Fiber dyeing agent composition for head decorative products

Abstract

To provide a fiber dyeing agent composition for a head ornament product, containing an anionic direct dye, excellent in dyeability of a fiber for a head ornament product such as a regenerated collagen fiber, and capable of obtaining a colored fiber having good compatibility with hair without impairing good combing property even after dyeing.SOLUTION: A fiber dyeing agent composition for a head decorative product contains an anionic direct dye (A) and water, wherein the total content of lactic acid, citric acid and salts thereof is 4.5 mass% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dye composition for use in dyeing fibers for head accessories. [Background technology]

[0002] As a non-oxidative one-component hair dye, a hair dye using an acid dye is known. For example, Patent Document 1 discloses a non-oxidative one-component hair dye containing a certain proportion or more of Black No. 401, which has good hair dyeing properties and little skin coloring. The non-oxidative one-component hair dye contains predetermined amounts of a specific acid dye component, benzyl alcohol, diethylene glycol monoalkyl ether, and ethanol, and further contains an organic carboxylic acid or a salt thereof, and has a pH of 2 to 5. Because this hair dye is non-oxidative and does not need to contain an oxidizing agent such as hydrogen peroxide, hair damage caused by the hair dye can be suppressed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-270025 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, the use of fibers other than human hair as fibers for head accessories such as hair extensions has been investigated. Among these, regenerated collagen fiber, a protein fiber, is suitable for use as a raw material for artificial hair because its properties are similar to those of human hair. Fibers used as raw materials for artificial hair are required to have high aesthetic appeal, such as colorability and texture.

[0005] However, dyeing regenerated collagen fibers can cause them to crimp, widen the fiber bundles, and impair their texture. As a result, it has been found that when a head accessory containing dyed regenerated collagen fibers is worn on the head, it can be difficult to comb the fibers because the fibers do not blend well with the hair.

[0006] The present invention relates to a fiber dye composition for head accessories, which contains an anionic direct dye and has excellent dyeability for fibers for head accessories such as regenerated collagen fibers, and which can give colored fibers that do not lose combability even after dyeing and that blend well with hair. [Means for solving the problem]

[0007] The present inventors have discovered that the above-mentioned problems can be solved by a fiber dye composition for headwear products, which contains an anionic direct dye and water and has a total content of a specific organic acid and an organic acid salt that is not more than a predetermined amount.

[0008] That is, the present invention relates to the following. [1] A fiber dye composition for headwear products, comprising an anionic direct dye (A) and water, and having a total content of lactic acid, citric acid and salts thereof of 4.5 mass % or less. [2] A method for dyeing fibers for head accessories, comprising a step of applying the fiber dye composition for head accessories according to [1] to fibers for head accessories. [3] [1] A colored fiber for a headwear product dyed using the fiber dye composition for a headwear product. [4] A head accessory comprising the colored head accessory fiber according to [3]. [Effects of the Invention]

[0009] According to the present invention, there can be provided a fiber dye composition for head accessories, which contains an anionic direct dye, has excellent dyeability for fibers for head accessories such as regenerated collagen fibers, does not impair ease of combing even after dyeing, and can give colored fibers that blend well with hair. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Definition] As used herein, "head accessories" refers to, for example, hair wigs, hairpieces, weaving, hair extensions, braided hair, hair accessories, doll hair, etc. Furthermore, "fibers for head accessories" refers to fibers used in the head accessories. However, human hair is excluded from the fibers for head accessories to be dyed with the dye composition of the present invention, but human hair may be mixed with the fibers for head accessories in the head accessories. In this specification, "excellent dyeability of fibers for head accessories" means that there is a large change in color of the fibers for head accessories before and after dyeing with the dye composition for fibers for head accessories. In this specification, "good compatibility with hair after dyeing" means that there is little change in appearance such as widening of the fiber bundle due to crimping of the fiber for a head accessory after dyeing, the fiber is well aligned with the hair, and the hair can be easily combed when attached to the hair. The dyeability and compatibility with hair can be specifically evaluated by the method described in the examples.

