KR20190095244A - 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 is represented by the following general formula (1):
[Tue 1]

(In formula, R <_1> is respectively independently 1 type selected from the group which consists of a C4-C8 branched alkyl group and a C9-19 arylalkyl group, n is 1-3. The said branched alkyl group is quaternary And carbon atoms, and the alkyl portion of the arylalkyl group contains a quaternary carbon atom.

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.

Polypropylene resin is a crystalline thermoplastic resin to which the propylene addition polymerization was carried out. This polypropylene resin is inexpensive because it is made of propylene, which is a waste gas used in petroleum refining, and is light in weight because of its low density (0.90 to 0.92 g / cm3). A) Quick drying because of moisture content of 0.0%). Moreover, polypropylene resin has many outstanding characteristics and characteristics, such as chemical resistance, abrasion resistance, bending resistance, antistatic property, etc. (refer nonpatent literature 1, 2).

Polypropylene is a polymer of simple branched hydrocarbons and may be a methyl group as a pendant group, but has no effective functional group for chemical reaction with dyes. In addition, polypropylene is relatively dense in crystals, highly hydrophobic, and hardly swells in water. For this reason, coloring of polypropylene using conventional dyeing techniques has been very difficult.

The colored polypropylene fiber structures currently on the market are mostly raw yarns according to the undiluted solution coloring method (primary method) to which a pigment is added at the manufacturing stage of the polymer tip. The original method is inconvenient that the color must be determined at the earliest stage in the manufacture of the fiber product, that is, melt spinning, and timely color cannot be selected. In addition, since the original yarn is added with a pigment that is a foreign material, the sandability is worse than that of the regular colored yarn which is not colored, and the single yarn fineness of 1 dtex or less cannot be stably produced. . In addition, when changing the color of the yarn to be manufactured, since the resin of the previous color in the melt spinning apparatus must be extruded and substituted with the resin of the following color, a large amount of waste resin and a lot of time are required. Considering profitability and market price, the original yarn has to produce more than a certain amount of one color, and the number of colors will naturally be limited.

Polypropylene as a synthetic resin is one of four general-purpose synthetic resins comparable to polyethylene, polyvinyl chloride, and polystyrene, and has been used in a wide range of fields due to its 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 the main reason for the low number of color indexes due to the inability to dye polypropylene regular yarn, and the single yarn fineness in the original method, which is the only effective coloring method.

When the method of dyeing a polypropylene fiber with material becomes practical, the limitation of the number of colors is eliminated, and it becomes possible to color regular yarn which is small (thin) and cheap (thin). Therefore, in order to increase the designability required, new application development that exhibits its characteristics is expected in fields in which polypropylene fibers have not been applied so far, for example, vehicle interior materials and medical fields.

In the 1960s, it has been attempted to dye polypropylene fibers in water according to a change in the molecular structure of the dye. Patent Documents 1 to 5 and Non-Patent Document 5 include several dyes for dyeing polypropylene. In addition, according to a study of water-based dyeing of polypropylene fibers described in Non-Patent Documents 6 to 11, dyes for very high hydrophobic fibers such as polypropylene have much higher hydrophobicity than dyes commonly used for polyester fibers. It is necessary. However, the dye which can carry out the dyeing polypropylene fiber which is excellent in all fastnesses, such as light resistance, washing | cleaning, friction, sublimation, by aqueous dyeing has not been found until now.

