JPWO2005123845A1 - Dye composition and polylactic acid molded article dyed with the composition - Google Patents

Abstract

Provided is a black or navy dye composition that is excellent in dyeability and can dye polylactic acid in black or navy with reduced redness. This composition contains the main black disperse dye (a1) or the main navy disperse dye (a2) and a predetermined blue disperse dye in a predetermined ratio. The main black disperse dye (a1) and the main navy disperse dye (a2) are disperse dyes having dyeability with respect to polyester and polylactic acid, and the blue disperse dye dyes a polylactic acid molded product with the dye. In this case, the disperse dye has a maximum absorption between 640 nm and 700 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded article.

Description

  The present invention relates to a dye composition for dyeing a polylactic acid molded article and a polylactic acid product obtained using the same. More specifically, the present invention relates to a dye composition capable of dyeing a polylactic acid molded article such as polylactic acid fiber into a deep black or navy color and a polylactic acid molded article dyed with the dye composition.

Conventionally, in the fiber processing field, polyester molded bodies (for example, polyester fibers, woven fabrics, knitted fabrics, and nonwoven fabrics made of the fibers) have high versatility. Therefore, much development of the dye composition for dyeing a polyester molded body has been performed especially.
When dyeing a molded product such as the above-mentioned polyester fiber in black or navy, a mixed dye in which several dye components are combined is used. Such a combination dye usually contains a blue disperse dye, a yellow disperse dye and / or an orange disperse dye, and, if necessary, a red disperse dye. Here, each disperse dye contained may cause a difference in dyeability depending on the type of polyester fiber to be dyed.
Furthermore, even if the dyeing property of each dye is the same in the polyester molded body to be dyed, the dyed color may appear different depending on the wavelength component of light and their intensity. In other words, artificial light consisting of various light wavelength components is used in real life, so when you see the same dyed molded product, it is under natural light or under artificial light. Depending on whether or not there is a slight difference in the visually recognized colors. Furthermore, there may be a slight difference in visually recognized colors between artificial light composed of a certain light wavelength component and artificial light composed of another light wavelength component. The phenomenon in which the color visually recognized depending on the type of the light source is generally called “color rendering”, and even in the polyester fiber, there may be some color rendering depending on the dye used and the light source. . Thereby, for example, when the polyester fiber is dyed black as described above, the reflected light when irradiating the dyed product with light is reddish black, greenish black, etc. There are times when it shows the depth of many colors.
Dye compositions capable of dyeing polyester fibers in black or navy have variations that exhibit such subtle color differences, but in recent years, their color depth has become relatively common due to people's preference. Tend to. More specifically, both reddish black and navy colors have a tendency for consumers to feel the dyed product itself at a low price, and those skilled in the art have such a dye composition. I want to avoid using it. Therefore, development of a dye composition capable of dyeing polyester into a deep black or navy color without redness has been advanced. As a result, recently, many polyester molded articles dyed with such a dye composition are commercially available. For example, the color of already-dyed polyester fiber products on the market is slightly reddish black to slightly green as long as it suits the consumer's taste and does not cause a decline in purchasing motivation. There are black variations up to tasted black. The range of this variation is only a relatively narrow difference from the viewpoint of hue. However, due to the high versatility of polyester fiber products, this black variation is strongly impressed with consumer awareness as a standard in black fiber products. Therefore, the black color that deviates from this variation is considered to cause a sense of incongruity to the consumer, which makes the product perceived to be inexpensive, or to reduce the willingness to purchase.
On the other hand, instead of conventional polyester products, today, environmental measures are required, and after use, it is decomposed into water and carbon dioxide by bacteria or enzymes present in the soil or river, and returns to nature. There are great expectations for plastic. In particular, polylactic acid resins are prepared from plants that absorb carbon dioxide during growth, and thus are attracting attention as resins that not only reduce the environmental burden during disposal but can also build a natural circulation system.
Conventionally, in order to dye a molded body made of such a polylactic acid resin (for example, polylactic acid fiber), as a dye capable of obtaining a good color and improving build-up, wet fastness, and / or sunlight fastness In general, disperse dyes having an I / O value according to acetate dyes are mainly used among disperse dyes generally used for dyeing polyester moldings (Mogaki et al., “Journal of Textile Science”, 2001, 57, p.234-243; and Yamaguchi, “Processing Technology”, 2001, 36, p.458-463). Japanese Patent Application Laid-Open No. 8-311781 describes that a disperse dye is used to dye an aliphatic polyester fiber such as polylactic acid by selecting a predetermined dyeing temperature, pH, and dyeing time.
However, even when dyed in black or navy using such a combination of disperse dyes, there is a problem with the dyed polylactic acid molded article. That is, it is difficult to obtain the same color depth as when the dyed molded product is polyester. For example, a polylactic acid molded article dyed in black using a combination of disperse dyes used in conventional dyeing for polyester has a significant color difference compared to a polyester molded article dyed with the dye. For example, the polylactic acid molded body seems to have a slightly reddish black color. Furthermore, depending on the light wavelength component constituting the artificial light, the difference is remarkably enlarged, and it feels almost brown.
Such a color difference (difference in color depth) is considered to be derived from the fact that the dispersibility of disperse dyes is different because the polarity of polyester molecules and polylactic acid molecules are different from one technical aspect. It is done. From another aspect, it is considered that the absorption wavelength of the disperse dye on the polylactic acid molded product shifts to the short wavelength side as compared with the absorption wavelength on the polyester fiber.
The phenomenon in which the color difference as described above occurs is disadvantageous for both the manufacturer and the consumer. For example, in a case where a manufacturer manufactures a target product in large quantities using a plurality of factories or production lines, even if an attempt is made to produce a product of the same color, the lighting used in those factories or production lines Depending on the type, lighting conditions, etc., there may be differences in the color perceived by those engaged in manufacturing. As a result, even if products of the same standard manufactured at multiple factories or production lines are compared with each other, the subtle differences in the dyeing conditions adjusted for each plant or line are different between products of the same standard. It is considered that the difference (ie, variation) appears. Variation between products is a problem to be avoided because it reduces the reliability of the product itself. In other words, there is a demand for a technique for dyeing a polylactic acid molded product with little difference in color regardless of the difference in conditions at the manufacturing site.
On the consumer side, there is a tendency to judge the appearance of the product based on the color of black or navy polyester moldings that are widely available in the market, so for example, reddish black is cheap. There is a problem that it is felt or is visually uncomfortable as compared to conventional polyester products, which affects consumers' willingness to purchase. Therefore, while polylactic acid moldings are highly expected as an alternative to conventional polyester moldings, polylactic acid moldings dyed in various colors are widely used in society as an alternative to dyed polyester moldings. Is difficult.
An object of the present invention is to solve the above problems, and the object of the present invention is to have excellent dyeing properties and be comparable to a conventional polyester molded body dyed black or navy. An object of the present invention is to provide a dye composition capable of forming a dyed polylactic acid molded article having a color depth, and a dyed polylactic acid molded article using the same.

The black dye composition of the present invention is a dye composition for dyeing a polylactic acid molded product in black and contains a main black disperse dye (a1) and a blue disperse dye (b1), and the main black disperse dye (A1) is an absorbance indicating the absorbance of the dyed surface of the dyed molded article when dyed with a blue disperse dye (b1) and having a dyeing property with respect to polyester and polylactic acid. In the wavelength region of 550 nm to 700 nm of the curve, there is a maximum absorption between 640 nm and 700 nm, and when the total amount of the main black disperse dye (a1) and the blue disperse dye (b1) is 100 parts by mass, The dye (a1) is contained in a proportion of 85 to 95 parts by mass, and the dye (b1) is contained in a proportion of 5 to 15 parts by mass.
The black dye composition of the present invention is a dye composition for dyeing a polylactic acid molded product black, and comprises a main black disperse dye (a1), a blue disperse dye (b1), and a blue disperse dye (c1). The main black disperse dye (a1) has a dyeing property with respect to polyester and polylactic acid, and when the polylactic acid molded product is dyed with the blue disperse dye (b1), the dyed molded product In the absorbance region showing the absorbance of the dyed surface of the dye, there is a maximum absorption between 640 nm and 700 nm in the wavelength region of 550 nm to 700 nm, and the polylactic acid molded product is stained with the blue disperse dye (c1). There is a maximum absorption between 550 nm and 660 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve showing the absorbance of the dyed surface of the molded body, and the main black disperse dye When the total amount of (a1), the blue disperse dye (b1), and the blue disperse dye (c1) is 100 parts by mass, the dye (a1) is in a proportion of 65 to 90 parts by mass. b1) is contained in a proportion of 5 to 15 parts by mass, and the dye (c1) is contained in a proportion of 5 to 20 parts by mass.
In one embodiment, the black dye composition further includes 5 masses with respect to a total of 100 mass parts of the main black disperse dye (a1), blue disperse dye (b1), and blue disperse dye (c1). 15 parts by mass of an anionic dispersant is contained.
In another embodiment, the blue disperse dye (b1) has a color index (CI) of Disperse Blue 7, Disperse Blue 60, Disperse Blue 87, Disperse Blue 87.1, Disperse Blue 198, And at least one disperse dye corresponding to a color index selected from the group consisting of Disperse Green 9.
In still another embodiment, the blue disperse dye (c1) has a color index (CI) of Disperse Blue 3, Disperse Blue 56, Disperse Blue 73, Disperse Blue 73.1, Disperse Blue 77. , Disperse Blue 81, Disperse Blue 149, Disperse Blue 153, Disperse Blue 165, Disperse Blue 291, Disperse Blue 291.1, Disperse Blue 268, Disperse Blue 284, and Disperse Blue 367 And at least one disperse dye corresponding to a color index selected from the group.
The navy dye composition of the present invention is a dye composition for dyeing a polylactic acid molded article in a navy color, and contains a main navy disperse dye (a2) and a blue disperse dye (b2), and the main navy The disperse dye (a2) has a dyeing property to polyester and polylactic acid. When the polylactic acid molded product is dyed with the blue disperse dye (b2), the absorbance of the dyed surface of the dyed molded product is expressed. In the wavelength range of 550 nm to 700 nm in the absorbance curve shown, there is a maximum absorption between 640 nm and 700 nm, and the total amount of the main navy disperse dye (a2) and blue disperse dye (b2) is 100 parts by mass. The dye (a2) is contained in a proportion of 85 to 95 parts by mass, and the dye (b2) is contained in a proportion of 5 to 15 parts by mass.
The navy color dye composition of the present invention is a dye composition for dyeing a polylactic acid molded product in a navy color, and comprises a main navy disperse dye (a2), a blue disperse dye (b2), and a blue disperse dye (c2). The main navy disperse dye (a2) has a dyeing property with respect to polyester and polylactic acid, and was dyed when the polylactic acid molded product was dyed with the blue disperse dye (b2). In the wavelength region from 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the molded product, there is a maximum absorption between 640 nm and 700 nm, and when the polylactic acid molded product is dyed with the blue disperse dye (c2), There is a maximum absorption between 550 nm and 660 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded article. When the total amount of the ivy disperse dye (a2), the blue disperse dye (b2), and the blue disperse dye (c2) is 100 parts by mass, the dye (a2) is in a ratio of 65 parts by mass to 90 parts by mass, The dye (b2) is contained in a proportion of 5 to 15 parts by mass, and the dye (c2) is contained in a proportion of 5 to 20 parts by mass.
In one embodiment, the navy dye composition further includes 100 parts by mass of the main navy disperse dye (a2), the blue disperse dye (b2), and the blue disperse dye (c2). 5 to 15 parts by mass of an anionic dispersant is contained.
In another embodiment, the blue disperse dye (b2) has a color index (CI) of Disperse Blue 7, Disperse Blue 60, Disperse Blue 87, Disperse Blue 87.1, Disperse Blue 198, And at least one disperse dye corresponding to a color index selected from the group consisting of Disperse Green 9.
In still another embodiment, the blue disperse dye (c2) has a color index (CI) of Disperse Blue 3, Disperse Blue 56, Disperse Blue 73, Disperse Blue 73.1, Disperse Blue 77. , Disperse Blue 81, Disperse Blue 149, Disperse Blue 153, Disperse Blue 165, Disperse Blue 291, Disperse Blue 291.1, Disperse Blue 268, Disperse Blue 284, and Disperse Blue 367 And at least one disperse dye corresponding to a color index selected from the group.
The dyed polylactic acid molded article of the present invention is obtained by dyeing a polylactic acid molded article with any of the black dye compositions described above.
The dyed polylactic acid molded article of the present invention is obtained by dyeing a polylactic acid molded article with any one of the above navy dye compositions.
Therefore, the present invention can achieve the following objects: To provide a dye composition capable of dyeing a polylactic acid molded product in black or navy with a color similar to that of a conventional dye for dyeing polyester. A polyester molding dyed with the above-mentioned compounding dye for polyester because the light reflectance in the wavelength region (about 650 nm to about 700 nm) that can affect redness when dyeing the polylactic acid molding is reduced. To provide a dye composition capable of achieving a black or navy color having a color depth equivalent to that of the body; and polylactic acid having a color similar to that of a polyester molded body dyed in a conventional black or navy color To provide a molded body.

FIG. 1 is a graph showing optical reflectance spectra in the wavelength region from 400 nm to 750 nm of the black dyed products obtained in Example 1.2 and Comparative Examples 1.2 to 1.5.
FIG. 2 is a graph showing optical reflectance spectra in the wavelength region of 400 nm to 750 nm of the navy-colored dyes obtained in Example 2.2, Comparative Example 2.2, and Comparative Example 2.3.