[0011] [Textile dye composition for head accessories] The fiber dye composition for head accessories of the present invention contains an anionic direct dye (A) and water, and the total content of lactic acid, citric acid and salts thereof is 4.5 mass % or less. In the following description, the fiber dye composition for head accessories may be simply referred to as the "composition (of the present invention)" or "dye composition (of the present invention)." By virtue of the above-described constitution, the composition of the present invention can provide colored fibers for head accessories, such as regenerated collagen fibers, that have excellent dyeability, do not lose combability even after dyeing, and blend well with hair.

[0012] The reason why the composition of the present invention exhibits the above-mentioned effects is not clear, but is presumed to be as follows. Dye compositions (hair dyes) for human hair containing anionic direct dyes typically must contain an organic acid or an organic acid salt to improve dyeability. This is because human hair is negatively charged, which causes charge repulsion with anionic direct dyes, which also have a negative charge, resulting in poor dyeability. In contrast, fibers for head accessories, such as regenerated collagen fibers, generally contain polyvalent metals such as aluminum, which are positively charged. Therefore, electrical interaction occurs between the polyvalent metal and the anionic direct dye in the fibers for head accessories, which is thought to facilitate fixation to the fibers and provide good dyeability, regardless of the content of the organic acid or organic acid salt. On the other hand, it has been found that, among the organic acids or organic acid salts, lactic acid, citric acid, and their salts, when applied to fibers for head accessories such as regenerated collagen fibers, coordinate with the polyvalent metals in the fibers, resulting in the elution of the polyvalent metals. Therefore, by limiting the content of lactic acid, citric acid, and their salts in the dye composition of the present invention to a predetermined amount or less, it is believed that problems caused by the elution of polyvalent metals when applied to fibers for head accessories such as regenerated collagen fibers can be avoided. This effect is believed to ensure both good dyeability and compatibility with dyed hair. The mechanism of action of the present invention is not limited to the above.

[0013] <Anionic direct dyes (A)> The dye composition contains an anionic direct dye (A) as a dyeing component for fibers for headwear. The anionic direct dye (A) can be one or more compounds known as anionic direct dyes.

[0014] From the viewpoint of improving the dyeability of fibers for head accessories such as regenerated collagen fibers, the anionic direct dye (A) preferably contains one or more anionic direct dyes selected from the group consisting of the following components (A1) and (A2):

[0015] (A1) An anionic direct dye having a sulfonic acid group and satisfying at least one of the following (1) and (2): (1) Molecular weight of 500 or more (2) When the molecular weight is Mw, the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic sites (b) divided by Mw [(ab) / Mw] is 0.0010 or more. (A2) One or more anionic direct dyes selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16

[0016] The molecular weight of component (A1) here refers to the molecular weight of component (A1) in an undissociated (acid) state. For example, even if at least a portion of the sulfonic acid groups in component (A1) are in the form of a salt (sulfonate salt), the molecular weight of component (A1) refers to the molecular weight in the undissociated sulfonic acid state, and does not include the molecular weight of the counter ion. This also includes cases where component (A1) has an onium group such as a quaternary ammonium group, but in such cases, the counter ion is similarly not included in the molecular weight.

[0017] Component (A1) may be an anionic direct dye that satisfies either one of the above (1) and (2), or may be an anionic direct dye that satisfies both the above (1) and (2). From the viewpoint of improving the dyeability of fibers for head accessories, such as regenerated collagen fibers, it is preferable that component (A1) satisfies at least the above (2).

[0018] The reason why the component (A1) is preferable as the anionic direct dye (A) is thought to be as follows. As an anionic direct dye used for dyeing human hair, a low molecular weight anionic direct dye is usually preferred from the viewpoint of penetrating into the interior of human hair and improving dyeability. In contrast, fibers for head accessories, such as regenerated collagen fibers, which are the subject of dyeing with the composition of the present invention, differ from human hair in that they do not have a barrier structure, such as a cuticle, that separates the inside and outside of the fiber. Therefore, when a low molecular weight anionic direct dye is used, the color tends to fade easily after dyeing. In contrast, the anionic direct dye (A1) that satisfies the above condition (1) is thought to have a large molecular weight and therefore is less likely to fade after dyeing. Furthermore, since the subject of dyeing is fibers for head accessories such as regenerated collagen fibers, it is thought that it will be possible to dye the fibers by penetrating the anionic direct dye with a large molecular weight into the interior of the fibers.