As a method of dyeing polypropylene fibers instead of water-based dyeing, a method of dyeing using supercritical carbon dioxide (scCO ₂ ), called supercritical (fluid) dyeing, as a dyeing medium is already known. For example, Patent Document 6 discloses dyeing hydrophobic fiber materials such as polyester fiber materials and polypropylene fiber materials with various dyes using scCO ₂ . Non-Patent Documents 12 to 17 describe dyeing of polypropylene fibers by supercritical dyeing with dyes for polyester 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 , and dyeing polypropylene fibers having excellent dyeing fastnesses by dyeing with such dyes is 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 Patent Document 5: US Patent No. 3, 536, 735 Patent Document 6: Japanese Patent No. 3253649

[Non-Patent Document 1] M? Ahmed, Polypropylene? Fibers, science? And? Technology (Amsterdam; New? York: Elseier? Scientific? Pub. Co., 1982). [Non-Patent Document 2] J. Akrman, & J. Prikryl, J. Appl. Polym. Sci., 62 (1996) 235. [Non-Patent Document 3] P. Galli, S. Danesi &amp; 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] SJ 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' Stadenmayer, Melliand 'Textilberichte-Int. Text. Rep., 77 (1996) 588. [Non-Patent Document 13] E. Bach, E. Cle. And E. Schollmeyer, J. Text. Inst. Part. 1 Fiber. Sci. Text. Tecnol., 89 (1998) 647. Non-Patent Document 14: E Bach, E Cle e andE Schollmeyer, J.Text.Inst.Part 1 Fiber Sci.Text.Tecnol., 89 (1998) 657. Non-Patent Document 15: D Knittel, W SausandandE 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 dyed polypropylene fiber structures having excellent dyeing fastnesses (see Non-Patent Documents 18 and 19). However, in order to obtain the color of the material, at least one kind of dye (yellow, red, blue) close to the subtractive tricolor (yellow, magenta, cyan) is required, and the red dye constituting the three primary colors is still required. Not found For that reason, tint dyeing of materials by dye blending could still not be realized with polypropylene fiber structures.

Patent document 6 discloses neutral dyes such as disperse dyes and oil-soluble dyes in a comprehensive manner, and only comprehensively enumerates hydrophobic synthetic fibers to be dyed. In fact, even when the polypropylene fiber structure is dyed using the dye described in Patent Document 6, most of the dyes are not dyed at all, or even if dyed, the dyeing fastness of the dyed polypropylene fiber structure is remarkably poor. .

This invention is made | formed in view of such a subject, The objective is to provide the polypropylene fiber structure dyed with the dye which shows the redness which has the outstanding dyeing fastness and can comprise a subtractive trichromatic primary color.

The form with this invention is following General formula (1):

[Tue 1]

(In formula, R <_1> is respectively independently 1 type chosen from the group which consists of a C4-C8 branched alkyl group and a C9-19 arylalkyl group, n is an integer of 1-3. Dyed polypropylene fiber structure comprising a quaternary carbon atom, wherein the alkyl portion of the arylalkyl group comprises a quaternary carbon atom. As used herein, "a quaternary carbon atom" means a carbon atom bonded to four other carbon atoms.

In General Formula (1), n may be 2.

In said general formula (1), n may be 2 and R <_1> group may each independently be the said branched alkyl group. In addition, in said General formula (1), n may be 1 and R <_1> group may be the said branched alkyl group.

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

Another aspect of the present invention is a medical product, characterized in that the dyed polypropylene fiber structure is used.

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

BRIEF DESCRIPTION OF THE DRAWINGS The schematic which shows the apparatus used for the dyeing test in an Example.
2 is a schematic diagram illustrating an apparatus for a supercritical fluid staining process in an embodiment.

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

[Tue 2]

(In formula, R <_1> is respectively independently 1 type chosen from the group which consists of a C4-C8 branched alkyl group and a C9-19 arylalkyl group, n is an integer of 1-3. A quaternary carbon atom, and the alkyl portion of the arylalkyl group contains a quaternary carbon atom.)

It is dyed with the red dye represented by the above.

The polypropylene fiber structure dyed with the dye may exhibit a red color of subtractive tricolor. In addition, the dyed polypropylene fiber structure, washing fastness, light fastness, sublimation fastness is also excellent.