Below, the polylactic acid molded object which can be dye | stained with the dye composition of this invention, the black and navy dye composition of this invention, and the polylactic acid molded object dye | stained with the dye which consists of this composition are demonstrated one by one.
(I) Polylactic acid molded body
The polylactic acid molded body that can be dyed with the dye composition of the present invention includes a molded body formed of polylactic acid (PLA) alone or a molded body containing PLA and another polymer. For example, when the molded body is a fiber and includes PLA and another polymer, the other polymer may be in the form of natural fiber, synthetic fiber other than PLA, or the like. Examples of natural fibers include cotton, hemp, silk, and wool. Examples of the synthetic fiber include polyethylene terephthalate (2GT), polypropylene terephthalate (3GT), polybutylene terephthalate (4GT), acetate, nylon, cationic diable polyester (CDP), and vinylon. When the polylactic acid molded product used in the present invention contains PLA and another polymer, the content ratio is not particularly limited and can be appropriately determined by those skilled in the art.
Examples of the polylactic acid molded body used in the present invention include textile products (for example, filaments, yarns and fabrics), films, sheets, and other structures having a predetermined shape. Examples of the filaments and yarns include monofilaments, multifilaments, staple fibers, tows, high bulk staples, high bulk tows, spun yarns, blended yarns, processed yarns, false twisted yarns, irregular cross-sectional yarns, hollow yarns, conjugate yarns, partially oriented yarns ( POY), drawn yarn (DTY), POY-DTY, and sliver. Examples of the fabric include a woven fabric; a knitted fabric; a nonwoven fabric; a braid including a string and a rope; a cotton-like high bulk fabric; a sliver; and a porous sponge.
The size, thickness, dimensions, and the like of the polylactic acid molded body are not particularly limited. The polylactic acid molded body may contain various additives generally used in the field depending on the purpose. Additives include plasticizers, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, light stabilizers, lubricants, fillers, anti-adhesive agents, antistatic agents, surface wetting improvers, incineration aids, There are anti-slip agents and pigments.
(II) Black dye composition
The black dye composition of the present invention contains a main black disperse dye (a1) and a blue disperse dye (b1) and, if necessary, other components such as a blue disperse dye (c1), a dispersant and various auxiliary agents. . These will be described below.
(II-1) Main black disperse dye (a1)
The main black disperse dye (a1) used in the present invention has a dyeing property with respect to both polyester and polylactic acid, and is preferably a dye capable of dyeing the polyester black. This main black disperse dye is itself a blend of various disperse dyes, as described below. The main black disperse dye (a1) alone has a dyeing property of preferably 70% by mass or more, more preferably 80% by mass or more based on the polyester. The main black disperse dye (a1) alone has a dyeing property of preferably 50% by mass or more, more preferably 70% by mass or more based on polylactic acid.
The main black disperse dye (a1) used in the present invention is preferably capable of dyeing polyester so that it can be recognized as black when visually observed by irradiating with standard light from a D65 light source, Preferably, CIE Lab. When a dyed product obtained by dyeing polyester is irradiated with standard light of a D65 light source is used. The value C (saturation) is 10 or less (indicating an achromatic color), and the L (lightness) value is 20 or less (indicating high density). In this specification, “irradiating standard light of D65 light source” means CIE Technical Report (Publication CIE) No. Using the light source and observation conditions described in 15.2, direct light emitted from the light source (that is, light in which the wavelength and / or intensity is not controlled by means such as an arbitrary filter) is irradiated. Say to point to.
The main black disperse dye (a1) can be obtained by combining a dye that can be dyed blue in a broad sense, a dye that can be dyed yellow in a broad sense, and, if necessary, a dye that can be dyed red in a broad sense. In this specification, “blue in a broad sense” refers to a color belonging to “blue” when classified in terms of the three primary colors (blue, yellow and red) of the colorant, and is always visually blue. It is not limited to the color recognized as. Similarly, yellow and red in the broad sense refer to colors belonging to “yellow” and “red”, respectively, when classified in terms of the three primary colors (blue, yellow and red) of the colorant. The main black disperse dye (a1) is specifically obtained by combining a blue-based disperse dye and a yellow-based disperse dye, and optionally a red-based disperse dye.
The polylactic acid molded article dyed using this main black disperse dye (a1) alone has both a relatively low saturation and a high concentration. Such saturation and density can be obtained by visually observing a dyed product (polylactic acid molded article dyed using the main black disperse dye (a1) alone) under irradiation of standard light from a D65 light source, and / or It can be quantified by measuring the reflected light of the dyed product and using a certain calculation formula. Preferably, the low saturation is CIE Lab. Under the standard light irradiation of the D65 light source. The C (saturation) value is 10 or less, and the high density means the L (lightness) value is 20 or less. However, the above L value is not constant depending on the concentration of the dye component used, the dyeing property of the dye component to the molded product, the light absorption efficiency, etc. For example, the smaller the amount of the dye component used, or the molded product used. The value tends to increase as the thickness of (for example, fiber) decreases. When the polylactic acid molded product is dyed using the black dye composition of the present invention containing the main black disperse dye (a1) that can satisfy the range of the above C value and L value, the main black disperse dye (a1) It is preferable that each of the blue-based disperse dye, the yellow-based disperse dye, and the red-based disperse dye contained in the dye has a dyeing property of 50% by mass or more with respect to the polylactic acid molded article. More preferably, it has a dyeing property of 70% by mass or more, and more preferably 80% by mass or more.
The kind of the blue base, yellow base and red base disperse dyes constituting the main black disperse dye (a1) is not particularly limited. All of these are preferably disperse dyes such as azo disperse dyes, quinophthalone disperse dyes, pyridone disperse dyes, anthraquinone disperse dyes, nitro disperse dyes, methine disperse dyes, and blended disperse dyes. These blue-based, yellow-based and red-based disperse dyes are described below.
(II-1-1) Blue-based disperse dye in main black disperse dye (a1)
Examples of blue-based disperse dyes contained in the main black disperse dye (a1) include Disperse Blue 148, Disperse Blue 79.1, Disperse Blue 291 or Disperse Blue of Color Index (CI). Examples thereof include disperse dyes corresponding to 291.1, other disperse dyes corresponding to CI, and blended dyes which are mixtures of these dyes. Specific examples include the following disperse dyes: DIANIX Blue F2B-SE (manufactured by Dystar), DIANIX Dark Blue SE-3RT (manufactured by Dystar), DIANIX Navy S-2G 200% (manufactured by Dyster), KAYALON POLYESTER Blue 2R-SF (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Navy Blue R-SF (manufactured by Nippon Kayaku Co., Ltd.), MIKETON POLYESTER Blue G-ADW (manufactured by Dystar), MIKETON POLYESTER 3plu Dystar), MIKETON POLYESTER Blue 3RSF (Dystar), MIKETON POLYESTER Blue 7GSF (Dystar), MIKE TON POLYESTER Navy Blue 3GS (manufactured by Daistar Co., Ltd.), MIKETON POLYESTER Navy Blue RRSF (manufactured by Daistar Co., Ltd.), etc .; TEROSIL Blue BGE-01 (manufactured by Ciba Specialty Chemicals Co., Ltd.) . (Dystar), MIKETON POLYESTER Blue TSF (Dystar) and other anthraquinone disperse dyes; DIANIX Blue PAL (Dystar), DIANIX Blue K-FBL (Dystar), DIANIX Blue ACE (Dystar) DIANIX Blue PLUS (manufactured by Dystar), DIANIX Dark Blue S-LF (manufactured by Dystar), DIANIX Navy CC (manufactured by Dystar), CIBACET Blue EL-B (manufactured by Ciba Specialty Chemicals), CIBACET Blue -FG (manufactured by Ciba Specialty Chemicals), CIBACET Tuequoise EL-FG (manufactured by Ciba Specialty Chemicals), KAYALON PO YESTER Blue B-SF conc (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Blue T-S new (manufactured by Nippon Kayaku Co., Ltd.), SUMIKARON Blue E-RPD (manufactured by Sumika Chemtex Co., Ltd.), SUMIKARON Blue Formulated disperse dyes with trade names such as SE-RPD (manufactured by Sumika Chemtex Co., Ltd.); and trade names such as DIANIX Blue AM-SLR (manufactured by Dystar), CIBACET Navy FL-R (manufactured by Ciba Specialty Chemicals) Other disperse dyes. The blue-based disperse dye may be contained alone or in combination in the main black disperse dye (a1).
The blue-based disperse dye is preferably contained in a proportion of 30% by mass to 60% by mass, more preferably 40% by mass to 50% by mass, based on the mass of the main black disperse dye (a1) used in the present invention. Is done.
(II-1-2) Yellow-based disperse dye in main black disperse dye (a1)
Examples of yellow-based disperse dyes contained in the main black disperse dye (a1) include Disperse Yellow 42, Disperse Yellow 126, Disperse Orange 30, Disperse Orange 31 and Disperse of Color Index (CI). Disperse dyes corresponding to Perth Orange 55 or Disperse Orange 61, other disperse dyes corresponding to CI, and blended dyes containing these dyes may be mentioned. Specific examples thereof include the following disperse dyes: DIANIX Yellow Brown SE-R (Dystar), DIANIX Yellow Brown S-2R 150% (Dystar), DIANIX Orange E-3R (Dystar), KAYALON POLYESTER Yellow 4GE (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Yellow 5R-SE200 (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Orange R-SF (manufactured by Nippon Kayaku Co., Ltd.), KAYALONRYPO 2RL-S (manufactured by Nippon Kayaku Co., Ltd.), MIKETON POLYESTER Yellow 5G (manufactured by Dystar), MIKETON POLYESTER Orange SF (manufactured by Dystar), MIKETON POLYESTER Orange SC (manufactured by Dystar), MIKETON POLYESTER Orange SC e / c (manufactured by Dystar), MIKETON POLYESTER Yellow Brown REL (manufactured by Dystar), KETERON POLL Azo-type disperse dyes with trade names such as: DIANIX Yellow S-3G (manufactured by Dystar), MIKETON POLYESTER Yellow 3GSL (manufactured by Dystar), MIKETON POLYESTER Yellow F3G (manufactured by Dystar), MIKETON POLYESTER Yellow Star (manufactured by Dystar) ) And other product names for quinophthalone A dye; a pyridone-based disperse dye having a trade name such as DIANIX Flavine XF (manufactured by Dystar); an anthraquinone-based disperse dye having a trade name such as MIKETON POLYESTER Yellow HLS (manufactured by Dystar); a DIANIX Yellow AM-42 (manufactured by Dystar); Nitro-based disperse dyes such as MIKETON POLYESTER Yellow YL (manufactured by Dystar), TERATOP Yellow GWL (manufactured by Ciba Specialty Chemicals); methine-based disperse dyes such as DIANIX Yellow 7GL (manufactured by Dystar); and DIANIX Yellow PAL (Dystar), DIANIX Yellow N-TAN (Dystar), DIANIX Yellow AC-Enew (Da Star Co., Ltd.), DIANIX Yellow Brown CC (Daistar Co., Ltd.), CIBACET Yellow EL-F2G (Ciba Specialty Chemicals Co., Ltd.), SUMIKARON Yellow E-RPD (manufactured by Sumika Chemtex Co., Ltd.), SUMIKARON Yellow SE-RPD Compounded disperse dyes with trade names such as Kachemtechs Co., Ltd.). The main black disperse dye (a1) used in the present invention contains the above yellow-based disperse dyes alone or in combination.
The yellow-based disperse dye is preferably contained in a proportion of 30% by mass to 50% by mass, more preferably 30% by mass to 40% by mass, based on the mass of the main black disperse dye (a1) used in the present invention. Is done.
(II-1-3) Red base disperse dye in main black disperse dye (a1)
Examples of red-based disperse dyes contained as necessary in the main black disperse dye (a1) correspond to Disperse Thread 73, Disper Thread 167.1, or Disperse Violet 39 of Color Index (CI) And disperse dyes corresponding to other CIs, and blended dyes containing these dyes. Specific examples include the following disperse dyes: DIANIX Rubine SE-B (Dystar), DIANIX Rubine C-B 150% (Dystar), DIANIX Rubine SE-FG (Dystar), DIANIX Deep Red SF (manufactured by Dystar), DIANIX Red C-4G 150% (manufactured by Dystar), DIANIX Violet S-4R (manufactured by Dystar), TERASI Rubine 2GFL (manufactured by Ciba Specialty Chemicals), KAYALON POLYESTER Red BR-S ( Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Red BL-E (Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Red 3BL-S200 (Nippon Kayaku Co., Ltd.), KA ALON POLYESTER Ruby GL-SE200 (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER violet 3RL-S200 (manufactured by Nippon Kayaku Co., Ltd.), MIKETON POLYESTER Scarlet 3R (manufactured by Dystar), MIKETON RCS Made by Dystar), MIKETON POLYESTER Red FL (made by Dystar), MIKETON POLYESTER Red BSF (made by Dystar), MIKETON POLYESTER Red 2BSF (made by Dystar), MIKETON POLYESTER Red 3BSF (made by Dystar) Manufactured by Dystar), MIKETON Azo-based disperse dyes with trade names such as OLYESTER Violet ADW (Dystar); DIANIX Red AM-86 (Dystar), DIANIX Brilliant Violet R (Dystar), TERATOP Pink 3G (Ciba Specialty Chemicals), TERAIL Red FB 200% (manufactured by Ciba Specialty Chemicals), TERAIL Violet BL 150% (manufactured by Ciba Specialty Chemicals), KAYALON POLYESTER Pink RCL-E (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Red Vollet F (Nippon Kayaku Co., Ltd.) and other quinone-based disperse dyes; MIKETON POLYESTER Red FB extra onc. (Dystar Co., Ltd.), MIKETON POLYESTER Red 4BF # 300 (Dystar Co., Ltd.), MIKETON POLYESTER Red SL (Dystar Co., Ltd.) and other anthraquinone disperse dyes; DIANIX Rubin CC (Dystar Co., Ltd.), DIANIX Rubine PLUS Dystar), DIANIX Red ACE-01 (Dyster), DIANIX Red CC (Dystar), DIANIX Red PAL (Dystar), TERATOP Red NF-R (Ciba Specialty Chemicals), CIBACET Red EL -FR (Ciba Specialty Chemicals), CIBACET Scallet EL-F2G (Ciba Specialty Chemicals), KAYAL N POLYESTER SCARlet 2R-E (manufactured by Nippon Kayaku Co., Ltd.), SUMIKARON Red E-RPD (manufactured by Sumika Chemtex Co., Ltd.), SUMIKARON Red SE-RPD (manufactured by Sumika Chemtex Co., Ltd.) Formulated disperse dyes; and other disperse dyes with trade names such as MIKETON POLYESTER Brown GF # 700 (manufactured by Dystar). In the main black disperse dye (a1) used in the present invention, the red-based disperse dye may be contained singly or in combination.
The red-based disperse dye is contained as necessary as described above. When contained, the ratio of 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, based on the mass of the main black disperse dye (a1) used in the present invention. Contained.
(II-1-4) Preparation of main black disperse dye (a1)
The main black disperse dye (a1) can be obtained, for example, by mixing the blue-based disperse dye, the yellow-based disperse dye, and, if necessary, the red-based disperse dye. This dye (a1) can dye polyester so that it becomes black when visually observed by irradiating the standard light of a D65 light source.
When the main black disperse dye (a1) dyes a polylactic acid molded article using the dye alone, the absorbance in the wavelength range of 400 nm to 600 nm on the stained surface of the dyed molded article is almost constant. It is preferable that the dye has a high value. That is, the main black disperse dye (a1) is preferably a dye having a low optical reflectance in the wavelength region of 400 nm to 600 nm on the dyed surface. Specifically, the reflectance is preferably 5% or less, more preferably 0.1% to 3.5%, and particularly preferably 0.1% to 3%.
Further, the main black disperse dye (a1) is a standard light of an artificial light source D65 of a dyed fiber when a polylactic acid fiber having a general thickness (for example, 1 denier to 5 denier) is dyed with the dye. CIE Lab. The value is preferably an L (lightness) value of 20 or less and a C (saturation) value of 10 or less.
Accordingly, the main black disperse dye (a1) is further added to CIE Lab. So that the optical reflectance of the dyed surface of the dyed molded product becomes the above value. It is preferable to prepare a combination of the blue-based disperse dye, the yellow-based disperse dye, and the red-based disperse dye so that the L (lightness) value and the C (saturation) value are the above values.
When the black dye composition of the present invention contains only the main black disperse dye (a1) and the blue disperse dye (b1) described below as main components, the main black disperse dye (a1) and the blue disperse dye When the total amount of (b1) is 100 parts by mass, the dye (a1) is contained in a proportion of 85 to 95 parts by mass. When the black dye composition of the present invention contains a blue disperse dye (c1) in addition to the main black disperse dye (a1) and the blue disperse dye (b1) described later as the dye, the main black disperse dye ( When the total amount of a1), blue disperse dye (b1), and blue disperse dye (c1) is 100 parts by mass, the dye (a1) is contained in a proportion of 65 to 90 parts by mass.
(II-2) Blue disperse dye (b1)
The blue disperse dye (b1) contained in the composition of the present invention has an absorbance curve of 550 nm indicating the absorbance of the dyed surface of the dyed molded product when the polylactic acid molded product is dyed with the dye (b1) alone. To 700 nm, a blue disperse dye having a maximum absorption between 640 nm and 700 nm, preferably between 650 nm and 690 nm. This blue disperse dye (b1) is a disperse dye capable of dyeing polylactic acid in a broad blue color, and when the polylactic acid molded product is dyed using the dye, the above wavelength range of the above-described absorption curve. Including disperse dyes, which have maximum absorption. The blue disperse dye (b1) used in the composition of the present invention is preferably also a disperse dye having dyeability with respect to a conventional polyester by itself.
The blue disperse dye (b1) having the maximum absorption in such a range is exemplified by a disperse dye corresponding to a specific color index (CI). Examples of blue disperse dyes (b1) include Disperse Blue 7, Disperse Blue 60, Disperse Blue 87, Disperse Blue 87.1, Disperse Blue 198, or Disperse Green 9 of Color Index (CI). The disperse dye applicable to is mentioned. In particular, disperse dyes corresponding to Disperse Blue 60, Disperse Blue 87, or Disperse Green 9 of color index (CI) are preferable.
Examples of blue disperse dyes corresponding to the CI Disperse Blue 7 include the following disperse dyes: Cibaset Turquoise G (manufactured by Ciba Specialty Chemicals), Intraverse Blue Green C (manufactured by Yorkshire Japan) Name disperse dye.
Examples of blue disperse dyes corresponding to the CI Disperse Blue 60 include the following disperse dyes: DIANIX Turquoise S-BG (manufactured by Dystar), DIANIX Brilliant Blue AM-60 (manufactured by Dystar), DIANIX Brilliant Blue BG. (Dystar Co., Ltd.), SUMIKARON Turquoise Blue S-GL (manufactured by Sumika Chemtex Co., Ltd.), SUMIKARON Turquoise Blue S-GLF (manufactured by Sumika Chemtex Co., Ltd.), KAYALON POLYESTRE Turquoise G Co., Ltd.), TERASIL Blue BGE (manufactured by Ciba Specialty Chemicals), SERILENE Brilliant Blue 2GN (Yorkshire) Yapan Co., Ltd.) disperse dyes of the product name, such as.
Examples of the blue disperse dye corresponding to the CI disperse blue 87 include disperse dyes having a trade name such as FORON Turquoise S-BLN (manufactured by Clariant).
Examples of the blue disperse dye corresponding to the CI Disperse Blue 87.1 include disperse dyes having a trade name such as SUMIKARON Brilliant Blue S-BL (manufactured by Sumika Chemtex Co., Ltd.).
Examples of the blue disperse dye corresponding to the CI Disperse Blue 198 include disperse dyes having a trade name such as DIANIX Turquoise Blue G-FS (manufactured by Dystar).
Blue disperse dyes corresponding to the CI Disperse Blue 9 are trade names such as DIANIX Green C-6B (manufactured by Dystar), DIANIX Green CC (manufactured by Dystar), SERILENE Green HWF (manufactured by Yorkshire Japan). Of disperse dyes.
As the blue disperse dye (b1) used in the present invention, any one of disperse dyes included in the above color index or a combination thereof may be used. When the disperse dyes are used in combination, the mixing ratio is not particularly limited.
The blue disperse dye (b1) functions as a component for achieving color correction capable of giving color depth. Therefore, when the black dye composition of the present invention containing the dye and the main black disperse dye (a1) in a predetermined ratio is used, the polylactic acid molded product is dyed deep black without being reddish. And the dyeing property to the polylactic acid molded article is also good.
When the black dye composition of the present invention contains only the main black disperse dye (a1) and the blue disperse dye (b1) as main components as a dye, and in addition to this, the following blue disperse dye (c1) is contained. In any case, when the total amount of each dye is 100 parts by mass, the blue disperse dye (b1) is contained in a proportion of 5 to 15 parts by mass.
(II-3) Blue disperse dye (c1)
The blue disperse dye (c1) contained as necessary in the composition of the present invention shows the absorbance of the dyed surface of the dyed molded article when the polylactic acid molded article is dyed with the dye (c1) alone. It is a blue disperse dye having a maximum absorption between 550 nm and 660 nm, preferably between 560 nm and 630 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve. This blue disperse dye (c1) is a disperse dye capable of dyeing polylactic acid in a broad blue color, and when the polylactic acid molded product is dyed using the dye, the above-mentioned wavelength range of the above-mentioned absorption curve. Including disperse dyes, which have maximum absorption. The blue disperse dye (c1) used in the composition of the present invention is preferably also a disperse dye having dyeability with respect to a conventional polyester by itself.
The blue disperse dye (c1) having the maximum absorption in such a range is exemplified by a disperse dye corresponding to a specific color index (CI). Examples of blue disperse dyes (c1) include Disperse Blue 3, Disperse Blue 56, Disperse Blue 73, Disperse Blue 73.1, Disperse Blue 77, Disperse Blue 81 of Color Index (CI), Disperse dyes corresponding to Disperse Blue 149, Disperse Blue 153, Disperse Blue 165, Disperse Blue 291, Disperse Blue 291.1, Disperse Blue 268, Disperse Blue 284, or Disperse Blue 367 are listed. . In particular, a disperse dye corresponding to Disperse Blue 56, Disperse Blue 73, Disperse Blue 77, or Disperse Blue 367 of the color index (CI) is preferable. The blue disperse dye (c1) may be a disperse dye having the same color index as the blue-based disperse dye constituting the main black disperse dye.
Examples of blue disperse dyes corresponding to the CI Disperse Blue 3 include disperse dyes having trade names such as Cibaset Blue F3R (manufactured by Ciba Specialty Chemicals), Intraverse Brilliant Blue B (manufactured by Yorkshire Japan). .
Examples of blue disperse dyes corresponding to the CI Disperse Blue 56 include DIANIX Blue E-R150 (manufactured by Dystar), MIKETON POLYESTER Blue FBL # 500 (manufactured by Dystar), and SUMIKARON Blue E-FBL (Sumika Chemtex ( And disperse dyes having trade names such as TERASIL Blue S-BG (manufactured by Ciba Specialty Chemicals).
Examples of blue disperse dyes corresponding to the CI Disperse Blue 73 include DIANIX Blue S-BG (manufactured by Dystar), FORON Blue S-BGL (manufactured by Clariant), and SUMIKARON Blue S-BGL (Sumika Chemtex Co., Ltd.). ))) And the like.
Examples of the blue disperse dye corresponding to the CI Disperse Blue 73.1 include disperse dyes having a trade name such as KAYACELON Blue E-BG (manufactured by Nippon Kayaku Co., Ltd.).
Examples of blue disperse dyes corresponding to the CI Disperse Blue 77 include disperse dyes having trade names such as DIANIX Blue AM-77 (manufactured by Dystar) and KIWALON POLYESTER Blue BRLL (manufactured by Kiwa Chemical Industry Co., Ltd.). It is done.
Examples of blue disperse dyes corresponding to the CI Disperse Blue 81 include disperse dyes having a trade name such as SUMIKARON Blue E-GRL (N) (manufactured by Sumika Chemtex Co., Ltd.).
Examples of blue disperse dyes corresponding to the CI Disperse Blue 149 include disperse dyes having a trade name such as KIWALON Polyester Blue D5G (manufactured by Kiwa Chemical Industry Co., Ltd.).
Examples of blue disperse dyes corresponding to the CI Disperse Blue 153 include disperse dyes having a trade name such as SERILENE Blue CBLS (manufactured by Yorkshire Japan).
Examples of blue disperse dyes corresponding to the CI Disperse Blue 165 include KAYALON Polyester Blue GLSF (manufactured by Nippon Kayaku Co., Ltd.), KIWALON Polyester Blue 2BFL (manufactured by Kiwa Chemical Industry Co., Ltd.), and SERILENE Blue RBLS (Yorkshire). And disperse dyes having trade names such as TERASIL Blue BG (manufactured by Ciba Specialty Chemicals).
Examples of blue disperse dyes that fall under the CI Disperse Blue 291 include disperse dyes with trade names such as KAYACELON Blue E-5G (manufactured by Nippon Kayaku Co., Ltd.).
Examples of the blue disperse dye corresponding to the CI disperse blue 268 include disperse dyes having a trade name such as MCP Blue HP-2R (manufactured by Hayashi Chemical Industry Co., Ltd.).
Examples of blue disperse dyes corresponding to the CI Disperse Blue 284 include disperse dyes having a trade name such as DIANIX Blue XF (manufactured by Dystar).
Examples of the blue disperse dye corresponding to the CI disperse blue 367 include disperse dyes having a trade name such as DIANIX Blue S-2G (manufactured by Dystar).
As the blue disperse dye (c1) used in the present invention, any one or combination of disperse dyes corresponding to the color index as described above may be used. Moreover, when using the disperse dye applicable to the said color index in combination, the mixing ratio is not specifically limited.
When the blue disperse dye (c1) is contained, when the total amount of the main black disperse dye (a1), the blue disperse dye (b1), and the blue disperse dye (c1) is 100 parts by mass, Blue disperse dye (c1) is contained in an amount of 5 to 20 parts by mass, preferably 5 to 15 parts by mass.
This blue disperse dye (c1) functions as a component for achieving color correction capable of giving a color depth, similar to the blue disperse dye (b1) described above. Therefore, when a polylactic acid molded article is dyed using a dye composition containing a blue disperse dye (c1) in addition to the main black disperse dye (a1) and the blue disperse dye (b1), a dyed molded article is obtained. Exhibits a deeper black color without being reddish. The composition containing such a main black disperse dye (a1), blue disperse dye (b1), and blue disperse dye (c1) is also excellent in dyeability on the polylactic acid molded article.
(II-4) Other ingredients
As described above, the black dye composition of the present invention contains a dispersant, various auxiliary agents, and the like as necessary. Among these, the dispersant is contained for the purpose of stabilizing the concentration and hue of the dye component and maintaining the stability of the disperse dye during dyeing. Such a dispersing agent is preferably an anionic dispersing agent, and examples of the dispersing agent include natural polymers such as sodium salt of naphthalenesulfonic acid condensate and sodium lignin sulfonate. In particular, a sodium salt of a naphthalenesulfonic acid condensate is preferable because of less coloring over time and a better dye dispersion effect.
When the anionic dispersant is contained in the black dye composition of the present invention, the content thereof is the main black disperse dye (a1), the blue disperse dye (b1), and the blue contained as necessary. Preferably they are 5 mass parts-15 mass parts with respect to a total of 100 mass parts of disperse dye (c1), More preferably, they are 5 mass parts-10 mass parts. By adding the anionic dispersant within the above range, the black dye composition of the present invention has good reproducibility of dyeing density and hue, and can reduce the risk of spec dyeing and contamination of the dyeing machine itself. it can.
Auxiliaries that can be included in the black dye composition include bulking agents, pH adjusters, dispersion leveling agents, dyeing aids, and penetrants (such as sodium dodecylbenzenesulfonate). The content of these auxiliaries is not particularly limited, and can be appropriately set according to the purpose.
(II-5) Black dye composition
As described above, the black dye composition of the present invention contains the main black disperse dye (a1) and the blue disperse dye (b1), and, if necessary, the blue disperse dye (c1), the dispersant, and the auxiliary agent. To do.
In the black dye composition (for dyeing a polylactic acid molded product) of the present invention, the mixing order of the components in the production is not particularly limited as long as the components described above are contained in a predetermined ratio. For example, the following method (i) or (ii) may be employed.
(I) The main black dye (a1) is prepared in advance alone, and then the blue disperse dye (b1) and, if necessary, the blue disperse dye (c1), the dispersing agent, auxiliary agent, etc. Or by mixing in multiple batches;
(Ii) Without preparing the main black disperse dye (a1) in advance, the disperse dyes of each color constituting the main black disperse dye (a1) (ie, a blue-based disperse dye, a yellow-based disperse dye, and necessary Red-based disperse dye used depending on the color), blue disperse dye (b1), blue disperse dye (c1) used if necessary, the above-mentioned dispersants, auxiliaries, etc. simultaneously or multiple times. Manufactured by dividing and mixing.
Furthermore, when the disperse dye (for example, the same kind of dye) corresponding to the same color index is used for the blue-based disperse dye and the blue disperse dye (c1) constituting the main black disperse dye (a1) In addition to the above method (i) or (ii), the following method (iii) can be employed.
(Iii) Blue disperse dyes corresponding to the same color index, and dyes other than blue disperse dyes among the color disperse dyes constituting the main black dye (a1) (that is, yellow-based disperse dyes, and used as necessary) Red-based disperse dyes), blue disperse dyes (b1), and, if necessary, the above-mentioned dispersants, auxiliaries and the like at the same time or divided into several times.
(III) Navy dye composition
The navy dye composition of the present invention contains the main navy disperse dye (a2) and the blue disperse dye (b2), and other components such as a blue disperse dye (c2), a dispersant, and various auxiliary agents as necessary. To do. These will be described below.
(III-1) Main navy disperse dye (a2)
The main navy disperse dye (a2) used in the present invention has a dyeing property with respect to both polyester and polylactic acid, and is preferably a dye capable of dyeing the polyester so as to have a navy color. This main navy dye is itself a blend of various disperse dyes, as described below. This main navy disperse dye (a2) alone has a dyeing property of preferably 70% by mass or more, more preferably 80% by mass or more, based on the polyester. The main navy disperse dye (a2) alone has a dyeing property of preferably 50% by mass or more, more preferably 70% by mass or more, relative to polylactic acid.
The main navy disperse dye (a2) used in the present invention is preferably capable of dyeing polyester so that it can be recognized as a navy color when visually observed by irradiating standard light from a D65 light source.
The main navy disperse dye (a2) may be a dye capable of dyeing polylactic acid in a broad sense of blue, or a dye capable of being dyed in a broad sense of blue, a dye capable of being dyed in a broad sense of yellow, and a broad sense of red In combination with at least one of the dyes that can be dyed. Specifically, it is obtained by combining at least one of a yellow-based disperse dye and / or at least one of a red-based disperse dye with at least one of a blue-based disperse dye, if necessary.
The polylactic acid molded article dyed by using the main navy disperse dye (a2) alone has hue, saturation and density as navy colors. Being navy is confirmed by visual observation under the irradiation of the standard light of the artificial light source D65, or the hue, saturation, and density as a navy color are determined by reflecting the reflected light on the dyed surface of the dyed molded product. It can be quantified by measuring and using certain formulas. Specifically, CIE Lab. Under the standard light irradiation of the artificial light source D65. The values are 15-30 for the C (saturation) value, 250-290 for the H (hue) value, and 15-35 for the L (brightness) value. It is regarded. When the polylactic acid molded article is dyed using the navy color dye composition of the present invention containing an amount of the main navy disperse dye (a2) that can satisfy the range of the above C value and L value, the main navy disperse dye Each of the blue-based disperse dye, the yellow-based disperse dye, and the red-based disperse dye included in (a2) has a dyeing property of 50% by mass or more with respect to the polylactic acid molded article. preferable. More preferably, it has a dyeing property of 70% or more.
The kind of the blue base, yellow base and red base disperse dyes constituting the main navy disperse dye (a2) is not particularly limited. Any of these is preferably an azo disperse dye, a quinophthalone disperse dye, a pyridone disperse dye, an anthraquinone disperse dye, a nitro disperse dye, a methine disperse dye, a compound disperse dye, or other disperse dyes. These blue-based, yellow-based and red-based disperse dyes are described below.
(III-1-1) Blue-based disperse dye in main navy disperse dye (a2)
Examples of blue-based disperse dyes contained in the main navy disperse dye (a2) include Disperse Blue 148, Disperse Blue 79.1, Disperse Blue 291 or Disperse of Color Index (CI). Examples thereof include disperse dyes corresponding to Blue 291.1, other disperse dyes corresponding to CI, and compounding dyes. Specific examples include the following disperse dyes: DIANIX Blue F2B-SE (manufactured by Dystar), DIANIX Dark Blue SE-3RT (manufactured by Dystar), DIANIX Navy S-2G 200% (manufactured by Dyster), KAYALON POLYESTER Blue 2R-SF (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Navy Blue R-SF (manufactured by Nippon Kayaku Co., Ltd.), MIKETON POLYESTER Blue G-ADW (manufactured by Dystar), MIKETON POLYESTER 3plu Dystar), MIKETON POLYESTER Blue 3RSF (Dystar), MIKETON POLYESTER Blue 7GSF (Dystar), MIKE TON POLYESTER Navy Blue 3GS (manufactured by Daistar Co., Ltd.), MIKETON POLYESTER Navy Blue RRSF (manufactured by Daistar Co., Ltd.), etc .; TEROSIL Blue BGE-01 (manufactured by Ciba Specialty Chemicals Co., Ltd.) . (Dystar), MIKETON POLYESTER Blue TSF (Dystar) and other anthraquinone disperse dyes; DIANIX Blue PAL (Dystar), DIANIX Blue K-FBL (Dystar), DIANIX Blue ACE (Dystar) DIANIX Blue PLUS (manufactured by Dystar), DIANIX Dark Blue S-LF (manufactured by Dystar), DIANIX Navy CC (manufactured by Dystar), CIBACET Blue EL-B (manufactured by Ciba Specialty Chemicals), CIBACET Blue -FG (manufactured by Ciba Specialty Chemicals), CIBACET Tuequoise EL-FG (manufactured by Ciba Specialty Chemicals), KAYALON PO YESTER Blue B-SF conc (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Blue T-S new (manufactured by Nippon Kayaku Co., Ltd.), SUMIKARON Blue E-RPD (manufactured by Sumika Chemtex Co., Ltd.), SUMIKARON Blue Formulated disperse dyes with trade names such as SE-RPD (manufactured by Sumika Chemtex Co., Ltd.); and trade names such as DIANIX Blue AM-SLR (manufactured by Dystar), CIBACET Navy FL-R (manufactured by Ciba Specialty Chemicals) Other disperse dyes are mentioned. In the main navy disperse dye (a2) used in the present invention, the above blue-based disperse dye may be contained singly or in combination.
The blue-based disperse dye is preferably contained in a proportion of 45 to 75% by mass, more preferably 55 to 70% by mass, based on the mass of the main navy disperse dye (a2) used in the present invention. Can be done.
(III-1-2) Yellow base disperse dye in main navy disperse dye (a2)
Examples of yellow-based disperse dyes contained in the main navy disperse dye (a2) include Disperse Yellow 42, Disperse Yellow 126, Disperse Orange 29, Disperse Orange 30 and Disperse of Color Index (CI). Examples thereof include disperse dyes corresponding to Perth Orange 31, Disperse Orange 55, or Disperse Orange 61, other disperse dyes corresponding to CI, and blended dyes containing these dyes. Specific examples thereof include the following disperse dyes: DIANIX Yellow Brown SE-R (Dystar), DIANIX Yellow Brown S-2R 150% (Dystar), DIANIX Orange E-3R (Dystar), KAYALON POLYESTER Yellow 4GE (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Yellow 5R-SE200 (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Orange R-SF (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLLOWRELLERLOW -S (made by Nippon Kayaku Co., Ltd.), MIKETON POLYESTER Yellow 5G (made by Dystar), MIKETON POLYESTER Orange SF (manufactured by Dystar), MIKETON POLYESTER Orange SC (manufactured by Dystar), MIKETON POLYESTER Orange SC e / c (manufactured by Dystar), MIKETON POLYESTER Yellow Brown REL (manufactured by Dystar), KETERON POLL Azo-type disperse dyes with trade names such as: DIANIX Yellow S-3G (manufactured by Dystar), MIKETON POLYESTER Yellow 3GSL (manufactured by Dystar), MIKETON POLYESTER Yellow F3G (manufactured by Dystar), MIKETON POLYESTER Yellow Star (manufactured by Dystar) ) Quinophthalone-based dispersion Materials: Pyridone-based disperse dyes having a trade name such as DIANIX Flavine XF (manufactured by Dystar); Anthraquinone disperse dyes having a trade name such as MIKETON POLYESTER Yellow HLS (manufactured by Dystar); Nitro-based disperse dyes such as MIKETON POLYESTER Yellow YL (manufactured by Dystar), TERATOP Yellow GWL (manufactured by Ciba Specialty Chemicals); methine-based disperse dyes such as DIANIX Yellow 7GL (manufactured by Dystar); and DIANIX Yellow PAL (Dystar), DIANIX Yellow N-TAN (Dystar), DIANIX Yellow AC-Enew (Die ), DIANIX Yellow Brown CC (manufactured by Dystar), CIBACET Yellow EL-F2G (manufactured by Ciba Specialty Chemicals), SUMIKARON Yellow E-RPD (manufactured by Sumika Chemtex Co., Ltd.), SUMIKARON Yellow SE-RPD Compounded disperse dyes with trade names such as Kachemtechs Co., Ltd.). In the main navy disperse dye (a2) used in the present invention, the above yellow-based disperse dye may be contained singly or in combination.
The yellow-based disperse dye is preferably contained in a proportion of 5% by mass to 20% by mass, more preferably 10% by mass to 20% by mass, based on the mass of the main navy disperse dye (a2) used in the present invention. Can be done.
(III-1-3) Red base disperse dye in main navy disperse dye (a2)
Examples of red-based disperse dyes that can be included in the main navy disperse dye (a2) correspond to Disper Thread 73, Disper Thread 82, Disper Thread 167.1, or Disperse Violet 39 of Color Index (CI) And disperse dyes corresponding to other CIs, and blended dyes containing these dyes. Specific examples thereof include the following disperse dyes: DIANIX Rubine SE-B (Dystar), DIANIX Rubin C-B 150% (Dystar), DIANIX Rubin SE-FG (Dystar), DIANIX Deep Red SF (manufactured by Dystar), DIANIX Red C-4G 150% (manufactured by Dystar), DIANIX Violet S-4R (manufactured by Dystar), TERAIL Rubine 2GFL (manufactured by Ciba Specialty Chemicals), KAYALON POLYESTER Red BR-S (Japan) Kayaku Co., Ltd.), KAYALON POLYESTER Red BL-E (Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Red 3BL-S200 (Nihon Kayaku Co., Ltd.), KAY LON POLYESTER Ruby GL-SE200 (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Violet 3RL-S200 (manufactured by Nippon Kayaku Co., Ltd.), MIKETON POLYESTER Scarlet 3R (manufactured by Dystar), MIKETON ROLEcCLE TECLE TEC TECLECLE TEC TECRETCOL Made by Dystar), MIKETON POLYESTER Red FL (made by Dystar), MIKETON POLYESTER Red BSF (made by Dystar), MIKETON POLYESTER Red 2BSF (made by Dystar), MIKETON POLYESTER Red 3BSF (made by Dystar) Manufactured by Dystar), MIKETON P Azo-based disperse dyes with trade names such as LYESTER Violet ADW (Dystar); DIANIX Red AM-86 (Dystar), DIANIX Brilliant Violet R (Dystar), TERATOP Pink 3G (Ciba Specialty Chemicals), TERAIL Red FB 200% (manufactured by Ciba Specialty Chemicals), TERAIL Violet BL 150% (manufactured by Ciba Specialty Chemicals), KAYALON POLYESTER Pink RCL-E (manufactured by Nippon Kayaku Co., Ltd.), KAYALON POLYESTER Red Vollet F A quinone-based disperse dye having a trade name such as Nippon Kayaku Co., Ltd .; MIKETON POLYESTER Red FB extra c nc. (Dystar Co., Ltd.), MIKETON POLYESTER Red 4BF # 300 (Dystar Co., Ltd.), MIKETON POLYESTER Red SL (Dystar Co., Ltd.) and other anthraquinone disperse dyes; DIANIX Rubin CC (Dystar Co., Ltd.), DIANIX Rubine PLUS Manufactured by Dystar), DIANIX Red ACE-01 (manufactured by Dystar), DIANIX Red CC (manufactured by Dystar), DIANIX Red PAL (manufactured by Dystar), TERATOP Red NF-R (manufactured by Ciba Specialty Chemicals), CIBACET Red EL -FR (manufactured by Ciba Specialty Chemicals), CIBACET Scallet EL-F2G (manufactured by Ciba Specialty Chemicals), KAYAL N POLYESTER SCARlet 2R-E (manufactured by Nippon Kayaku Co., Ltd.), SUMIKARON Red E-RPD (manufactured by Sumika Chemtex Co., Ltd.), SUMIKARON Red SE-RPD (manufactured by Sumika Chemtex Co., Ltd.) Formulated disperse dyes; and other disperse dyes with trade names such as MIKETON POLYESTER Brown GF # 700 (manufactured by Dystar). In the main navy disperse dye (a2) used in the present invention, the red-based disperse dye may be contained singly or in combination.
When the red-based disperse dye is contained, it is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5%, based on the mass of the main navy disperse dye (a2). It is contained at a rate of mass%.
(III-1-4) Preparation of main navy disperse dye (a2)
The main navy disperse dye (a2) may be, for example, at least one of the blue-based disperse dyes, or the blue-based disperse dye, and a yellow-based disperse dye and a red-based disperse dye. It can be obtained by mixing at least one kind. Preferably, the polyester can be dyed so that it becomes navy when visually observed by irradiating with standard light from a D65 light source.
This main navy disperse dye (a2) is 480 nm more than the average absorbance in the wavelength region of 400 nm to 480 nm on the dyed surface of the dyed molded article when the polylactic acid molded article is dyed using the dye alone. It is preferable that the dye has a high average absorbance in the wavelength region of ˜600 nm (low average optical reflectance). Specifically, the optical reflectance of the dyed surface in the wavelength region of 400 nm to 480 nm is preferably 3% to 12%, more preferably 4% to 11%, and even more preferably 4.5% to 10%. And the optical reflectance in the wavelength region of 480 nm to 600 nm is preferably 8% or less, more preferably 0.1% to 7%, and even more preferably 0.1% to 6.5%. Is in range.
Further, the main navy disperse dye (a2) is a standard light of an artificial light source D65 of a dyed fiber when a polylactic acid fiber having a general thickness (for example, 1 denier to 5 denier) is dyed with the dye. CIE Lab. The values are preferably C (saturation) values of 15-30, H (hue) values of 250-290, and L (lightness) values of 15-35.
Therefore, the main navy disperse dye (a2) is further added to CIE Lab. So that the reflectance of the dyed surface of the dyed molded product becomes the above value. Preferably, the blue-based disperse dye, the yellow-based disperse dye, and the red-based disperse dye are appropriately combined so that the L (lightness) value and the C (saturation) value are the above values. .
When the navy dye composition of the present invention contains only the main navy disperse dye (a2) and the blue disperse dye (b2) described below as main components, the main navy disperse dye (a2) and the blue disperse dye When the total amount of the dye (b2) is 100 parts by mass, the main navy disperse dye (a2) is contained in a proportion of 85 to 95 parts by mass. When the navy color dye composition of the present invention contains a blue disperse dye (c2) in addition to the main navy disperse dye (a2) and the blue disperse dye (b2) described later as the dye, the main navy disperse dye When the total amount of (a2), blue disperse dye (b2), and blue disperse dye (c2) is 100 parts by mass, the main navy disperse dye (a2) is contained in a proportion of 65 to 90 parts by mass. .
(III-2) Blue disperse dye (b2)
The blue disperse dye (b2) contained in the composition of the present invention has an absorbance curve of 550 nm indicating the absorbance of the dyed surface of the dyed molded product when the polylactic acid molded product is dyed with the dye (b2) alone. To 700 nm, and a blue disperse dye having a maximum absorption between 640 nm and 700 nm, preferably between 650 nm and 690 nm. The blue disperse dye (b2) used in the composition of the present invention is preferably also a disperse dye having dyeability with respect to a conventional polyester by itself.
As such a blue disperse dye, any disperse dye corresponding to the specific color index (CI) in the blue disperse dye (b1) used in the black dye composition of the present invention can be suitably used. The example of the brand name of the blue disperse dye corresponding to the CI is the same as the example of the blue dye (b1).
As the blue disperse dye (b2) used in the present invention, any one of disperse dyes included in the color index as described above or a combination thereof may be used. When the above disperse dyes are used in combination, the mixing ratio is not particularly limited.
The blue disperse dye (b2) is contained in the navy dye composition of the present invention in a proportion of 5% by mass to 15% by mass, preferably 5% by mass to 10% by mass, based on the mass of the composition. The The blue disperse dye (b2) functions as a component for achieving color correction capable of giving a color depth. Therefore, when the navy color dye composition of the present invention containing the dye and the main navy disperse dye (a2) in a predetermined ratio is used, the polylactic acid molded body is dyed in a deep navy color without being reddish. And the dyeing property to the polylactic acid molded article is also good.
When the navy color dye composition of the present invention contains only the main navy disperse dye (a2) and the blue disperse dye (b2) as main components as a dye, and in addition, a blue disperse dye (c2) described later In any case, when the total amount of each dye is 100 parts by mass, the blue disperse dye (b2) is contained in a proportion of 5 to 15 parts by mass.
(III-3) Blue disperse dye (c2)
The blue disperse dye (c2) contained as necessary in the composition of the present invention shows the absorbance of the dyed surface of the dyed molded article when the polylactic acid molded article is dyed with the dye (c2) alone. It is a blue disperse dye having a maximum absorption between 550 nm and 660 nm, preferably between 560 nm and 630 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve. The blue disperse dye (c2) used in the composition of the present invention is preferably also a disperse dye having dyeability with respect to a conventional polyester by itself.
As such a blue disperse dye, any disperse dye corresponding to the specific color index (CI) in the blue disperse dye (c1) used in the black dye composition of the present invention can be suitably used. The example of the trade name of the blue disperse dye corresponding to the CI is the same as the example of the blue dye (c1). The blue disperse dye (c2) may be a disperse dye having the same color index as that of the blue-based disperse dye constituting the main navy disperse dye (a2), as in the case of the black dye composition.
As the blue disperse dye (c2) used in the present invention, any one of disperse dyes corresponding to the color index as described above or a combination thereof may be used. When the above disperse dyes are used in combination, the mixing ratio is not particularly limited.
When the blue disperse dye (c2) is contained, the total amount of the main navy disperse dye (a2), the blue disperse dye (b2), and the blue disperse dye (c2) is 100 parts by mass. Blue disperse dye (c2) is contained in a proportion of 5 to 20 parts by mass.
The blue disperse dye (c2) functions as a component for achieving color correction capable of giving a color depth, similar to the blue disperse dye (b2) described above. Therefore, when the polylactic acid molded product is dyed using a dye composition containing the blue disperse dye (c2) in addition to the main navy disperse dye (a2) and the blue disperse dye (b2), the dyed molded product is It has a deep navy color without being reddish. The composition containing such a main navy disperse dye (a2), a blue disperse dye (b2), and a blue disperse dye (c2) also has good dyeability on the polylactic acid molded article.
(III-4) Other ingredients
As described above, the navy dye composition of the present invention contains a dispersant, various auxiliary agents, and the like as necessary. Among these, the dispersant is contained for the purpose of stabilizing the concentration and hue of the dye component and maintaining the stability of the disperse dye during dyeing. Such a dispersing agent is preferably an anionic dispersing agent, and examples of the dispersing agent include natural polymers such as sodium salt of naphthalenesulfonic acid condensate and sodium lignin sulfonate. In particular, a sodium salt of a naphthalenesulfonic acid condensate is preferable because of less coloring over time and a better dye dispersion effect.
When the anionic dispersant is contained in the navy dye composition of the present invention, the content thereof is contained in the main navy disperse dye (a2), the blue disperse dye (b1), and if necessary. Preferably they are 5 mass parts-15 mass parts with respect to a total of 100 mass parts of blue disperse dye (c1), More preferably, they are 5 mass parts-10 mass parts. By adding an anionic dispersant within the above range, the navy dye composition of the present invention has good reproducibility of dyeing density and hue, and can reduce the risk of spec dyeing and contamination of the dyeing machine itself. it can.
Auxiliaries that can be included in the navy dye composition include bulking agents, pH adjusters, dispersion leveling agents, dyeing aids, and penetrants (such as sodium dodecylbenzenesulfonate). The content of these auxiliaries is not particularly limited, and can be appropriately set according to the purpose.
(III-5) Navy dye composition
As described above, the navy color dye composition of the present invention contains the main navy disperse dye (a2) and the blue disperse dye (b2), and the blue disperse dye (c2), the dispersant, and the auxiliary agent as necessary. contains.
In the navy dye composition (for dyeing a polylactic acid molded article) of the present invention, the order of mixing the components in the production is not particularly limited as long as the components described above are contained in a predetermined ratio. For example, the following method (i ′) or (ii ′) may be employed.
(I ′) The main navy dye (a2) is prepared alone in advance, and then the blue disperse dye (b2), and optionally the blue disperse dye (c2), the dispersant, and the auxiliary agent, Produced by mixing simultaneously or in several batches;
(Ii ′) Without preparing the main navy disperse dye (a2) in advance, the disperse dyes of each color constituting the main navy disperse dye (a2) (that is, a blue-based disperse dye, and optionally used) A yellow-based disperse dye and / or a red-based disperse dye), a blue disperse dye (b2), a blue disperse dye (c2) used as necessary, the above-described dispersant, auxiliary agent, Or it is manufactured by mixing in multiple times.
Furthermore, when the disperse dye (for example, the same kind of dye) corresponding to the same color index is used for the blue-based disperse dye and the blue disperse dye (c2) of the main navy disperse dye (a2), In addition to the method (i ′) or (ii ′), the following method (iii ′) can be employed.
(Iii ′) Blue disperse dye corresponding to the same color index, dye other than the blue disperse dye among the color disperse dyes constituting the main navy dye (a2) (that is, a yellow-based disperse dye used as necessary) And / or a red-based disperse dye), and a blue disperse dye (b2), and further, if necessary, the above-mentioned dispersant, auxiliary agent, and the like are mixed at the same time or divided into a plurality of times.
(IV) Dyeing of polylactic acid moldings using black or navy dye compositions
Using the black dye composition or the navy dye composition of the present invention, for example, a polylactic acid molded article can be dyed by a method generally used in the art. The dyeing method is not particularly limited, but conventional methods such as dip dyeing and printing can be employed. Alternatively, the dye composition of the present invention employs a dip dyeing method or a printing method as described below, thereby preventing embrittlement of the polylactic acid molded body itself and polylactic acid molding dyed at an excellent dyeing rate. The body can be manufactured.
(IV-1) Dyeing by dip dyeing method
A normal dip dyeing process is employed for dyeing the polylactic acid molded article by the dip dyeing method. However, following this dip dyeing process, for example, by adopting the following specific cleaning process, it is possible to suitably dye the polylactic acid molded article, and a method including such a series of processes is used. Thereby, the dyeing property to a polylactic acid molded object further improves.
In order to perform dyeing by this method, for example, a dye dispersant and a pH adjuster are first diluted and dissolved in a dyeing bath prepared so that the bath ratio is 10: 1 to 20: 1. Apart from this, each component of the black dye composition or the navy dye composition of the present invention is added to a solvent and sufficiently dispersed. This is added to a dyeing bath containing the dye dispersant and the pH adjuster and stirred uniformly to obtain a dye solution. Next, an undyed polylactic acid molded body is immersed in this. Regarding the dyeing conditions, considering the dyeability according to the type of the polylactic acid molded article and further suppressing the change in physical properties after dyeing, conditions such as dyeing temperature, dyeing time, and pH of the dyeing bath Is preferably selected in advance. The dyeing temperature is, for example, 70 ° C to 120 ° C, preferably 90 ° C to 110 ° C. The dyeing time is, for example, 10 minutes to 60 minutes, preferably 10 minutes to 30 minutes after the bath temperature reaches the target temperature. The pH of the dyeing bath is preferably set between 4 and 8, more preferably between 4 and 6.
Next, the dye solution is removed from the bath (that is, the remaining disperse dye is removed) while leaving the polylactic acid molded body, and then water is newly added to the bath. The amount of water to be added is not particularly limited and can be appropriately selected by those skilled in the art. In this method, at this stage, the bath does not contain an auxiliary agent such as caustic soda and / or hydrosulfite used for dyeing with ordinary disperse dyes (for example, dyeing of polyester fibers). This is very important.
Thereafter, the bath is heated, and when the temperature in the bath reaches 50 ° C. to 70 ° C., as described later, a reducing auxiliary agent and a reducing main agent are added to the bath, and reduction cleaning is performed.
The heating can be performed using heating means known to those skilled in the art. Further, the bath is preferably provided with a thermometer that can monitor the temperature in the bath periodically. After the start of heating of the bath, the temperature in the bath is monitored, and when the temperature reaches 50 ° C. to 70 ° C., preferably 60 ° C. to 65 ° C., and more preferably 60 ° C. to 62 ° C., Are respectively input. The reducing aid used in this method is preferably soda ash, and the reducing agent is preferably hydrosulfite. The soda ash that can be used in this process is less alkaline than the caustic soda and preferably exhibits a pH of 9 to 11.5 in the bath. The amount of soda ash that can be added is preferably 0.5 g / L to 3 g / L based on the total amount of the cleaning liquid present in the bath (the amount of water added above). On the other hand, the amount of hydrosulfite that can be added is preferably 1 g / L to 3 g / L based on the total amount of the cleaning solution in the bath.
In this method, it is preferable that the reducing aid and the reducing agent are added together in the bath. Or when adding separately, it is preferable that a reducing adjuvant is added previously and a reducing main agent is added after that.
After the addition of both the reducing aid and the reducing agent is completed, the polylactic acid molded body is taken out from the bath after a predetermined time has elapsed. Preferably, the polylactic acid molded article is taken out from the bath after 5 to 20 minutes have elapsed after the addition of both the reducing aid and the reducing main agent is completed. This is because if the polylactic acid molded body is left in the bath for an extremely long time, the polylactic acid molded body may be gradually eroded by the above-mentioned reducing aid.
The removed polylactic acid molded article is washed and dried using means known to those skilled in the art.
Conventionally, the reduction cleaning performed immediately after dyeing a molded body such as a fiber with a disperse dye is originally performed to increase the fastness of the dyed surface of the molded body. That is, when the disperse dye is brought into contact with the disperse dye, the disperse dye remaining on the surface of the molded body is decomposed with the reducing main agent in the presence of the reducing auxiliary agent, thereby improving the fastness of the surface of the molded body. However, polylactic acid (PLA), which is a main component of the polylactic acid molded product used in the present invention, is a biodegradable substance in the first place and has a property that it is easily eroded by alkali and the like. Therefore, as in the case of dyeing conventional polyester fibers, it is necessary to add a strong alkali such as caustic soda as a reducing aid and then perform heating for reduction cleaning to raise the temperature to a predetermined temperature by the heating. By a certain amount of time, the polylactic acid itself may be eroded. In addition, the use of caustic soda may also reduce the dispersibility of the disperse dye on the polylactic acid molded article, and the disperse dye once dyed by washing exudes from the polylactic acid molded article to contaminate the cleaning liquid itself. Problems can also arise. The contaminated cleaning liquid may further contaminate the polylactic acid molded body being cleaned, and may cause environmental pollution during drainage.
In the above-described method, the relationship between the type of the reducing auxiliary agent added to the bath and the temperature in the bath when the reducing auxiliary agent and the reducing main agent are added is appropriately adjusted. Therefore, the erosion of polylactic acid is minimized, only the remaining disperse dye is efficiently decomposed, and contamination to the cleaning liquid is prevented.
Thus, the polylactic acid molded object dye | stained by the dip dyeing method using the dye composition of this invention is obtained. When the above method is employed, the reductive decomposition of the disperse dye is sufficiently performed, the embrittlement of the polylactic acid molded body itself is prevented, and an effectively dyed polylactic acid molded body can be produced.
(IV-2) Dyeing by printing method
In the case of dyeing by a printing method using the dye composition of the present invention, for example, the composition is applied to the surface of a polylactic acid molded body by printing, or the composition is coated by a method other than printing. A method of applying to the surface of the lactic acid molded body is adopted.
In the former method of applying the dye composition of the present invention by printing, the dye composition of the present invention is usually mixed with a paste and processed into a color paste form. This color paste further contains a non-volatile acid, a dye reduction inhibitor, a deep dyeing agent, and the like as necessary. Specifically, the color paste is added to the paste for printing, each dye contained in the composition of the present invention, and if necessary, the non-volatile acid, the dye reduction inhibitor, the deep dye, and the addition. An agent or the like can be added and dispersed.
Examples of the paste used for the preparation of the above color paste include sodium alginate, locust bean gum, shiratsu gum, starch, modified starch, carboxymethylcellulose (CMC), Maypro gum, guar gum, British gum, tamarind gum, water-soluble Acrylic copolymers, galactomannans, polysaccharides and the like can be mentioned. Such pastes can be used alone or in combination at any ratio. Although the content of the paste in the color paste is not particularly limited, it is, for example, 2% by mass to 10% by mass based on the total amount of the color paste.
The non-volatile acid is contained for the purpose of preventing the disperse dye from being decomposed. Examples of such non-volatile acids include malic acid, tartaric acid, citric acid or combinations thereof, and are preferably contained in the color paste so as to exhibit weak acidity, more preferably pH 4-6.
Examples of the dye reduction inhibitor include sodium chlorate and potassium iodate. Examples of the deep dyeing agent include ethylene oxide blends (mixtures containing ethylene oxide as a main component), weak cationic activators, polyalkylene polyol blends, polyhydric alcohol ester activators, and the like. These contents are not particularly limited, and may be amounts generally employed in the field.
The color paste prepared as described above is applied to any location on the polylactic acid molded body. The application of the color paste may be performed continuously or intermittently. When the printing is continuously performed, means such as a roller printing machine, an automatic screen printing machine, and a rotary printing machine are used. When printing is performed intermittently or locally, means such as a hand-type screen printing machine and a semi-automatic screen printing machine are used.
As a method for applying the dye composition of the present invention to the surface of the polylactic acid molded body by a method other than the latter printing, the composition of the present invention is used as a dyeing liquid containing no paste, and this is directly applied to the polylactic acid by an ink jet method. A method of coating on a molded article; a method of directly applying a dyeing liquid not containing the paste onto the polylactic acid molded article by transfer printing; and an electrostatic electrophotographic method using the dyeing liquid not containing the glue as a dye toner Can be applied directly onto the polylactic acid molded article.
The polylactic acid molded article to which the dye composition of the present invention is applied by any one of the above methods is dried as necessary, and dyeing is performed by heating as described later. Although the said drying conditions are not specifically limited, For example, it is performed for 2 minutes-5 minutes at the temperature of 70 to 100 degreeC. This drying condition does not impair the physical properties of the polylactic acid molded body itself depending on various conditions such as the form of the polylactic acid molded body to be used, the amount of color paste or dye solution applied, the location of the dryer at the production site, and the production efficiency. The range can be freely changed as appropriate.
Dyeing of the dye onto the polylactic acid molded body is performed by applying a predetermined temperature under normal pressure and superheated steam atmosphere.
The dyeing step is preferably performed under either an open system high temperature normal pressure (a so-called HT steam (high temperature steam) condition or a closed system high pressure (a so-called high pressure steam) condition. It is preferable to carry out under the condition of HT steam because the production efficiency can be increased.When it is carried out under the condition of HT steam, the other dyeing condition is that the conventional polyester fiber is subjected to HT steam. Although the conditions for printing may be used, it is preferable to adopt the conditions described below from the viewpoint of improving productivity.
For example, when printing is carried out under the conditions of HT steam, the dye is contained in a housing (for example, a continuous superheated steamer) that is maintained at normal pressure (for example, in an open system) and is in a superheated steam atmosphere. Dyeing is achieved by exposing the applied polylactic acid molded body to a temperature of 105 ° C to 140 ° C, preferably 110 ° C to 140 ° C, more preferably 120 ° C to 130 ° C. Here, when the exposed temperature is lower than 105 ° C., the disperse dye cannot be sufficiently dyed on the polylactic acid molded article, and the color developability may be deteriorated. On the other hand, when the exposed temperature exceeds 140 ° C., the polylactic acid itself, which is the main component of the molded body, may be cured. Further, when a high temperature is used, not only polylactic acid itself is melted but also the disperse dye used is vaporized and diffused and diffused into the housing, which may cause problems such as in-machine contamination.
In the superheated steam atmosphere used in the above dyeing process, it is preferably managed at a wet bulb temperature of 90 ° C. to 100 ° C. in a housing (for example, a continuous superheated steamer) preferably heated to 105 ° C. to 210 ° C. Humidity conditions, more preferably humidity conditions managed at a wet bulb temperature of 95 ° C to 100 ° C are employed. Moreover, the temperature of the pressurized steam supplied into the housing to achieve this superheated steam atmosphere is preferably 105 ° C to 140 ° C, more preferably 125 ° C to 135 ° C.
In the printing under HT steam used for the conventional polyester fiber, the inside of the housing is usually adjusted to a temperature of 170 ° C. to 180 ° C. Rather, the disperse dye used can be sufficiently vaporized at a temperature lower than 170 ° C. Therefore, it is known that a satisfactory printed matter cannot be obtained. On the other hand, in the above method, the disperse dye is dyed on the polylactic acid molded article by a completely different mechanism without intentionally causing such vaporized diffusion of the disperse dye. More specifically, the relatively mild temperature condition used in the present invention prevents damage to the polylactic acid molded body itself, while the disperse dye applied on the polylactic acid molded body is polylactic acid by contact diffusion. It is thought to be dyed on the molded body. Furthermore, since this dyeing process is preferably performed in a superheated steam atmosphere below 170 ° C., which is the lowest temperature that has been used in printing under conventional HT steam, More water is present as compared with the printing conditions under HT steam used for conventional polyester fibers. For this reason, it is considered that not only the contact diffusion but also a part of the disperse dye is dissolved in this moisture, and both of them function synergistically through the dissolution and diffusion to dye the polylactic acid molded product.
Furthermore, in the above method, by adjusting the time in the dyeing process, the texture of the printed matter to be obtained (for example, appropriate flexibility and toughness inherent in polylactic acid) can be maintained and weakened. Curing due to (for example, strength deterioration) or excessive shrinkage can be prevented. The time for performing the dyeing step is preferably 4 minutes to 20 minutes, more preferably 4 minutes to 8 minutes.
In the said method, it is preferable to perform the said dyeing | staining process on the conditions in which the polylactic acid molded object is settled in the shrinkage within a certain range. In the present invention, based on the polylactic acid molded product before the dyeing process, the shrinkage rate of the obtained polylactic acid printed product is preferably 10% or less, more preferably 8% or less. Done. By performing the above-mentioned dyeing process within the range of such shrinkage rate, the obtained polylactic acid printed matter can avoid the possibility of problems such as weakening (for example, deterioration in strength) or curing itself. .
After the dyeing step, the dyed polylactic acid molded product is then washed with water as necessary, and the color paste or dye solution remaining on the molded product is removed. Further, this molded body is subjected to reduction cleaning with a solution containing a reducing agent and a reduction auxiliary agent, whereby unfixed disperse dyes adhering to the surface of the printed material are decomposed and removed. Examples of the reducing agent used for such reduction cleaning include hydrosulfite, and for example, the reducing agent can be prepared to a concentration of 1 g / L to 3 g / L. Moreover, as an example of the reducing auxiliary agent used for such reductive cleaning, alkali (a more specific example is soda ash) can be mentioned, for example, adjusted to a concentration of 0.5 g / L to 3 g / L. Can be used. The solution used for the reduction cleaning may contain any proportion of a nonionic surfactant for the purpose of improving the cleaning effect. Although the said reduction | restoration washing | cleaning is not specifically limited, For example, it is performed over 10 minutes-20 minutes under the temperature of 50 to 70 degreeC.
After the reduction cleaning, the dyed polylactic acid molded body is further washed with water as necessary to remove the dye degradation product, the residual reducing agent and the residual reducing auxiliary agent remaining on the molded body. Thereafter, drying may be performed.
(IV-3) Dyeing compact
A polylactic acid molded article dyed with the black or navy dye composition of the present invention can be obtained by a method such as dip dyeing or printing. As described later, the black or navy color obtained by dyeing is a color close to the color when the polyester molded body is dyed with the main black disperse dye (a1) or the main navy disperse dye (a2) contained in the composition. It becomes.
Both the main black disperse dye (a1) and the main navy disperse dye (a2) are preferably disperse dyes conventionally used for dyeing polyester fibers. When a polylactic acid molded product is dyed alone, the absorption wavelength of the dyed surface of the dyed molded product is usually about 10 nm as compared with that obtained by dyeing polyester fibers under the same conditions. It can shift to the short wavelength side in the range of ˜15 nm. Thereby, even if it is going to obtain the dyeing | staining which shows the color of the black or navy color similar to the conventional polyester molded object, the reddish black or navy color lacking in the color depth is exhibited. Furthermore, depending on the difference in the artificial light source, the defect is remarkably enlarged (that is, it has color rendering properties). On the other hand, the blue disperse dye (b1) and the blue disperse dye (c1) function as a dye component (correction dye component) capable of achieving color correction with respect to the main black disperse dye (a1). Similarly, the blue disperse dye (b2) and the blue disperse dye (c2) function as a dye component (correction dye component) capable of achieving color correction with respect to the main navy disperse dye (a2). Therefore, the shift on the short wavelength side as described above can be substantially prevented, and the same color as that obtained by dyeing a conventional polyester molded product can be exhibited.
As a result, the polylactic acid molded article dyed with the dye composition of the present invention has a light reflectance particularly in a wavelength region (about 650 nm to about 700 nm) that can affect redness on the dyed surface of the molded article. Reduced. The degree of such redness reduction can be easily determined by those skilled in the art by visual observation under different light sources. Alternatively, the difference in color (color rendering) at this time can be quantified by optically measuring the reflected light of the dyed object and using a certain calculation formula. That is, CIE Lab. This can be achieved by calculating the H (hue) value of the value. The H value (angle 0 to 360 degrees) starts from red 0 (= 360) and returns to red 360 (= 0) with orange 45, lemon yellow 90, green 180, blue-green 225, turkis 270, and violet 315. It is a value obtained by quantifying the hue. The degree of redness can be confirmed from such an H value.
The polylactic acid molded article dyed with the dye composition of the present invention also has improved color rendering under different light sources, and the color rendering is close to the dyed polyester molded article. This degree of color rendering can be easily determined by those skilled in the art by visual observation under different light sources. Alternatively, the reflected light of the dyed surface of the molded body is measured, and each CIE Lab. The color rendering property is determined by calculating the value and comparing the magnitudes. For example, in the black dye composition, the degree of such color rendering is improved when the polylactic acid molded body is dyed with the main black disperse dye (a1) alone, compared with the black dye composition (main black Color rendering properties by comparing values when a polylactic acid molded product is dyed using a disperse dye (a1), a blue disperse dye (b1), and a composition containing a blue disperse dye (c1) as necessary The degree of improvement can be confirmed. In the case of the navy dye composition of the present invention, the effect of improving the color rendering property can be confirmed by the same method.
As described above, according to the present invention, it is possible to provide a dyed polylactic acid molded product having a color similar to that of a general-purpose black or navy dyed polyester molded product. This dyed polylactic acid molded product can maintain the same product color depth even under different light sources used in various fields such as production, display and sales. Is expensive.