[0019] The anionic direct dye (A1) that satisfies the above condition (2) can be considered as follows. Among fibers for head accessories, regenerated collagen fibers generally contain a polyvalent metal such as aluminum. This polyvalent metal is positively charged. On the other hand, when the molecular weight of the anionic direct dye (A1) is Mw, and the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic moieties (b) in the dye is divided by Mw ((ab) / Mw), the anionicity of the anionic direct dye (A1) per molecular weight is strong. Therefore, anionic direct dyes (A1) that satisfy the above condition (2) exhibit strong electrical interactions with the polyvalent metal in the regenerated collagen fibers, which is thought to improve dye fixation and dyeability on the fibers for head accessories.

[0020] The reason why component (A2) is preferred as the anionic direct dye (A) is thought to be as follows: Component (A2) has a phenolic acidic hydroxyl group and a small molecular weight, and therefore, like component (A1), has a strong anionic character per molecular weight. Therefore, it is thought that the electrical interaction with the polyvalent metal in the regenerated collagen fibers is strong, improving dyeability.

[0021] (Component (A1)) Component (A1) is an anionic direct dye that has a sulfonic acid group and satisfies at least one of the following (1) and (2):

[0022] (1) Molecular weight of 500 or more (2) When the molecular weight is Mw, the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic sites (b) divided by Mw [(ab) / Mw] is 0.0010 or more. The number of sulfonic acid groups (a) in component (A1) may be 1 or more, and from the viewpoint of improving the dyeability of the fiber for head accessories, it is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, even more preferably 1 or more and 4 or less, still more preferably 1 or more and 3 or less, and even more preferably 1 or more and 2 or less. The "number (a) of sulfonic acid groups in component (A1)" herein means the number of sulfonic acid groups in component (A1) in the undissociated (acid) state.

[0023] Component (A1) may be at least partially in the form of a salt. From the viewpoint of improving the dyeability of the fiber for head accessories, the salt preferably includes an ammonium salt or a metal salt, more preferably an ammonium salt or one or more metal salts selected from the group consisting of alkali metals, alkaline earth metals, and transition metals, even more preferably an ammonium salt or one or more metal salts selected from the group consisting of potassium, sodium, calcium, iron, and chromium, still more preferably an ammonium salt or one or more metal salts selected from the group consisting of sodium, calcium, iron, and chromium, and even more preferably a sodium salt.

[0024] Component (A1) may further have a cationic moiety, such as a quaternary ammonium cationic moiety or an iminium cationic moiety, and preferably contains an iminium cationic moiety.

[0025] From the viewpoint of improving the dyeability of the fiber for head accessories, the number of cationic moieties (b) in component (A1) is preferably 0 or more and 5 or less, more preferably 0 or more and 4 or less, even more preferably 0 or more and 3 or less, and still more preferably 0 or more and 2 or less.

[0026] The difference (ab) between the number of sulfonic acid groups (a) and the number of cationic moieties (b) in component (A1) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less, from the viewpoint of improving the dyeability of the fiber for head accessories.

[0027] The component (A1) may have any number of carboxy groups.