(dyes)

The red dye which comprises the dyed polypropylene fiber structure of this invention is a compound represented by the said General formula (1). In order that the polypropylene fiber structure can be dyed satisfactorily with red that can form a subtractive mixed color three primary colors, and washing fastness, light fastness, and sublimation fastness are all good, R <_1> in said General formula (1) is respectively independently, It is 1 type chosen from the group which consists of a C4-C8 branched alkyl group, and a C9-19 arylalkyl group, n is an integer of 1-3, The said branched alkyl group contains a quaternary carbon atom, The said arylalkyl group The alkyl moiety in that it needs to contain a quaternary carbon atom.

When the alkyl moiety in the alkyl group and the arylalkyl group of R ₁ is branched and contains a quaternary carbon atom, a dye having better dyeing fastness is obtained. Moreover, since the dye represented by the said General formula (1) is solid, handling is easy, fine adjustment of the grade (darkness of color) is possible, 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 Pentan-2-yl (tert-octyl) group and 2-methylheptan-2-yl group are mentioned. Among these, 2-methylpropane-2-yl group, 2-methylbutan-2-yl group, 2, 4, 4-trimethylpentan-2-yl group, since there are less residual dyes at the time of dyeing and excellent dyeing fastness Is preferred.

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

When n is 2 or 3, two or three R <_1> may be the same or different, respectively.

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

[Tue 3]

In the formula, each of R _{2 to} R ₄ is independently one 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 dyeing fastness can be improved further, it is preferable that the number of substituents on a phenoxy group is two, ie n is 2 in the said General formula (1). In addition, for the same reason, it is preferable that in the general formula (2), two of R _{2 to} R ₄ each independently represent the branched alkyl group or the arylalkyl group, and the other one is a hydrogen atom.

It is preferable that R <_1> is the said branched alkyl group and n is 1 or 2 because there are few residual dyes at the time of dyeing, and the degree of dyeing can be adjusted reproducibly. In addition, for the same reason, in the above general formula (2), R _{2 to} R ₄ are each independently a hydrogen atom or the branched alkyl group, and one or two of R _{2 to} R ₄ is preferably the branched alkyl group. In particular, since dyeing fastness becomes more excellent and residual dye at the time of dyeing becomes less, it is more preferable that R <_1> is the said branched alkyl group and n is 2 in the said General formula (1). For the same reason, in the above 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} General Formula (1) is a 2, 4, 4-trimethylpentan-2-yl group, n is 1, and R _{1 is} positioned at 4 positions of the phenoxy group. This compound or R <_1> of the said General formula (1) is a 2-methyl-propan-2-yl group or 2-methyl-butan-2-yl group, n is 2, and R is the 2nd and 4th position of a phenoxy group. ₁ is a compound present. Such a compound has excellent dyeing fastness and dyeability, and in particular, no dye remains during dyeing, and it is possible to control the color of dyeing with good reproducibility.

By using the red dye represented by the said General formula (1) with the blue dye and yellow dye which can dye a polypropylene fiber structure, especially the blue dye and yellow dye which are described in nonpatent literature 3, 4, respectively, Polypropylene fiber structures can be dyed to the tint of the material.

The dye represented by the said General formula (1) is well-known and can be manufactured according to the method already known to a person skilled in the art. Commercially available branched alkyl groups with commercially available 1-amino-2-bromo-4-hydroxyanthracene 9,10-dione under known conditions described in, for example, Dyes &amp; Pigments, 95, 2012, 201-205. Or phenol substituted with an arylalkyl group.

(Polypropylene fiber structure)

The polypropylene fiber structure in the present invention includes polypropylene fibers. Here, as long as a polypropylene fiber contains a polypropylene resin, it will not specifically limit. The polypropylene fiber structure may be formed using the fiber comprised from polypropylene resin only, or the polypropylene fiber structure may be formed using the fiber which mix | blended and / or bonded the other polymer component to polypropylene resin.