次いで、この主ブラック分散染料（ａ１．１）に対し、さらに青色分散染料（ｂ１．１）および（ｃ１．１）として、各々０．５ｇのＤＩＡＮＩＸ Ｔｕｒｑｕｉｓｅ Ｓ−ＢＧ（ダイスター社製、ＣＩディスパースブルー６０；単独でポリ乳酸成形体を染色したときに、染色表面が５５０ｎｍから７００ｎｍの波長領域のうち６４０ｎｍから７００ｎｍの間で極大吸収を有する分散染料）および１ｇのＤＩＡＮＩＸ Ｂｌｕｅ Ｓ−ＢＧ（ダイスター社製、ＣＩディスパースブルー７３；単独でポリ乳酸成形体を染色したときに、染色表面が５５０ｎｍから７００ｎｍの波長領域のうち、５５０ｎｍから６６０ｎｍの間で極大吸収を有する分散染料）、ならびに１ｇのアニオン系分散剤（商品名：Ｓｅｔａｍｏｌ ＷＳ；ＢＡＳＦ社製）を仕込み、これらが均一になるまで混合して、黒色染料（α１）を得た。
（比較例１．１）：黒色染料（α１’）の調製
実施例１．１に記載の主ブラック分散染料（ａ１．１）に対し、青色分散染料（ｂ１．１）および（ｃ１．１）を添加することなく、０．８３ｇのアニオン系分散剤（商品名：Ｓｅｔａｍｏｌ ＷＳ；ＢＡＳＦ社製）のみを仕込み、これらが均一になるまで混合したこと以外は実施例１．１と同様にして、黒色染料（α１’）を得た。
（実施例１．２）：ポリ乳酸黒色染色物（黒色ポリ乳酸成形体）（Ｓα１）の製造
実施例１．１で得られた黒色染料（ａ１．１）０．３ｇ（６％ｏ．ｗ．ｆ．に相当）を、０．１ｇの分散剤（ニッカサンソルト７０００／日華化学（株）製）および０．４ｍｌの８％酢酸とともに、室温で水に加えて分散させ、１００ｍｌの染色液を調製した。次いで、この染色液と５ｇのポリ乳酸繊維１００％のスパン糸（５デニール）とを、３００ｍｌのポット容量を有するポット型高圧染色機（テクサム社製「ミニカラー」）に仕込み、高温高圧下での浸染染色を行った。染色条件は以下の通りであった：室温から１１０℃まで２℃／分の割合で昇温、さらに１１０℃で３０分染色を継続し、その後、５℃／分の割合で７０℃まで冷却；水洗の後、１．５ｇ／Ｌソーダ灰、２ｇ／Ｌハイドロサルハイト、１ｇ／Ｌリポトール ＰＥ（日華化学社製）の溶液を用い、６０℃、１０分の還元洗浄を行い、水洗の後室温で乾燥しさせた。この操作により、６．０％ ｏ．ｗ．ｆに相当するポリ乳酸成形体の染色物（Ｓα１）を得た。得られた染色物（Ｓα１）について、上記（１）〜（４）のそれぞれの評価を行った。
（１）の染色されたポリ乳酸繊維の明度、彩度、および色相の評価については、Ｄ６５光源下でのＬ値、Ｃ値、およびＨ値を表１．２に、Ａ光源下での該各値を表１．３に示す。（２）の目視による演色性の評価の結果を表１．４に示し、（３）の機器測定による演色性の評価の結果を表１．５に示す。（４）の反射率の測定結果については、測定波長と光学反射率との関係を図１に示す。後述の比較例１．２の結果についても同様に上記の表および図に示す。
（比較例１．２）：ポリ乳酸黒色染色物（Ｓα１’）の製造
実施例１．１で得られた黒色染料（α１）の代わりに、比較例１．１で得られた黒色染料（α１’）０．３ｇを用いたこと以外は、実施例２．１と同様に操作してポリ乳酸成形体の染色物（Ｓα１’）を得た。得られた染色物（Ｓα１’）について、上記（１）〜（４）のそれぞれの評価を行った。
（比較例１．３）：ポリエステル黒色染色物（Ｆα２）の製造
実施例１．１で得られた黒色染料組成物（α１）の代わりに、従来、その染色物が若干赤味を帯びた黒色を呈すると言われ、かつ市場にて広く普及しているポリエステル用黒色分散染料ＤＩＡＮＩＸ Ｂｌａｃｋ ＣＣ−Ｒ（α２）を０．１３ｇ用いて染色液を調製し、ポリ乳酸繊維１００％のスパン糸（５デニール）の代わりに、５ｇのポリエステルダブルピケ フィラメント加工糸（１５０デニール／３０フィラメント）を用いて、実施例１．２に準じて染色を行い、ポリエステル成形体の染色物（Ｆα２）を得た。染色の温度条件は、室温から１３０℃まで２℃／分の割合で昇温し、さらに１３０℃で３０分間の染色を継続する条件を採用した。得られた染色物（Ｆα２）について、上記（４）の評価を行った。得られた光学反射率のスペクトルを図１に示す。得られた染色物（Ｆα２）を、Ｄ６５光源の標準光照射下にて目視観察したところ、わずかに赤味を帯びた黒色を呈していた。
（比較例１．４）：ポリエステル黒色染色物（Ｆα３）の製造
実施例１．１で得られた黒色染料組成物（α１）の代わりに、従来、その染色物が若干緑味を帯びた黒色を呈すると言われ、かつ市場にて広く普及しているポリエステル用黒色分散染料ＤＩＡＮＩＸ Ｂｌａｃｋ ＣＣ−Ｇを０．１３ｇ用いて染色液を調製し、かつポリ乳酸繊維１００％のスパン糸（５デニール）の代わりに、５ｇのポリエステルダブルピケ フィラメント加工糸（１５０デニール／３０フィラメント）を用いて、実施例１．２に準じて染色を行い、ポリエステル成形体の染色物（Ｆα３）を得た。染色の温度条件は、室温から１３０℃まで２℃／分の割合で昇温、さらに１３０℃で３０分間の染色を継続する条件を採用した。得られた染色物（Ｆα３）について、上記（４）の評価を行った。得られた光学反射率のスペクトルを図１に示す。得られた染色物（Ｆα３）を、Ｄ６５光源の標準光照射下にて目視観察したところ、わずかに緑味を帯びた黒色を呈していた。
（比較例１．５）：ポリエステル黒色染色物（Ｆα４）の製造＞
実施例１．１で得られた黒色染料組成物（α１）の代わりに、従来、その染色物が若干緑味を帯びた黒色を呈すると言われる一方で、その色が消費者にも許容され得る黒色であるため市場にて広く普及しているポリエステル用黒色分散染料ＤＩＡＮＩＸ Ｂｌａｃｋ ＣＣ−３Ｇを０．１３ｇ用いて染色液を調製し、かつポリ乳酸繊維１００％のスパン糸（５デニール）の代わりに、５ｇのポリエステルダブルピケ フィラメント加工糸（１５０デニール／３０フィラメント）を用いて、実施例１．２に準じて染色を行い、ポリエステル成形体の染色物（Ｆα４）を得た。染色の温度条件は、室温から１３０℃まで２℃／分の割合で昇温、さらに１３０℃で３０分間の染色を継続する条件を採用した。得られた染色物（Ｆα４）について、上記（４）の評価を行った。得られた光学反射率のスペクトルを図１に示す。得られた染色物（Ｆα４）を、Ｄ６５光源の標準光照射下にて目視観察したところ、緑味を帯びた黒色を呈していた。