[0028] [Requirement (1)] The component (A1) that satisfies the above condition (1) has a sulfonic acid group and a molecular weight of 500 or more. When component (A1) satisfies the above (1), from the viewpoint of improving the dyeability of the fiber for head accessories, the molecular weight of component (A1) is preferably 520 or more, more preferably 540 or more, and is preferably 1,500 or less, more preferably 1,200 or less, even more preferably 1,000 or less, still more preferably 900 or less, still more preferably 800 or less, still more preferably 780 or less, still more preferably 750 or less, still more preferably 700 or less, and still more preferably 650 or less. That is, the molecular weight of component (A1) is preferably 500 or more and 1,500 or less, more preferably 500 or more and 1,200 or less, still more preferably 500 or more and 1,000 or less, still more preferably 500 or more and 900 or less, still more preferably 500 or more and 800 or less, still more preferably 500 or more and 780 or less, still more preferably 500 or more and 750 or less, still more preferably 520 or more and 700 or less, and still more preferably 540 or more and 650 or less.

[0029] [Requirement (2)] When component (A1) satisfies the above (2), the difference (ab) between the number of sulfonic acid groups (a) in component (A1) and the number of cationic moieties (b) in component (A1) divided by Mw, where Mw is the molecular weight of component (A1) (molecular weight in the undissociated (acid) state), is 0.0010 or more, preferably 0.0012 or more, and more preferably 0.0015 or more, from the viewpoint of improving the dyeability of fibers for head accessories. This is because the larger the difference between the number of sulfonic acid groups and the number of cationic moieties per molecular weight of component (A1), the stronger the anionic properties become, and the better the fixability to regenerated collagen fibers containing positively charged polyvalent metals and the like. Furthermore, [(ab) / Mw] is preferably 0.010 or less, more preferably 0.008 or less, even more preferably 0.007 or less, still more preferably 0.0050 or less, still more preferably 0.0045 or less, still more preferably 0.0040 or less, and still more preferably 0.003 or less. That is, the value [(ab) / Mw] is preferably 0.0010 or more and 0.010 or less, more preferably 0.0010 or more and 0.008 or less, still more preferably 0.0010 or more and 0.007 or less, still more preferably 0.0010 or more and 0.0050 or less, still more preferably 0.0012 or more and 0.0045 or less, still more preferably 0.0012 or more and 0.0040 or less, and still more preferably 0.0015 or more and 0.003 or less.

[0030] When component (A1) satisfies the above (2), the molecular weight Mw is preferably 250 or more, more preferably 280 or more, even more preferably 300 or more, and still more preferably 320 or more. Also, it is preferably 1,500 or less, more preferably 1,200 or less, even more preferably 1,000 or less, still more preferably 900 or less, still more preferably 800 or less, still more preferably 780 or less, still more preferably 750 or less, still more preferably 700 or less, and still more preferably 650 or less. That is, the molecular weight Mw is preferably 250 or more and 1,500 or less, more preferably 280 or more and 1,200 or less, even more preferably 300 or more and 1,000 or less, still more preferably 300 or more and 900 or less, still more preferably 300 or more and 800 or less, still more preferably 300 or more and 780 or less, still more preferably 300 or more and 750 or less, still more preferably 300 or more and 700 or less, and still more preferably 320 or more and 650 or less.

[0031] Component (A1) may satisfy both (1) and (2) above, in which case the molecular weight of component (A1) is 500 or more and [(ab) / Mw] is 0.0010 or more. The preferred ranges of the molecular weight and [(ab) / Mw] of component (A1) are the same as those described above.