From the polypropylene fibers, polypropylene fiber structures of various types can be produced according to existing methods in the art. As a form of a polypropylene fiber structure, for example, a thread-like structure (filament yarn, a spun yarn, a slit yarn, a split yarn), a cotton (cotton) structure, a string structure, a fabric structure (fabric, knitted fabric, nonwoven fabric, felt) , Tufts, and the like, and combinations thereof, but are not limited to these. In addition, commercially available polypropylene fiber structures can also be used. Moreover, you may mix and / or mix fiber, such as polyester, with polypropylene fiber, and manufacture a fiber structure.

(Method for producing 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. Methods of dyeing polypropylene fiber structures with a 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 red color of the subtractive tricolor. In addition, the range of "the red of the three mixed 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, saturation) of the color. Among the attributes of color perception, color H (JIS # Z8721: 1993), which is a color scale, ranges from 10 P to 10 R around 10 RP. Moreover, the dye represented by the said General formula (1) and the blue dye and yellow dye which were respectively described in the nonpatent literature 3, 4 are combined, and the polypropylene fiber structure is dyed, and the dyed polypropylene fiber structure May be prepared. In this case, the polypropylene fiber structure can be dyed in the color tone of the material.

(Use of dyed polypropylene fiber structures)

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

Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the present invention in any way.

Example

(material)

The chemical structures of the dyes 1 to 26 used in the test are shown in Table 1 below. In addition, about dye 1-23, 25, 26, the structural formula and substituent which were described in patent document 6 corresponding to these are also shown in following Table 1.

Table 1-1

TABLE 1-2

Table 1-3

Table 1-4

Table 1-5

Table 1-6

The dyes 1 to 5, 7, 8, 12, 14, 15, 24, 25, and 26 are ARIMOTO CHEMICAL CO., LTD. As starting compounds. Obtained from. Dye 9 is the product name KP Plast Blue G, dye 21 is the product name KP Plast Yellow 염료 HR, dye 22 is the product name KP Plast Yellow 2 HR, dye 23 is the product name KP Plast Brilliant RedMG, KIWA Chemical Industry Co., Ltd. Obtained from. Dye 6 was obtained from Nippon Kayaku Co., Ltd. as a product name Kayaset® Red® B, dye 10 was product name Kayaset® Blue® FR, and dye 11 was product name Kayaset® Red # 168. Dye 13, dye 16, and dye 20 were extracted and isolated from Teratop®Pink®3G, Terasil®Pink®2GLA, and Terasil®Blue®BGE manufactured by Huntsman Japan. 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 Dystar Japan Dianix®Blue®GL-FS and Dianix®Blue®AM-77, respectively.

Two kinds of polypropylene cloth are manufactured by Mitsubishi Rayon Co., Ltd. Obtained from. One consists of a polypropylene fiber yarn of 110 dtex / 36 filaments and is woven into a circular piece tester (polypropylene fabric No. 1). The loop density of this knitted fabric was coarse (Wale 20 / 2.54 cm; Course 32 / 2.54 cm), and therefore the magnetic stirrer could be easily homogenized with weak stirring force. The other one is a dense two-stage knit (polypropylene fabric No. 2; 250 g / m 2; thread of 190dtex / 48 firaments; wale 2 * 33 / 2.54cm; course 2 * 34 / 2.54cm to measure dyeing fastness) Was. 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.) was refine | purified at 80 degreeC in the water system with the liquid dyeing machine. Thereafter, the polypropylene cloth No. 2 was centrifugally dehydrated, and the cut was heat-set at 130 ° C as a pretreatment.