表１．２に示されるように、本発明による黒色染料（実施例１．１）を用いて得られた染色物（Ｓα１）および主ブラック分散染料のみ（比較例１．１）を用いて得られた染色物（Ｓα１’）のいずれもが、太陽光に近いＤ６５光源の標準光の下では、２０以下のＬ値、５以下のＣ値を達成しており、良好な黒色を呈していることがわかる。しかし、表１．２におけるＨ値を比較した場合、染色物（Ｓα１）のＨ値（７４．７１）は黄味領域に属するのに対し、染色物（Ｓα１’）のＨ値（５０．９８）はオレンジ味領域に属していたことがわかる。このことから、黒色染料（ａ１．１）に加えて青色分散染料（ｂ１．１）および（ｃ１．１）が含有される実施例１．１の黒色染料（α１）を用いた場合には、該青色分散染料（ｂ１．１）および（ｃ１．１）が、Ｄ６５光源の照射下において、染色物の黒色が赤味を帯びる程度を低減させることがわかる。
表１．３に示されるように、本発明による黒色染料（実施例１．１）を用いて得られた染色物（Ｓα１）は、人工光の一つであるＡ光源の照射下では、染色物（Ｓα１）のＬ値は１６．９４であり、Ｃ値は３．７０であることから、当該染色物の彩度は充分に低く、良好な黒色を呈していることがわかる。これに対して、主ブラック分散染料のみ（比較例１．１）を用いて得られた染色物（Ｓα１’）については、Ｌ値は１７．７０であり、Ｃ値は８．４９である。従って、比較例１．１では、得られた染色物の色は、一応黒色としての基準は満たしているが、彩度が高い。さらに、特にＨ値が３３．４６と赤味領域にあることを合わせて考えると、かなり赤味を帯びた黒色を呈していることがわかる。このことから、黒色染料（ａ１．１）に加えて青色分散染料（ｂ１．１）および（ｃ１．１）が含有される実施例１．１の黒色染料（α１）を用いた場合には、該青色分散染料（ｂ１．１）および（ｃ１．１）が、Ａ光源下において、染色物の黒色が赤味を帯びる程度を低減させることがわかる。
さらに、表１．４に示されるように、本発明による黒色染料（実施例１．１）を用いて得られた染色物（Ｓα１）と、主ブラック分散染料のみ（比較例１．１）を用いて得られた染色物（Ｓα１’）とは、人の視覚においても充分差異を認識し得るものであることがわかる。
表１．５に示されるように、異なる光源下での演色性を比較すると、本発明による黒色染料（実施例１．１）を用いて得られた染色物（Ｓα１）は、主ブラック分散染料のみ（比較例１．１）を用いて得られた染色物（Ｓα１’）と比較して、演色性が良好に改善されていることがわかる。特に、染色物（Ｓα１）は、欧州のスーパーマーケットで標準光源として多用されるＴＬ８４光源の下でも演色性が極めて低いことがわかる。
一方、図１に示されるように、本発明による黒色染料（実施例１．１）を用いて得られた染色物（Ｓα１）および各比較例の染色物のいずれにおいても、４００ｎｍ〜７５０ｎｍの波長領域のうち４００ｎｍ〜６００ｎｍにおける光学反射率は低い状態のまま一定している。しかし、赤色に対応する約６００ｎｍ〜約７００ｎｍの間の波長に対応する光学反射率については、染色物（Ｓα１）は、主ブラック分散染料のみ（比較例１．１）を用いて得られた染色物（Ｓα１’）の染色物と比較して、従来のポリエステル用黒色分散染料でポリエステルフィラメント加工糸を染色した比較例１．３〜１．５の染色物（Ｆα２、Ｆα３およびＦα４）により近似した曲線を示していることがわかる。このことから、本発明による黒色染料は、より赤味の低減させた黒色を呈する染色物を提供し得ることがわかる。特に、比較例１．３〜１．５で得られた染色物（Ｆα２、Ｆα３およびＦα４）の色は、それらの間では、上述のように、わずかに赤味を帯びた黒色から緑味を帯びた黒色までの黒色バリエーションとして目視観察された。この目視観察の結果を考慮すれば、これらの色の間には、目視的な差異は存在するが、いずれも従来より市販された場合に黒色として消費者に好まれる範囲の代表的な黒色のバリエーションである。しかし、図１に示される光学反射曲線の差異はほとんどなく、非常に近似した光学反射率を示していることがわかる。
ここで、実施例１．２および比較例１．２を各々比較例１．３〜１．５の光学反射率曲線と比較すれば、比較例１．２と比較例１．３〜１．５との差に対し、実施例１．２と比較例１．３〜１．５との差（特に赤色の有無または強弱を視覚的に感じると言われる約６００ｎｍ〜約７００ｎｍの間の差異）は、かなり低減されていることがわかる。このことからも、本発明による黒色染料を用いてポリ乳酸を染色した場合には、得られる染色物が帯びる赤色が極めて低減し、かつ従来から消費者に特に好まれている黒色に染色されたポリエステルにより近似した黒色が得られることがわかる。
（実施例２．１）：ネイビー色染料（β１）の調製
容器中に、表２．１に記載のベース分散染料を仕込み、これらが均一になるまで混合して、主ネイビー分散染料（ａ２．１）を調製した。