[0032] Component (A1) is more preferably Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Blown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 20470), Acid Red 18 (Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Red 184 (Color Index No. 15685), Solv.Green 7 (Color Index No. 59040), Acid Red 35 (Color Index No. 18065), Acid Red 14 (Color Index No. 14720), Food Red 6 (Color Index No. 16155), Acid Red 26 (Color Index No. 16150), Food Red 1 (Color Index No. 14700), Acid Yellow 3 (Color Index No. 47005), Acid Red 33 (Color Index No. 17200), Acid Blue 74 (Color Index No.73015)、Acid Orange 3(Color Index No.10385)、Food Yellow 3(Color Index No. 15985)、Acid Orange 24(Color Index No.20170)、Acid Violet 43(Color Index No.60730)、Acid Blue 62(Color Index No.62045)、Acid Red 88(Color Index No.15620)、Acid Yellow 11(Color Index No.18820)、Acid Yellow 36(Color Index No.13065)、Acid Yellow 1(Color Index No.10316)、Acid Orange 7(Color Index No.15510)、Acid Orange 20(Color Index No.14600)、Acid Yellow 9(Color Index No. 13015)、Acid Orange 6(Color Index No.14270)、Food Red 17(Color Index No.16035)、Acid Red 41(Color Index No.16290)、Acid Red 1(Color Index No.18050)、Acid Red 155(Color Index No.18130)、Acid Red 180(Color Index No.18736)、Acid Yellow 17(Color Index No.18965)、Acid Yellow 23(Color Index No.19140)、Acid Red 163(Color Index No.24790)、Food Black 2(Color Index No.27755)、Direct Orange 39(Color Index No.40215)、Acid Blue 7(Color Index No.42080)、Acid Green 9(Color Index No.42100)、Acid Green 22(Color Index No.42170)、Acid Blue 104(Color Index No.and one or more selected from the group consisting of Acid Violet 9 (Color Index No. 42735), Acid Red 50 (Color Index No. 45220), Acid Violet 50 (Color Index No. 50325), Acid Black 2 (Color Index No. 50420), Acid Blue 80 (Color Index No. 61585), Acid Blue 87 (Color Index No. 74180), Acid Red 195 (Color Index No. 18760), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102). Details of these anionic direct dyes are shown in Table 1.

[0033] [Table 1]

[0034] Among the above, from the viewpoint of improving the dyeability of the fiber for headwear and obtaining a desired color tone, component (A1) is more preferably Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Blue 9 (Color Index No. 42090), Acid Blue 5 (Color Index No. 42052), Acid Green 3 (Color Index No. 42085), Acid Green 25 (Color Index No. 61570), Acid Blown 13 (Color Index No. 10410), Acid Red 52 (Color Index No. 45100), Acid Black 1 (Color Index No. 20470), Acid Red 18 (Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index No. 42051), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Violet 43 (Color Index No. 60730), Acid Yellow 36 (Color Index No. 13065), Acid Yellow 1 (Color Index No. 10316), Acid Orange 7 (Color Index No. 15510), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102), and even more preferably Acid Black 52 (Color Index No.15711), Acid Green 1(Color Index No.10020), Food Black 1(Color Index No.28440), Food Green 3(Color Index No.42053), Acid Green 5(Color Index No.42095), Acid Blue 9(Color Index No.42090), Acid Blue 5(Color Index No.42052), Acid Green 3(Color Index No.42085), Acid Green 25(Color Index No.61570), Acid Blown 13(Color Index No.10410), Acid Red 52(Color Index No.45100), Acid Black 1(Color Index No.20470), Acid Red 18(Color Index No. 16255), Acid Red 27 (Color Index No. 16185), Acid Blue 3 (Color Index and more preferably, one or more selected from the group consisting of Acid Black 52 (Color Index No. 15711), Acid Green 1 (Color Index No. 10020), Food Black 1 (Color Index No. 28440), Food Green 3 (Color Index No. 42053), Acid Green 5 (Color Index No. 42095), Acid Violet 43 (Color Index No. 60730), Acid Orange 7 (Color Index No. 15510), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102). Blue 9 (Color Index No.42090), Acid Green 3(Color Index No.42085), Acid Green 25(Color Index No.61570), Acid Blown 13(Color Index No.10410), Acid Red 52(Color Index No.45100), Acid Black 1(Color Index No.20470), Acid Red 18(Color Index No.16255), Acid Red 27(Color Index No.16185), Acid Blue 3(Color Index No.42051), Acid Green 50(Color Index No.44090), Acid Red 73(Color Index No.27290), Acid Blue 1(Color Index No.42045), Acid Violet 43(Color Index No.60730), Acid Yellow 36(Color Index No.13065), Acid Yellow The color may include one or more selected from the group consisting of Acid Red 1 (Color Index No. 10316), Acid Orange 7 (Color Index No. 15510), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102), and even more preferably includes Acid Red 52 (Color Index No. 45100), Acid Violet 43 (Color Index No. 60730), and Acid Orange 7 (Color Index No. 15510).

