JIS # Z8721: 1993, the color H in the D65 light source was determined.

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

Table 2 shows the test results of Examples 1 to 6 and Comparative Examples 1 to 20 using dyes 1 to 26. For Examples 1 to 6, Comparative Examples 1 to 3, and Comparative Examples 6, 7, 19, and 20, in which satisfactory dyeing of the polypropylene fabric could be confirmed, the color fastness was also evaluated. In Comparative Example 3, since the dye 5 used for dyeing was in a tar state and weighing was difficult, the wash fastness and the sublimation fastness were not evaluated. In addition, the dyeing of the dyed polypropylene fabrics of Examples 1 to 6 and Comparative Examples 1, 2 and 20 was performed. Table 3 shows the results.

As shown in Table 2, the dyed polypropylene fabrics of Examples 1 to 6 exhibited both excellent dyeability and excellent color fastness. On the other hand, in Comparative Examples 1, 2 and 20, the dyeing ability was good, but in the comparative examples 4, 5, 8 to 18, where there were many residual dyes in the tank, and contamination of wash fastness and sublimation fastness was poor, polypropylene carriage It did not dye well with the dye. Comparative Examples 6, 7, and 19 showed good dyeability, but in Comparative Example 6, both the wash fastness and the light fastness were poor, in Comparative Example 7, the wash fastness was poor, and in Comparative Example 19, the light fastness was poor.

From the results of the dyeing test described above, among dyes 1 to 23 corresponding to typical dyes described in Patent Document 6, dyes 1 to 8, 11, 12, and 25 (Example 1) were able to satisfactorily dye polypropylene cloth. ~ 5, Comparative Examples 1 to 3, 6, 7, and Example 6), and it was understood that there were many dyes that were unable to dye polypropylene fabric even by supercritical carbon dioxide. On the other hand, dye 24 (Comparative Example 19), which corresponds to the positional isomer of a representative dye (1, 4-bis (octyl amino) -anthraquinone) described in Non-Patent Document 19, had good dyeing properties but poor light fastness. It can be understood that, by simply changing the substitution position, neither dyeing property nor color fastness can be achieved with a dye having a target color. In addition, from the comparison of Examples 1 to 6 and Comparative Examples 1 to 3, 6, 7, 8 to 11, 19, 20, dyeability (dyeability, residual dye in the bath), color fastness (washing fastness, light fastness, sublimation fastness) ) In order to make all of them good, the chemical structure of the dye is a branched alkyl group or an aryl group in which the substituent at position 1 of the anthraquinone ring contains an amino group and the substituent at position 2 contains a quaternary carbon, as represented by the general formula (1) above. It has been shown that a phenoxy group substituted with an alkyl group and a substituent at the 4-position are hydroxy groups.

In addition, all of the dyes used in Examples 1 to 6 are solid, whereas in the general formula (1), dye 8 (Comparative Example 3) corresponding to R ₂ being a straight-chain alkyl group having 9 carbons is in a tar state, The degree (color tone) cannot be controlled and is not suitable for industrial production.

As shown in Table 3, all of the dyed polypropylene fabrics of Examples 1 to 6 exhibited a red color of the subtractive mixed three primary colors. In Examples 1, 2, 4, and 6 in which the substituents on the phenoxy group in the general formula (1) were branched alkyl groups of dyes 1, 2, 4, and 20, residual dyes in the bath were less. In particular, the general formula (1) and R ₁ is 2-methyl-butane-2-yl group of a, n = 2, and the embodiment using the dye 4 to the R ₁ present in the 2-position and 4-position of the phenoxy group in Example 4, the and the general formula ₍₁₎ R 1 is 2-methylpropane-2-yl group of the, and n = 2, in example 6 using the dye 25 to the R ₁ present in the 2-position and 4-position of the phenoxy group, the dyeing The trace amount of dye remained in the bath as a stain on a paper wipe, indicating that almost all of the used dye was adsorbed on the fibers. In addition, in Examples 4 and 6, wash fastness, light fastness, and sublimation fastness were all excellent.

As described above, the present invention has been described with reference to the above-described embodiments, but the present invention is not limited to the above-described embodiments, but is also included in the present invention for appropriate combinations or substitutions of the configurations of the embodiments. Further, based on the knowledge of those skilled in the art, it is also possible to add new combinations of the combinations and processes in the embodiments as appropriate, and various modifications such as design changes can be added to the embodiments. It can be included in the scope of.

The present invention can be used for clothing, underwear, hats, socks, gloves, medical products such as medical care for sports, vehicle interior materials such as seat seats, interior products such as carpets, curtains, mats, sofa covers, cushion covers, and the like.

100: device used for dyeability test,
101: liquid CO ₂ cylinder,
102: stop valve,
103: needle valve,
104: cooler,
105: high pressure pump,
106: liquid pump,
107: stop valve,
108: safety valve,
109: pressure gauge,
110: stop valve,
111: preheater,
112: dyeing tank,
116: filter,
117: magnetic stirrer,
118: constant temperature air bath,
119: self-stirring constant temperature air bath,
120: temperature gauge,
121: stop valve,
122: back pressure valve,
123: burner,
124: semi-automatic back pressure 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: 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: burner,
221: cylinder,
222: high pressure stainless steel bath,
223: Dye cheap with paper wipe,
224: Impeller.

Claims (9)

The following general formula (1):
[Tue 1]

(Wherein, R ₁ are each 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 branched alkyl group is a fourth class A dyed polypropylene fiber structure characterized by being dyed using a supercritical carbon dioxide fluid as a dyeing medium with a red dye represented by a carbon atom, wherein the alkyl portion of the arylalkyl group includes a quaternary carbon atom.) . According to claim 1,
Dyed polypropylene fiber structure, characterized in that n is 2. According to claim 2,
A dyed polypropylene fiber structure, characterized in that n is 2 and R ₁ group is the branched alkyl group. According to claim 1,
A dyed polypropylene fiber structure, characterized in that n is 1 and the R ₁ group is the branched alkyl group. According to claim 1,
The dyed polypropylene fiber structure wherein the red dye is 1-amino-4-hydroxy-2- [2, 4-bis (2-methylpropan-2-yl) phenoxy] anthracene-9, 10-dione . According to claim 1,
The red dye is 1-amino-4-hydroxy-2- [4- (2, 4, 4-trimethylpentan-2-yl) phenoxy] anthracene-9, 10-dione, dyed polypropylene fiber structure. The method according to any one of claims 1 to 6,
A dyed polypropylene fiber structure having a color fastness of 4-5 or higher measured according to JIS L0849. The method according to any one of claims 1 to 6,
A dyed polypropylene fiber structure, characterized in that it is a foil. A medical article using the dyed polypropylene fiber structure according to any one of claims 1 to 6.

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