次いで、この主ネイビー分散染料（ａ２．１）に対し、さらに青色分散染料（ｂ２．１）および（ｃ２．１）として、各々０．４ｇのＤＩＡＮＩＸ Ｔｕｒｑｕｉｓｅ Ｓ−ＢＧ（ダイスター社製，ＣＩディスパースブルー６０；単独でポリ乳酸成形体を染色したときに、染色表面が５５０ｎｍから７００ｎｍの波長領域のうち６４０ｎｍから７００ｎｍの間で極大吸収を有する分散染料）および０．７ｇのＤＩＡＮＩＸ Ｂｌｕｅ Ｓ−ＢＧ（ダイスター社製，ＣＩディスパースブルー７３；単独でポリ乳酸成形体を染色したときに、染色表面が５５０ｎｍから７００ｎｍの波長領域のうち、５５０ｎｍから６６０ｎｍの間で極大吸収を有する分散染料）、ならびに１．１ｇのアニオン系分散剤（商品名：Ｓｅｔａｍｏｌ ＷＳ；ＢＡＳＦ社製）を仕込み、これらが均一になるまで混合して、ネイビー色染料（β１）を得た。
（比較例２．１）：ネイビー色染料（β１）の調製
実施例３に記載の主ネイビー分散染料（ａ２．１）に対し、青色分散染料（ｂ２．１）および（ｃ２．１）を添加することなく、０．９６ｇのアニオン系分散剤（商品名：Ｓｅｔａｍｏｌ ＷＳ；ＢＡＳＦ社製）のみを仕込み、これらが均一になるまで混合したこと以外は実施例２．１と同様にして、ネイビー色染料（β１’）を得た。
（実施例２．２）：ポリ乳酸ネイビー色染色物（Ｓβ１）の製造
実施例２．１で得られたネイビー色染料（β１）０．２ｇ（４％ｏ．ｗ．ｆ．に相当）を、０．１ｇの分散剤（ニッカサンソルト７０００／日華化学（株）製）および０．４ｍｌの８％酢酸とともに、室温で水に加えて分散させ、１００ｍｌの染色液を調製した。次いで、この染色液と５ｇのポリ乳酸繊維１００％のスパン糸（５デニール）とを、３００ｍｌのポット容量を有するポット型高圧染色機（テクサム社製「ミニカラー」）に仕込み、高温高圧下での浸染染色を行った。染色条件は以下の通りであった：室温から１１０℃まで２℃／分の割合で昇温、さらに１１０℃で３０分染色を継続し、その後、５℃／分の割合で７０℃まで冷却；水洗の後、１．５ｇ／Ｌソーダ灰、２ｇ／Ｌハイドロサルハイト、１ｇ／Ｌリポトール ＰＥ（日華化学社製）の溶液を用い、６０℃、１０分の還元洗浄を行い、水洗の後室温で乾燥しさせた。この操作により、４．０％ ｏ．ｗ．ｆに相当するポリ乳酸成形体の染色物（Ｓβ１）を得た。得られた染色物（Ｓβ１）について、上記（１）〜（４）のそれぞれの評価を行った。
（１）の染色ポリ乳酸繊維の明度、彩度、および色相の評価については、Ｄ６５光源の標準光の下でのＬ値、Ｃ値、およびＨ値を表２．２に、Ａ光源の標準光の下での該各値を表２．３に示す。（２）の目視による演色性の評価の結果を表２．４に示し、（３）の機器測定による演色性の評価の結果を表２．５に示す。（４）の反射率の測定結果については、測定波長と光学反射率との関係を図２に示す。後述の比較例２．２の結果についても同様に上記の表および図に示す。
（比較例２．２）：ポリ乳酸ネイビー色染色物（Ｓβ１’）の製造
実施例２．１で得られたネイビー色染料（β１）の代わりに、比較例２．１で得られたネイビー色染料（β１’）を０．２ｇ用いたこと以外は、実施例２．２と同様にしてポリ乳酸成形体の染色物（Ｓβ１’）を得た。得られた染色物（Ｓβ１’）について、上記（１）〜（４）のそれぞれの評価を行った。
（比較例２．３）：ポリエステルネイビー色染色物（Ｆβ２）の製造＞
実施例３で得られたネイビー色染料（β１）の代わりに、従来、その染色物が若干緑味を帯びたネイビー色を呈する一方で市販的に許容されている、ポリエステル用ネイビー色分散染料ＤＩＡＮＩＸ Ｎａｖｙ Ｓ−Ｇ ２００％を０．０９ｇを用いて染色液を調製し、かつポリ乳酸繊維１００％のスパン糸（５デニール）の代わりに、５ｇのポリエステルダブルピケ フィラメント加工糸（１５０デニール／３０フィラメント）を用い、実施例２．２に準じて染色を行い、ポリエステル成形体の染色物（Ｆβ２）を得た。染色の温度条件は、室温から１３０℃まで２℃／分の割合で昇温、さらに１３０℃で３０分間の染色を継続する条件を採用した。得られた染色物（Ｆβ２）について、上記（４）の評価を行った。得られた光学反射率のスペクトルを図２に示す。