[0035] [Ingredient (A2)] Component (A2) is one or more anionic direct dyes selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16. From the viewpoint of obtaining a desired color tone, component (A2) may contain two or more dyes selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16, or may contain three dyes selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16.

[0036] From the viewpoint of improving the dyeability of the fiber for head accessories and obtaining the desired color tone, the anionic direct dye (A) more preferably contains one or more members selected from the group consisting of the following components (A1) and (A2): (A1) Acid Black 52 (Color Index No.15711), Acid Green 1 (Color Index No.10020), Food Black 1 (Color Index No.28440), Food Green 3 (Color Index No.42053), Acid Green 5 (Color Index No.42095), Acid Blue 9 (Color Index No.42090), Acid Blue 5 (Color Index No.42052), Acid Green 3 (Color Index No.42085), Acid Green 25 (Color Index No.61570), Acid Blown 13 (Color Index No.10410), Acid Red 52 (Color Index No.45100), Acid Black 1 (Color Index No.20470), Acid Red 18 (Color Index No.16255), Acid Red 27(Color Index one or more selected from the group consisting of Acid Blue 3 (Color Index No. 16185), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Violet 43 (Color Index No. 60730), Acid Yellow 36 (Color Index No. 13065), Acid Yellow 1 (Color Index No. 10316), Acid Orange 7 (Color Index No. 15510), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102). (A2) One or more selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16

[0037] From the viewpoint of improving the dyeability of the fiber for head accessories and obtaining the desired color tone, the anionic direct dye (A) more preferably contains one or more members selected from the group consisting of the following components (A1) and (A2): (A1) One or more selected from the group consisting of Acid Blue 9 (Color Index No. 42090), Acid Red 52 (Color Index No. 45100), Acid Violet 43 (Color Index No. 60730), and Acid Orange 7 (Color Index No. 15510) (A2) One or more selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16

[0038] The total content of component (A1) and component (A2) in the anionic direct dye (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and still more preferably 95% by mass or more, but 100% by mass or less, from the viewpoint of improving the dyeability of the fiber for head accessories and obtaining the desired color tone.

[0039] The content of the anionic direct dye (A) in the dye composition is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and still more preferably 0.2% by mass or more, from the viewpoint of improving the dyeability of the fiber for headwear and obtaining the desired color tone; and is preferably 3% by mass or less, more preferably 2.0% by mass or less, still more preferably 1.5% by mass or less, and still more preferably 1.2% by mass or less, from the viewpoint of improving the formulation stability. That is, from the viewpoint of improving the dyeability of fibers for head accessories and obtaining a desired color tone, the content of the anionic direct dye (A) in the dye composition is preferably from 0.001 to 3% by mass, more preferably from 0.002 to 3% by mass, even more preferably from 0.005 to 3% by mass, still more preferably from 0.01 to 2.0% by mass, even more preferably from 0.02 to 2.0% by mass, still more preferably from 0.03 to 2.0% by mass, still more preferably from 0.05 to 2.0% by mass, still more preferably from 0.10 to 1.5% by mass, and still more preferably from 0.2 to 1.2% by mass.

[0040] The dye composition may further contain a dye other than the anionic direct dye (A). However, from the viewpoint of improving the dyeability of the fiber for head accessories and improving compatibility with the hair after dyeing, the content of the dye other than the anionic direct dye (A) in the dye composition is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.02% by mass or less, still more preferably 0.01% by mass or less, still more preferably 0.001% by mass or less, still more preferably 0.0001% by mass or less, and even more preferably 0.0001% by mass or less, and may even be 0% by mass.

[0041] <Water> The water used in the composition of the present invention is not particularly limited, and for example, ion-exchanged water, pure water, distilled water, etc. can be used. The water content in the stain composition is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and is preferably 99.999% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. That is, the water content in the stain composition is preferably 70% by mass or more and 99.999% by mass or less, more preferably 80% by mass or more and 95% by mass or less, and even more preferably 85% by mass or more and 90% by mass or less. The content of water in the dye composition may be the balance of the anionic direct dye (A).