,HASEGAWA MENKO CO., LTD. 으로부터 구입했다.Cotton yarn (30 / cotton), 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 fabric. One kind had a gauze structure (cotton No. 1: 30 warp / 2.54 cm, 30 horizontal yarns / 2.54 cm), and the second had a single-sided flannel structure (cotton No. 2). These fabrics were purchased from PIP CO., LTD. The third thing has plain weave structure (cotton cloth No. 3: warp 45 /2.54cm, horizontal 45 /2.54cm;

, HASEGAWA MENKO CO., LTD. Purchased from

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

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

(Dye test)

The apparatus used for the dyeability test is shown in FIG. The dyeing test apparatus 100 includes a liquid CO ₂ cylinder 101, a stop valve 102 107, 110, 121, a needle valve 103, a liquid feed 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, dye bath 112, filter 116, magnetic stirrer 117, constant temperature air bath 118), a temperature gauge 120, a semi-automatic back pressure valve 124 (comprising a back pressure valve 122, a heater 123). The magnetic stirring constant temperature air bath 119 utilized the 50 cm <3> stainless steel bath set (SCF-Sro type) in the temperature control oven by JASCO Corporation. As the liquid feeding pump 106, the carbon dioxide liquid feeding pump (SCF-Sro type) made from 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 kept as follows using a glass fiber filter (2x2 cm; ADVANTEC® GA-55; manufactured by Advantec Toyo Kaisha, Ltd.). First, one sheet of filter was immersed in acetone, and then dye was placed on the remaining filter and covered with the immersed filter. Acetone was used in order to laminate | stack two filters easily. Next, these were dried at room temperature and acetone was removed. The stirrer 115, the polypropylene cloth No. 1 (about 1.0 g) 114, and the dye 113 sandwiched between two filters are sequentially placed in the dyeing tank 112 and the dyeing tank 112 is sealed. did. The air in the dye bath 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 carbon dioxide feed pump 106 pressurizes the dye bath 112 to a carbon dioxide pressure of 25 MPa, and to a dyeing temperature (120 ° C). Reheated. By the back pressure valve 122, the pressure of the carbon dioxide in a dyeability test apparatus system was controlled to 25 MPa, and the salt bath was stirred with the magnetic stirrer. After 60 minutes, the dye bath 112 was gradually reduced to atmospheric pressure by the back pressure valve 122 while maintaining the stirring.

The treated polypropylene cloth was taken out from the dyeing tank 112. Next, when the dye precipitated on the fiber surface without diffusing into the fiber, the dyed cloth was immersed in acetone at room temperature for 30 seconds to remove the dye deposited on the surface of the dyed cloth. The dipped 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

Moreover, the presence or absence of the dye which remained between two filters was confirmed. Moreover, the presence or absence of the dye which precipitated on the inner wall of the dyeing tank 112 was also confirmed. The result was classified as follows about the residual dye in tank which combined what remained on the filter and what precipitated on the inner wall.

◎: no residue

(Circle): Remaining trace amount (visually, powder can be confirmed)

△: many residual

×: almost all residual

(Supercritical Fluid Staining Process)

For dyes with good dyeability (that is, good dyeing ability and few residual dyes in the tank), a dyeing cloth was prepared to evaluate dyeing fastness. Polypropylene fabric No. 2 was cut into 20 x 150 cm and weighed (about 75 g). Cotton cloth Nos. 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 order to a stainless steel cylinder (220 mm wide; 30 mm outer diameter, 26 mm inner diameter) having a punch hole (3 mm in diameter, number of holes / area 1.87 / cm 2, effective width 190 mm). All. In order to avoid the direct influence of the punch hole on polypropylene fabric No. 2 dyeing, such fabric was used as an undercross. Undercross was made to flow uniformly to a to-be-stained object, avoiding a linear passage of a fluid from a punching hole. Then, polypropylene cloth No. 2 and cotton cloth No. 3 were wound one by one. Cotton cloth No. 3 prevented the polypropylene fabric from shrinking due to the radiant heat from the bath. The rolled up roll was secured by loosely binding the edges with cotton yarns.

An 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. 209, the DC motor 210, the safety valves 211 and 212, the cooler 213, the stop valves 214 to 218, the needle valve 219, and the heater 220. The cylinder 221 wound around the fabric sample was placed in a high pressure stainless steel bath 222 (volume 2230 cm 3). Dye 223 (0.3% or 0.3% omf of the mass of polypropylene dye) wrapped with paper wipes (KimWipes S-200, manufactured by NIPPON PAPER CRECIA CO., LTD.), The cylinder 221 in the bath 222 Placed in the fluid passage above.