表２．２に示されるように、本発明によるネイビー色染料（実施例２．１）を用いて得られた染色物（Ｓβ１）と主ネイビー分散染料のみ（比較例２．１）を用いて得られた染色物（Ｓβ２）とを比較すると、染色物（Ｓβ１）の方が、太陽光に近いＤ６５光源の標準光の下におけるＬ値およびＣ値のいずれもが高い。このことから染色物（Ｓβ１）の方が高い濃度を有し、充分な彩度を有していることがわかる。これに対し、比較例２．２の染色物（Ｓβ１’）では、Ｌ値が高いものの、Ｃ値が低く、くすみ過ぎていることがわかる。一方、Ｈ値（色相）は、染色物（Ｓβ１）と（Ｓβ１’）との間ではほとんど差異が見られていない。以上の結果から、主ネイビー分散染料のみ（比較例２．１）を用いて得られた染色物（Ｓβ１’）は、Ｄ６５光源の標準光の下では、やや赤味でくすんだネイビー色を呈するといえる一方で、本発明によるネイビー色染料（実施例２．１）を用いて得られた染色物（Ｓβ１）は、彩度が大きいためよりネイビーらしい色相を示していることがわかる。
このことから、ネイビー色染料（ａ２．１）に加えて青色分散染料（ｂ２．１）および（ｃ２．１）が含有される実施例２．１のネイビー色染料（β１）を用いた場合には、該青色分散染料（ｂ２．１）および（ｃ２．１）が、Ｄ６５光源の標準光の下において、染色物が赤味を帯びる程度を低減させることがわかる。
表２．３に示されるように、本発明によるネイビー色染料（実施例２．１）を用いて得られた染色物（Ｓβ１）および主ブラック分散染料のみ（比較例２．１）を用いて得られた染色物（Ｓβ１’）は、人工光の一つであるＡ光源の照射下では、Ｈ値に大きな差異が生じる。染色物（Ｓβ１）は染色物（Ｓβ２）と比較して、より黄青味に寄っており、本来要求されるべきよりネイビー色らしい色相を呈しているといえる。このことから、使用したネイビー色染料（ａ２．１）に加えて青色分散染料（ｂ２．１）および（ｃ２．１）が含有される実施例２．１のネイビー色染料（β１）を用いた場合には、該青色分散染料（ｂ２．１）および（ｃ２．１）が、Ａ光源下において、彩度を向上させるだけでなく、赤味を帯びる程度をより低減させていることがわかる。
さらに、表２．４に示されるように、本発明によるネイビー色染料（実施例２．１）を用いて得られた染色物（Ｓβ１）と、主ネイビー分散染料のみ（比較例２．１）を用いて得られた染色物（Ｓβ１’）とは、人の視覚においても充分差異を認識し得るものであることがわかる。
表２．５に示されるように、異なる光源下での演色性を比較すると、本発明のネイビー色染料組成物（実施例２．１）を用いて得られた染色物（Ｓβ１）は、主ネイビー分散染料のみ（比較例２．１）を用いて得られた染色物（Ｓβ１’）と比較して、演色性が良好に改善されていることがわかる。特に、染色物（Ｓβ１）は、欧州のスーパーマーケットで標準光源として多用されるＴＬ８４光源の下でも演色性が極めて低いことがわかる。
一方、図２を参照し、４００ｎｍ〜７５０ｎｍの波長領域における光学反射率のスペクトルのうち、特に、４００ｎｍ〜５００ｎｍのスペクトル、および赤色に対応する約６００ｎｍ〜約７００ｎｍの間のスペクトルについて、本発明によるネイビー色染料（実施例２．１）を用いて得られた染色物（Ｓβ１；実施例２．２）および主ネイビー分散染料のみ（比較例２．１）を用いて得られた染色物（Ｓβ１’；実施例２．２）を比較すると、染色物（Ｓβ１）の方が、従来のポリエステル用ネイビー色分散染料でポリエステルフィラメント加工糸を染色した比較例２．３の染色物（Ｆβ３）により近似した曲線を示していることがわかる。このことから、本発明によるネイビー色染料は、より赤味を低減させたネイビー色を呈する染色物を提供し得ることがわかる。Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited by these.
Below, the evaluation method used in this invention is demonstrated.
(1) Evaluation of lightness, saturation, and hue of dyed polylactic acid fiber The optical reflectance of the dyed fiber was measured twice with a COLOR-EYE 7000 manufactured by Machbeth, and the standard light of a D65 light source and tungsten CIE Lab. Under standard light of lamp (A light source). Each value (L value, C value, and H value) is obtained.
(2) Redness reduction effect and color rendering improvement effect of dyed polylactic acid fiber (evaluation of color rendering properties by visual observation)
Adopt a visual evaluation of five experts engaged in the dyeing field. This visual evaluation includes fluorescent lamp F40T12 / 65 (color temperature 6500K) manufactured by GREDAMACBETH, USA, which is said to be close to natural light, and PRS500WD (color) manufactured by Iwasaki Electric Co., Ltd. Using a temperature of 5900 K), irradiation is performed from 40 cm directly above the dyed product, and each color is evaluated by visual observation. Further, the difference in color (color rendering) by these light sources is determined.
(3) Evaluation of color rendering (evaluation of color rendering by instrument measurement)
The optical reflectance of the dyed surface of the dyed polylactic acid molded body was measured twice with a COLOR-EYE 7000 manufactured by Machbeth, and the value under the standard light irradiation of the artificial light source D65 that is said to be closest to natural sunlight. The “color rendering value” under a different light source is obtained as a standard. This “color rendering property value” is a value defined by Kurabo Industries, Inc. AUCOLOR NF2 CCM system. When there is no color rendering property, the value is 100, and the smaller the value, the greater the color rendering property. As a type of light source to be compared with D65, a tungsten light source (A light source) close to an incandescent lamp and TL84, which is frequently used as a standard light source for color judgment in European supermarkets (for example, Marks & Spencer), are adopted.
(4) Measurement of optical reflectance The optical reflectance of the dyed surface of the dyed product is measured in a wavelength region of 400 nm to 750 nm using COLOR-EYE 7000 manufactured by Machbeth.
(Example 1.1): Preparation of black dye (α1) Into a container, the base disperse dyes listed in Table 1.1 were charged and mixed until they became uniform. ) Was prepared.