[0042] <Lactic acid, citric acid and their salts> From the viewpoint of improving the dyeability of the fiber for head accessories and improving compatibility with dyed hair, the composition of the present invention has a total content of lactic acid, citric acid and salts thereof of 4.5% by mass or less, preferably 3.5% by mass or less, more preferably 2.5% by mass or less, even more preferably 1.5% by mass or less, still more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less, with the lower limit being 0% by mass. In this specification, even when the composition of the present invention contains a lactate or a citrate, the "total content of lactic acid, citric acid, and their salts" means the total amount converted into lactic acid and citric acid.

[0043] The salts of lactic acid and citric acid preferably include ammonium salts or metal salts, more preferably include one or more selected from the group consisting of ammonium salts, alkali metal salts, and alkaline earth metal salts, even more preferably include one or more selected from the group consisting of ammonium salts, potassium salts, sodium salts, and calcium salts, and even more preferably include one or more selected from the group consisting of ammonium salts and sodium salts.

[0044] <Organic acid or its salt> From the viewpoint of improving the dyeability of the fiber for head accessories and improving compatibility with dyed hair, the composition of the present invention preferably has a total content of organic acids and organic acid salts of 4.5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less. The lower limit is 0% by mass. The organic acids and organic acid salts referred to here include the aforementioned lactic acid, citric acid, and salts thereof. The content of organic acid salts refers to the amount converted into organic acid.

[0045] Examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; polycarboxylic acids such as polyglutamic acid; hydroxycarboxylic acids other than lactic acid and citric acid, such as glycolic acid, hydroxyacrylic acid, glyceric acid, malic acid, and tartaric acid; and acidic amino acids such as glutamic acid and aspartic acid. Salts of these organic acids preferably include ammonium salts or metal salts, more preferably one or more selected from the group consisting of ammonium salts, alkali metal salts, and alkaline earth metal salts, even more preferably one or more selected from the group consisting of ammonium salts, potassium salts, sodium salts, and calcium salts, and even more preferably one or more selected from the group consisting of ammonium salts and sodium salts.

[0046] <Other ingredients> In addition to the above components, the dye composition may contain penetration enhancers, antioxidants, fragrances, preservatives, thickeners, pH adjusters, surfactants, feel improvers, etc. Among these, it is preferable that the composition of the present invention contains at least a penetration enhancer, from the viewpoint of improving the dyeability of fibers for head accessories.

[0047] (penetration enhancer) Examples of the penetration enhancer include one or more selected from the group consisting of alkylene carbonates such as propylene carbonate; aromatic ring-containing alcohols such as benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, γ-phenylpropyl alcohol, cinnamic alcohol, p-methylbenzyl alcohol, α,α-dimethylphenethyl alcohol, and α-phenylethanol; and lactones such as γ-valerolactone and γ-caprolactone. Among these, the penetration enhancer preferably contains one or more selected from the group consisting of alkylene carbonate and aromatic ring-containing alcohol, more preferably contains one or more selected from the group consisting of propylene carbonate and benzyl alcohol, and even more preferably contains propylene carbonate.

[0048] When the dye composition contains a penetration enhancer, the content of the penetration enhancer in the composition is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, still more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of improving the dyeability of the fiber for head accessories. Furthermore, from the viewpoint of improving compatibility with the dyed hair, the content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. That is, the content of the penetration enhancer in the dye composition is preferably 1% by mass or more to 30% by mass or less, more preferably 2% by mass or more to 30% by mass or less, even more preferably 3% by mass or more to 30% by mass or less, still more preferably 5% by mass or more to 30% by mass or less, still more preferably 10% by mass or more to 25% by mass or less, and even more preferably 10% by mass or more to 20% by mass or less.