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

After the temperature and pressure circulation rate reached a certain value (ie, 120 ° C., 25 MPa, 750 rpm), these conditions were maintained for 60 minutes, and the polypropylene fabric 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 fell to the critical pressure (8.0-7.4 MPa) substantially. Thereafter, the dyed polypropylene fabric was taken out of the bath 222. The dyeing ability in the case of using polypropylene cloth No. 2 and the residual dye in the bath were equivalent to the results of the dyeing test using polypropylene cloth No. 1.

The dye which precipitated on the surface of a polypropylene cloth is removed by operation which continues circulation and slowly discharges pressure. Therefore, if the dye concentration does not become excessive, the subsequent washing process becomes unnecessary. The frictional fastness (JIS # L0849, type II, attached white cloth: cotton), which tends to exhibit unusually low performance when the surface precipitates dye, becomes normal by this pressure-pressure operation. In the examples of the present invention, dry friction and wet friction represented grades 4-5 through fifth. The dyeing ability in the case of using polypropylene cloth No. 2 and the residual dye in the bath were equivalent to the results of the dyeing test using polypropylene cloth No. 1.

(Washing fastness)

Washing fastness test was carried out using the multi-woven teaching cloth (Teaching No. 1: JIS # L0803: 2005; fabric woven from cotton, nylon, acetate, wool, rayon, acrylic, silk, and polyester), and JIS L0844 : 2005 A-2 method (based on ISO # 105-C02: 1989 test 2). In the contamination of multi-woven fabrics, the most contaminated parts were evaluated. In addition, the contamination of the test solution as well as the contamination of the fabric was also evaluated with reference to ISO # 105-D01: 1994. In the evaluation of the contamination of the test solution, the test solution remaining in the container was passed through the filter paper. The staining of the contaminated 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 on a gray scale for contamination evaluation.

Light fastness

The light fastness of the dyed polypropylene fabric was evaluated based on JIS # L0842 (third exposure method). The light fastness test was performed by the 3rd exposure method about grade 3 and / or grade 4 using light, such as an ultraviolet-carbon arc.

(Sublimation fastness)

The sublimation fastness of the dyed polypropylene fabric was evaluated based on JIS # L0854 using nylon (single fiber cloth (I) 7: JIS # L0803: 2005) for the attached back fabric.

(Side color)

A spectrophotometer (CM-600d: manufactured by Konica Minolta, Japan Inc.) was used for the coloration of the dyed polypropylene fabric. The measurement conditions of spectral reflectance were four sheets of samples on a non-fluorescence white paper, measuring diameter φ 8 mm, observation condition 2 ° field of view, observation light source D65, measurement wavelength range 400-700 nm, measurement wavelength interval 10 nm, Specular reflection is excluded (SCE: Specular Component Exclude). L *, a *, and b * were calculated | required based on CIE1976L * a * b * from the spectral reflectance. Moreover, based on JIS Z8721: 1993, the color H in the D65 light source was calculated | required.

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

Table 2 shows the test results of Examples 1 to 6 and Comparative Examples 1 to 20 using dyes 1 to 26, respectively. In Examples 1 to 6, Comparative Examples 1 to 3, Comparative Examples 6, 7, 19, and 20 in which good dyeing of the polypropylene fabric was confirmed, the dyeing fastnesses were also evaluated. In Comparative Example 3, since dye 5 used for dyeing was in a tar state and weighing was difficult, washing fastness and sublimation fastness were not evaluated. In addition, the coloration of the dyed polypropylene fabrics of Examples 1 to 6 and Comparative Examples 1 and 2 and 20 was carried out. The results are shown in Table 3.