Next, for this main black disperse dye (a1.1), 0.5 g of DIANIX Turquoise S-BG (manufactured by Dystar, CI Disperse) was further added as blue disperse dyes (b1.1) and (c1.1). Blue 60: Disperse dye having a maximum absorption in a wavelength range of 640 nm to 700 nm in a wavelength region of 550 nm to 700 nm when dyeing a polylactic acid molded product alone and 1 g of DIANIX Blue S-BG (Dystar) CI Disperse Blue 73; disperse dye having a maximum absorption between 550 nm and 660 nm in the wavelength region of 550 nm to 700 nm when dyeing a polylactic acid molded product alone, and 1 g of anion System dispersant (trade name: Setamol WS; manufactured by BASF) It was mixed until they became homogeneous, to obtain a black dye ([alpha] 1).
(Comparative Example 1.1): Preparation of black dye (α1 ′) Blue disperse dyes (b1.1) and (c1.1) with respect to the main black disperse dye (a1.1) described in Example 1.1 In the same manner as in Example 1.1, except that 0.83 g of an anionic dispersant (trade name: Setamol WS; manufactured by BASF) was charged and mixed until they were uniform, A black dye (α1 ′) was obtained.
(Example 1.2): Production of polylactic acid black dyed product (black polylactic acid molded article) (Sα1) 0.3 g (6% ow) of black dye (a1.1) obtained in Example 1.1 .F.) With 0.1 g dispersant (Nikkasan Salt 7000 / Nikka Chemical Co., Ltd.) and 0.4 ml of 8% acetic acid added to water at room temperature to disperse, and 100 ml of dyeing A liquid was prepared. Next, this dyeing solution and 5 g of polylactic acid fiber 100% spun yarn (5 denier) were charged into a pot-type high-pressure dyeing machine (“Mini Color” manufactured by Tecsum Co.) having a pot capacity of 300 ml, under high temperature and high pressure. Was subjected to dyeing. The staining conditions were as follows: the temperature was increased from room temperature to 110 ° C. at a rate of 2 ° C./minute, and further dyeing was continued at 110 ° C. for 30 minutes, and then cooled to 70 ° C. at a rate of 5 ° C./minute; After washing with water, using a solution of 1.5 g / L soda ash, 2 g / L hydrosulfite, 1 g / L lipotol PE (manufactured by Nikka Chemical Co., Ltd.), perform a reduction washing at 60 ° C. for 10 minutes. Dry at room temperature. By this operation, 6.0% o. w. A dyed product (Sα1) of a polylactic acid molded product corresponding to f was obtained. About the obtained dyeing | staining (S (alpha) 1), each of said (1)-(4) was evaluated.
For the evaluation of the lightness, saturation and hue of the dyed polylactic acid fiber of (1), the L value, C value and H value under the D65 light source are shown in Table 1.2, Each value is shown in Table 1.3. The results of evaluation of color rendering properties by visual observation in (2) are shown in Table 1.4, and the results of evaluation of color rendering properties by instrument measurement in (3) are shown in Table 1.5. About the measurement result of the reflectance of (4), the relationship between the measurement wavelength and the optical reflectance is shown in FIG. The results of Comparative Example 1.2, which will be described later, are similarly shown in the above table and figure.
(Comparative Example 1.2): Production of Polylactic Acid Black Dye (Sα1 ′) Instead of the black dye (α1) obtained in Example 1.1, the black dye (α1) obtained in Comparative Example 1.1 ') Except having used 0.3g, it operated similarly to Example 2.1 and obtained the dyeing | staining (S (alpha) 1') of the polylactic acid molded object. The obtained dyed product (Sα1 ′) was evaluated in each of the above (1) to (4).
(Comparative Example 1.3): Production of Polyester Black Dye (Fα2) Instead of the black dye composition (α1) obtained in Example 1.1, conventionally, the dyed product has a slightly reddish black color. A dyeing solution is prepared using 0.13 g of a black disperse dye for polyester DIANIX Black CC-R (α2), which is widely used in the market, and a spun yarn (100% polylactic acid fiber) Instead of denier), 5 g of polyester double picket filament processed yarn (150 denier / 30 filament) was used for dyeing in accordance with Example 1.2 to obtain a dyed polyester product (Fα2). The temperature condition for dyeing was such that the temperature was raised from room temperature to 130 ° C. at a rate of 2 ° C./min and dyeing for 30 minutes at 130 ° C. was continued. The obtained dyed product (Fα2) was evaluated in the above (4). The obtained optical reflectance spectrum is shown in FIG. The obtained dyed product (Fα2) was visually observed under standard light irradiation of a D65 light source. As a result, a slightly reddish black color was exhibited.
Comparative Example 1.4: Production of Polyester Black Dye (Fα3) Instead of the black dye composition (α1) obtained in Example 1.1, conventionally, the dyed product has a slightly greenish black color. A dyeing solution is prepared using 0.13 g of a black disperse dye for polyester DIANIX Black CC-G, which is widely used in the market, and a spun yarn of polylactic acid fiber 100% (5 denier) Instead of this, dyeing was performed according to Example 1.2 using 5 g of polyester double picket filament processed yarn (150 denier / 30 filament) to obtain a dyed product (Fα3) of a polyester molded product. The temperature condition for dyeing was such that the temperature was increased from room temperature to 130 ° C. at a rate of 2 ° C./min, and further dyeing was continued at 130 ° C. for 30 minutes. Evaluation of said (4) was performed about the obtained dyeing | staining (F (alpha) 3). The obtained optical reflectance spectrum is shown in FIG. When the obtained dyed product (Fα3) was visually observed under standard light irradiation of a D65 light source, it exhibited a slightly greenish black color.
(Comparative Example 1.5): Production of Polyester Black Dye (Fα4)>
Instead of the black dye composition (α1) obtained in Example 1.1, it is conventionally said that the dyed product exhibits a slightly greenish black color, while its color is acceptable to consumers. A dyeing solution is prepared using 0.13 g of black disperse dye DIANIX Black CC-3G for polyester, which is widely used in the market because it is black, and instead of 100% polylactic acid fiber spun yarn (5 denier) In addition, dyeing was performed in accordance with Example 1.2 using 5 g of polyester double picket filament processed yarn (150 denier / 30 filament) to obtain a dyed product (Fα4) of a polyester molded body. The temperature condition for dyeing was such that the temperature was increased from room temperature to 130 ° C. at a rate of 2 ° C./min, and further dyeing was continued at 130 ° C. for 30 minutes. Evaluation of said (4) was performed about the obtained dyeing | staining (F (alpha) 4). The obtained optical reflectance spectrum is shown in FIG. When the obtained dyed product (Fα4) was visually observed under standard light irradiation of a D65 light source, it exhibited a greenish black color.