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

From the results of the dyeing test described above, among the dyes 1 to 23 corresponding to the representative dyes described in Patent Document 6, it was possible to satisfactorily dye the polypropylene fabric, and the dyes 1 to 8, 11, 12, and 25 (Example 1 5, Comparative Examples 1-3, 6, 7, and Example 6), it can understand that there existed many dye which was not able to dye polypropylene cloth by supercritical carbon dioxide. On the other hand, dye 24 (Comparative Example 19) corresponding to the positional isomer of the representative dye (1, 4-bis (octylamino) -anthraquinone) described in Non-Patent Document 19 had good dyeing resistance but poor light fastness. It can be understood that both dyeability and color fastness cannot be obtained with a dye having a desired color by simply changing the substitution position. Moreover, from the comparison of Examples 1-6 and Comparative Examples 1-3, 6, 7, 8-11, 19, 20, dyeability (dyeability, residual dye in a tank), dyeing fastness (washing fastness, light fastness, sublimation fastness) In order to make all of them good, the chemical structure of a dye is a branched alkyl group or an aryl whose substituent at the 1-position of an anthraquinone ring contains an amino group, and the substituent at the 2-position contains quaternary carbon, as shown by the said General formula (1). It was shown that the phenoxy group substituted by the alkyl group and the substituent at the 4-position need to be a hydroxy group.

In addition, all the dyes used in Examples 1-6 are solid, but dye 8 (comparative example 3) corresponding to R <_2> is a C9 linear alkyl group in the said General formula (1) is a tar state, It is not possible to control the degree (darkness of color) and is not suitable for industrial production.

As shown in Table 3, all the dyed polypropylene fabrics of Examples 1 to 6 exhibited red of subtractive trichromatic color. In Examples 1, 2, 4, and 6 in which the substituents on the phenoxy group in the general formula (1) used dyes 1, 2, 4, and 20, which are branched alkyl groups, there were fewer residual dyes in the bath. In particular, Example 4, wherein R ₁ of the general formula (1) is a 2-methylbutan-2-yl group, n = 2, using dye 4 in which R ₁ is present at 2 and 4 positions of the phenoxy group 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 Only trace amounts of dye remained in the bath as stains on paper wipes, indicating that almost all of the dye used was adsorbed onto the fibers. In Examples 4 and 6, washing fastness, light fastness, and sublimation fastness were all excellent.

As mentioned above, although this invention was demonstrated with reference to above-mentioned embodiment, this invention is not limited to the above-mentioned embodiment, It is contained in this invention also about what combined suitably and substituted the structure of embodiment. Moreover, based on the knowledge of those skilled in the art, it is also possible to appropriately add a combination of the embodiment and the order of a process in the embodiment, or to add various modifications, such as various design changes, to the embodiment. It may be included in the range of.

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

100: the device used for the 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: magnetic 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 unit,
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 jaw,
223: cheap dye with paper wipes,
224: impeller.

Claims (8)

General formula (1) below:
[Tue 1]

(In formula, R <_1> is respectively independently 1 type selected from the group which consists of a C4-C8 branched alkyl group and a C9-19 arylalkyl group, n is 1-3. The said branched alkyl group is quaternary Dyed polypropylene fiber structure, comprising a carbon atom, wherein the alkyl portion of the arylalkyl group comprises a quaternary carbon atom. The method of claim 1,
Stained polypropylene fiber structure, characterized in that n is 2. The method according to claim 1 or 2,
A dyed polypropylene fiber structure, wherein n is 2 and the R ₁ group is the branched alkyl group. The method of claim 1,
A dyed polypropylene fiber structure, wherein n is 1 and the R ₁ group is the branched alkyl group. The method of claim 1,
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 . The method of claim 1,
Dyed polypropylene fiber, wherein said red dye is 1-amino-4-hydroxy-2- [4- (2, 4,4-trimethylpentan-2-yl) phenoxy] anthracene-9, 10-dione structure. The method according to any one of claims 1 to 6,
A dyed polypropylene fiber structure, characterized in that a poin. A medical product using the dyed polypropylene fiber structure according to any one of claims 1 to 7.

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