As shown in Table 1.2, the dyed product (Sα1) obtained using the black dye according to the present invention (Example 1.1) and the main black disperse dye alone (Comparative Example 1.1) were used. All of the dyed products (Sα1 ′) achieved an L value of 20 or less and a C value of 5 or less under standard light of a D65 light source close to sunlight, and exhibited a good black color. I understand that. However, when comparing the H values in Table 1.2, the H value (74.71) of the dyed product (Sα1) belongs to the yellowish region, whereas the H value (50.98) of the dyed product (Sα1 ′). ) Was found to belong to the orange flavor region. From this, when the black dye (α1) of Example 1.1 containing the blue disperse dyes (b1.1) and (c1.1) in addition to the black dye (a1.1) was used, It can be seen that the blue disperse dyes (b1.1) and (c1.1) reduce the degree to which the black color of the dyed product becomes reddish under irradiation of the D65 light source.
As shown in Table 1.3, the dyed product (Sα1) obtained by using the black dye (Example 1.1) according to the present invention is stained under irradiation of the A light source which is one of artificial light. Since the L value of the product (Sα1) is 16.94 and the C value is 3.70, it can be seen that the color of the dyed product is sufficiently low and exhibits a good black color. On the other hand, for the dyed product (Sα1 ′) obtained using only the main black disperse dye (Comparative Example 1.1), the L value is 17.70 and the C value is 8.49. Therefore, in Comparative Example 1.1, the color of the dyed product obtained satisfies the standard of black, but has high saturation. Furthermore, especially considering that the H value is 33.46, which is in the reddish region, it can be seen that the black color is considerably reddish. From this, when the black dye (α1) of Example 1.1 containing the blue disperse dyes (b1.1) and (c1.1) in addition to the black dye (a1.1) was used, It can be seen that the blue disperse dyes (b1.1) and (c1.1) reduce the degree to which the black color of the dyed product becomes reddish under the light source A.
Further, as shown in Table 1.4, a dyed product (Sα1) obtained using the black dye according to the present invention (Example 1.1) and only the main black disperse dye (Comparative Example 1.1). It can be seen that the dyed product (Sα1 ′) obtained by use can sufficiently recognize a difference even in human vision.
As shown in Table 1.5, when the color rendering properties under different light sources are compared, the dyed product (Sα1) obtained using the black dye (Example 1.1) according to the present invention is the main black disperse dye. It can be seen that the color rendering properties are improved satisfactorily as compared with the dyed product (Sα1 ′) obtained using only (Comparative Example 1.1). In particular, it can be seen that the dyed product (Sα1) has extremely low color rendering even under a TL84 light source that is frequently used as a standard light source in European supermarkets.
On the other hand, as shown in FIG. 1, the wavelength of 400 nm to 750 nm in both the dyed product (Sα1) obtained using the black dye according to the present invention (Example 1.1) and the dyed product of each comparative example. In the region, the optical reflectance at 400 nm to 600 nm is constant while being in a low state. However, for optical reflectivity corresponding to wavelengths between about 600 nm and about 700 nm corresponding to red, the dyed product (Sα1) was dyed using only the main black disperse dye (Comparative Example 1.1). Compared with the dyed product (Sα1 ′), it was approximated by the dyed products (Fα2, Fα3 and Fα4) of Comparative Examples 1.3 to 1.5 in which the polyester filament processed yarn was dyed with a conventional black disperse dye for polyester. It can be seen that it shows a curve. From this, it can be seen that the black dye according to the present invention can provide a dyed product exhibiting a black color with reduced redness. In particular, the color of the dyed products (Fα2, Fα3 and Fα4) obtained in Comparative Examples 1.3 to 1.5 has a slightly reddish black color to a green color as described above. It was visually observed as a black variation up to blackish. Considering the result of this visual observation, there is a visual difference between these colors, but both of them are representative black colors in the range preferred by consumers as black when commercially available. It is a variation. However, it can be seen that there is almost no difference in the optical reflection curve shown in FIG. 1, and the optical reflectance is very approximate.
Here, when Example 1.2 and Comparative Example 1.2 are respectively compared with the optical reflectance curves of Comparative Examples 1.3 to 1.5, Comparative Example 1.2 and Comparative Examples 1.3 to 1.5 are compared. The difference between Example 1.2 and Comparative Examples 1.3 to 1.5 (particularly, the difference between about 600 nm and about 700 nm, which is said to visually sense the presence or absence of redness or intensity), is It can be seen that it is considerably reduced. For this reason, when the polylactic acid was dyed using the black dye according to the present invention, the red color of the dyed product obtained was extremely reduced, and it was dyed in black, which has been particularly preferred by consumers. It can be seen that a black color approximated to polyester is obtained.
(Example 2.1): Preparation of Navy Color Dye (β1) In a container, the base disperse dyes listed in Table 2.1 were charged and mixed until they became uniform to obtain a main navy disperse dye (a2. 1) was prepared.

Next, 0.4 g of DIANIX Turquoise S-BG (manufactured by Dystar, CI Disperse) was further added to the main navy disperse dye (a2.1) as blue disperse dyes (b2.1) and (c2.1). Blue 60; a disperse dye having a maximum absorption between 640 nm and 700 nm in a wavelength region of 550 nm to 700 nm when dyeing a polylactic acid molded product alone, and 0.7 g of DIANIX Blue S-BG ( CI Disperse Blue 73, manufactured by Dystar, a disperse dye having a maximum absorption between 550 nm and 660 nm in a wavelength region of 550 nm to 700 nm when a polylactic acid molded product is dyed alone), and 1 .1 g of anionic dispersant (trade name: Setamol WS; manufactured by BASF) They were charged and mixed until they became homogeneous, to obtain a navy dye (.beta.1).
(Comparative Example 2.1): Preparation of Navy Color Dye (β1) To the main navy disperse dye (a2.1) described in Example 3, blue disperse dyes (b2.1) and (c2.1) were added. Without charging, only the 0.96 g of an anionic dispersant (trade name: Setamol WS; manufactured by BASF) was charged and mixed until they became uniform. A dye (β1 ′) was obtained.
(Example 2.2): Production of polylactic acid navy color dye (Sβ1) 0.2 g (corresponding to 4% owf) of the navy dye (β1) obtained in Example 2.1. In addition, 0.1 g of a dispersant (Nikka Sun Salt 7000 / manufactured by Nikka Chemical Co., Ltd.) and 0.4 ml of 8% acetic acid were added and dispersed in water at room temperature to prepare 100 ml of a staining solution. Next, this dyeing solution and 5 g of polylactic acid fiber 100% spun yarn (5 denier) were charged into a pot-type high-pressure dyeing machine (“Mini Color” manufactured by Tecsum Co.) having a pot capacity of 300 ml, under high temperature and high pressure. Was subjected to dyeing. The staining conditions were as follows: the temperature was increased from room temperature to 110 ° C. at a rate of 2 ° C./minute, and further dyeing was continued at 110 ° C. for 30 minutes, and then cooled to 70 ° C. at a rate of 5 ° C./minute; After washing with water, using a solution of 1.5 g / L soda ash, 2 g / L hydrosulfite, 1 g / L lipotol PE (manufactured by Nikka Chemical Co., Ltd.), perform a reduction washing at 60 ° C. for 10 minutes. Dry at room temperature. By this operation, 4.0% o. w. A dyed product (Sβ1) of a polylactic acid molded product corresponding to f was obtained. About the obtained dyeing | staining (S (beta) 1), each of said (1)-(4) was evaluated.
For the evaluation of lightness, saturation and hue of the dyed polylactic acid fiber of (1), the L value, C value and H value under the standard light of the D65 light source are shown in Table 2.2. The respective values under light are shown in Table 2.3. The results of evaluation of color rendering properties by visual observation in (2) are shown in Table 2.4, and the results of evaluation of color rendering properties by instrument measurement in (3) are shown in Table 2.5. Regarding the measurement result of the reflectance of (4), the relationship between the measurement wavelength and the optical reflectance is shown in FIG. The results of Comparative Example 2.2, which will be described later, are similarly shown in the above table and figure.
(Comparative Example 2.2): Production of Polylactic Acid Navy Color Dye (Sβ1 ′) Instead of the navy color dye (β1) obtained in Example 2.1, the navy color obtained in Comparative Example 2.1 A dyed product (Sβ1 ′) of a polylactic acid molded product was obtained in the same manner as in Example 2.2 except that 0.2 g of the dye (β1 ′) was used. The obtained dyed product (Sβ1 ′) was evaluated in each of the above (1) to (4).
(Comparative Example 2.3): Production of Polyester Navy Color Dye (Fβ2)>
Instead of the navy dye (β1) obtained in Example 3, a navy color disperse dye for polyesters DIANIX, which is conventionally commercially acceptable while the dyed product exhibits a slightly greenish navy color A dyeing solution is prepared using 0.09 g of Navy S-G 200%, and 5 g of polyester double picket filament processed yarn (150 denier / 30 filament) instead of 100% polylactic acid fiber 100% spun yarn (5 denier) ) Was used according to Example 2.2 to obtain a dyed polyester product (Fβ2). The temperature condition for dyeing was such that the temperature was raised from room temperature to 130 ° C. at a rate of 2 ° C./min, and further dyeing was continued at 130 ° C. for 30 minutes. The obtained dyed product (Fβ2) was evaluated in the above (4). The obtained optical reflectance spectrum is shown in FIG.

As shown in Table 2.2, the dyed product (Sβ1) obtained using the navy dye according to the present invention (Example 2.1) and only the main navy disperse dye (Comparative Example 2.1) are used. Comparing the obtained dyed product (Sβ2), the dyed product (Sβ1) has a higher L value and C value under the standard light of the D65 light source close to sunlight. This shows that the dyed product (Sβ1) has a higher density and sufficient saturation. In contrast, the dyed product of Comparative Example 2.2 (Sβ1 ′) has a high L value but a low C value and is too dull. On the other hand, the H value (hue) shows almost no difference between the dyed products (Sβ1) and (Sβ1 ′). From the above results, the dyed product (Sβ1 ′) obtained using only the main navy disperse dye (Comparative Example 2.1) exhibits a slightly reddish and dull navy color under the standard light of the D65 light source. On the other hand, it can be seen that the dyed product (Sβ1) obtained by using the navy color dye (Example 2.1) according to the present invention shows a more navy hue due to its high saturation.
From this, when the navy color dye (β1) of Example 2.1 containing the blue disperse dyes (b2.1) and (c2.1) in addition to the navy color dye (a2.1) is used. It can be seen that the blue disperse dyes (b2.1) and (c2.1) reduce the degree to which the dyed product is reddish under the standard light of the D65 light source.
As shown in Table 2.3, using only the dyed product (Sβ1) obtained using the navy dye according to the present invention (Example 2.1) and the main black disperse dye (Comparative Example 2.1). The obtained dyed product (Sβ1 ′) has a large difference in H value under the irradiation of the A light source which is one of artificial light. It can be said that the dyed product (Sβ1) is closer to yellowish blue than the dyed product (Sβ2), and has a hue more like a navy color that should be originally required. From this, the navy color dye (β1) of Example 2.1 containing the blue disperse dyes (b2.1) and (c2.1) in addition to the used navy color dye (a2.1) was used. In this case, it can be seen that the blue disperse dyes (b2.1) and (c2.1) not only improve the saturation but also reduce the reddish degree under the A light source.
Further, as shown in Table 2.4, the dyed product (Sβ1) obtained using the navy color dye according to the present invention (Example 2.1) and the main navy disperse dye only (Comparative Example 2.1) It can be seen that the dyed product (Sβ1 ′) obtained by using this can sufficiently recognize the difference in human vision.
As shown in Table 2.5, when the color rendering properties under different light sources were compared, the dyed product (Sβ1) obtained using the navy dye composition of the present invention (Example 2.1) was mainly It can be seen that the color rendering is improved satisfactorily as compared with the dyed product (Sβ1 ′) obtained using only the navy disperse dye (Comparative Example 2.1). In particular, the dyed product (Sβ1) has a very low color rendering property even under a TL84 light source that is frequently used as a standard light source in European supermarkets.
On the other hand, referring to FIG. 2, among the spectra of optical reflectance in the wavelength region of 400 nm to 750 nm, in particular, the spectrum of 400 nm to 500 nm and the spectrum of about 600 nm to about 700 nm corresponding to red are according to the present invention. Dye (Sβ1) obtained using a navy dye (Example 2.1) (Sβ1; Example 2.2) and a main navy disperse dye alone (Comparative Example 2.1) When comparing Example 2.2), the dyed product (Sβ1) is more similar to the dyed product of Comparative Example 2.3 (Fβ3) in which the polyester filament processed yarn is dyed with a conventional navy disperse dye for polyester. It can be seen that this curve is shown. From this, it can be seen that the navy dye according to the present invention can provide a dyed product exhibiting a navy color with reduced redness.

  When the black or navy dye composition of the present invention is used, it is possible to dye the polylactic acid molded body in black or navy color with reduced redness as compared with the case of using the conventional dye composition. Become. Color rendering is also reduced. The dyed polylactic acid molded body thus obtained is useful in the fiber processing field, film processing field, sheet processing field, and the like.

Claims (12)

A black dye composition for dyeing a polylactic acid molded body in black,
Containing a main black disperse dye (a1) and a blue disperse dye (b1);
The main black disperse dye (a1) has dyeability with respect to polyester and polylactic acid,
When the polylactic acid molded article is dyed with the blue disperse dye (b1), the maximum absorption is observed between 640 nm and 700 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded article. Exists,
When the total amount of the main black disperse dye (a1) and the blue disperse dye (b1) is 100 parts by mass, the dye (a1) is in a ratio of 85 to 95 parts by mass, and the dye (b1) Is contained in a proportion of 5 to 15 parts by mass,
Black dye composition. A black dye composition for dyeing a polylactic acid molded body in black,
Containing a main black disperse dye (a1), a blue disperse dye (b1), and a blue disperse dye (c1);
The main black disperse dye (a1) has dyeability with respect to polyester and polylactic acid,
When the polylactic acid molded article is dyed with the blue disperse dye (b1), the maximum absorption is observed between 640 nm and 700 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded article. Exists,
When the polylactic acid molded article is dyed with the blue disperse dye (c1), the maximum absorption is observed between 550 nm and 660 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded article. Exists,
When the total amount of the main black disperse dye (a1), blue disperse dye (b1), and blue disperse dye (c1) is 100 parts by mass, the proportion of the dye (a1) is from 65 parts by mass to 90 parts by mass The dye (b1) is contained in a proportion of 5 to 15 parts by mass, and the dye (c1) is contained in a proportion of 5 to 20 parts by mass.
Black dye composition. 5 to 15 parts by mass of an anionic dispersant is further contained with respect to a total of 100 parts by mass of the main black disperse dye (a1), blue disperse dye (b1), and blue disperse dye (c1). The composition according to claim 2. The blue disperse dye (b1) comprises Disperse Blue 7, Disperse Blue 60, Disperse Blue 87, Disperse Blue 87.1, Disperse Blue 198, and Disperse Green 9 of color index (CI). The composition according to any one of claims 1 to 3, which is at least one disperse dye corresponding to a color index selected from the group. Disperse Blue 3, Disperse Blue 56, Disperse Blue 73, Disperse Blue 73.1, Disperse Blue 77, Disperse Blue 81, Disperse of the blue disperse dye (c1) of Color Index (CI) A color index selected from the group consisting of Blue 149, Disperse Blue 153, Disperse Blue 165, Disperse Blue 291, Disperse Blue 291.1, Disperse Blue 268, Disperse Blue 284, and Disperse Blue 367 The composition according to claim 2, which is at least one corresponding disperse dye. A navy dye composition for dyeing a polylactic acid molded body in a navy color,
Containing a main navy disperse dye (a2) and a blue disperse dye (b2);
The main navy disperse dye (a2) has dyeability with respect to polyester and polylactic acid,
When the polylactic acid molded product is dyed with the blue disperse dye (b2), the maximum absorption is observed between 640 nm and 700 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded product. Exists,
When the total amount of the main navy disperse dye (a2) and the blue disperse dye (b2) is 100 parts by mass, the dye (a2) is in a proportion of 85 to 95 parts by mass, and the dye (b2) Is contained in a proportion of 5 to 15 parts by mass,
Navy dye composition. A navy dye composition for dyeing a polylactic acid molded body in a navy color,
Containing a main navy disperse dye (a2), a blue disperse dye (b2), and a blue disperse dye (c2);
The main navy disperse dye (a2) has dyeability with respect to polyester and polylactic acid,
When the polylactic acid molded product is dyed with the blue disperse dye (b2), the maximum absorption is observed between 640 nm and 700 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded product. Exists,
When the polylactic acid molded article is dyed with the blue disperse dye (c2), the maximum absorption is observed between 550 nm and 660 nm in the wavelength region of 550 nm to 700 nm of the absorbance curve indicating the absorbance of the dyed surface of the dyed molded article. Exists,
When the total amount of the main navy disperse dye (a2), blue disperse dye (b2), and blue disperse dye (c2) is 100 parts by mass, the proportion of the dye (a2) is from 65 parts by mass to 90 parts by mass The dye (b2) is contained in a proportion of 5 to 15 parts by mass, and the dye (c2) is contained in a proportion of 5 to 20 parts by mass.
Navy dye composition. 5 to 15 parts by mass of an anionic dispersant is further contained with respect to 100 parts by mass in total of the main navy disperse dye (a2), the blue disperse dye (b2), and the blue disperse dye (c2). The composition according to claim 7. The blue disperse dye (b2) comprises Disperse Blue 7, Disperse Blue 60, Disperse Blue 87, Disperse Blue 87.1, Disperse Blue 198, and Disperse Green 9 of color index (CI). The composition according to claim 6, which is at least one disperse dye corresponding to a color index selected from the group. The disperse blue 3, disperse blue 56, disperse blue 73, disperse blue 73, disperse blue 73.1, disperse blue 77, disperse blue 81, disperse of the blue disperse dye (c2) is color index (CI) A color index selected from the group consisting of Blue 149, Disperse Blue 153, Disperse Blue 165, Disperse Blue 291, Disperse Blue 291.1, Disperse Blue 268, Disperse Blue 284, and Disperse Blue 367 The composition according to claim 7, which is at least one applicable disperse dye. A dyed polylactic acid molded article obtained by dyeing a polylactic acid molded article with the black dye composition according to any one of claims 1 to 5. A dyed polylactic acid molded article obtained by dyeing a polylactic acid molded article with the navy dye composition according to any one of claims 6 to 10.

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