[0049] From the viewpoint of improving the dyeability of fibers for head accessories, the mass ratio of the penetration enhancer to the anionic direct dye (A) in the dye composition [penetration enhancer / anionic direct dye (A)] is preferably 0.3 or more, more preferably 1 or more, even more preferably 2 or more, even more preferably 5 or more, and still more preferably 8 or more. Furthermore, from the viewpoint of improving compatibility with hair after dyeing, this mass ratio [penetration enhancer / anionic direct dye (A)] is preferably 30,000 or less, more preferably 5,000 or less, even more preferably 1,000 or less, still more preferably 100 or less, still more preferably 60 or less, and still more preferably 30 or less. That is, this mass ratio [penetration enhancer / anionic direct dye (A)] is preferably 0.3 or more and 30,000 or less, more preferably 1 or more and 5,000 or less, even more preferably 2 or more and 1,000 or less, still more preferably 5 or more and 1000 or less, still more preferably 8 or more and 60 or less, and still more preferably 8 or more and 30 or less.

[0050] <ph> The pH of the dye composition is preferably 2.0 or higher, more preferably 2.2 or higher, and even more preferably 2.5 or higher. From the viewpoint of improving the dyeability of fibers for head accessories, the pH is preferably 6 or lower, more preferably 5 or lower, even more preferably 4 or lower, and still more preferably 3.5 or lower. That is, the pH of the dye composition is preferably 2.0 or higher and 6 or lower, more preferably 2.2 or higher and 6 or lower, even more preferably 2.2 or higher and 5 or lower, still more preferably 2.5 or higher and 4 or lower, and even more preferably 2.5 or higher and 3.5 or lower. The pH can be measured at 25°C by the method described in the Examples.

[0051] <Dosage form, manufacturing method> The formulation of the dye composition is not particularly limited, and can be liquid, paste, cream, gel, foam, spray, wax, or other formulation depending on the product form, with liquid being preferred. The method for producing the dye composition is not particularly limited, and the dye composition can be produced by mixing the components by any method. The dye composition of the present embodiment can be preferably obtained by mixing a medium (e.g., water) and other components under heating (e.g., 60 to 80°C) to dissolve them uniformly, and then adding the anionic direct dye (A) and mixing them uniformly.

[0052] <Fiber for headdress products> The fibers for head accessories to be dyed with the dye composition of the present invention are fibers other than human hair and may be either naturally-derived or synthetic, although naturally-derived fibers are preferred. Naturally-derived fibers refer to fibers collected from natural plants and animals, or artificially produced fibers made from proteins derived from collagen, casein, soybeans, peanuts, corn, silk waste, silk proteins (e.g., silk fibroin), etc., or polymers or oligomers such as polysaccharides. Among these, artificially produced fibers made from animal hair, or polymers or oligomers such as proteins or polysaccharides derived from keratin, collagen, casein, soybeans, peanuts, corn, silk waste, silk proteins (e.g., silk fibroin), etc., are preferred. Regenerated protein fibers made from proteins derived from keratin, collagen, casein, soybean proteins, peanut proteins, corn proteins, silk proteins (e.g., silk fibroin), etc. are more preferred. Regenerated protein fibers, such as regenerated collagen fibers made from collagen and regenerated silk fibers made from silk fibroin, are even more preferred, with regenerated collagen fibers being even more preferred. Regenerated collagen fibers can be produced by known techniques. The composition of regenerated collagen fibers does not need to be 100% collagen, and they may contain natural polymers, synthetic polymers, additives, etc. to improve quality. Furthermore, regenerated collagen fibers may be post-processed or post-treated. Filaments are preferred as the form of regenerated collagen fibers. Filaments are generally removed from bobbins or boxes. In addition, filaments emerging from the drying process in the regenerated collagen fiber production process can also be used directly.

[0053] Examples of synthetic fibers include fibers containing a synthetic resin as a main component. From the viewpoint of ease of production of synthetic fibers and of obtaining a texture similar to that of human hair, the synthetic resin is preferably a thermoplastic resin, more preferably one or more selected from the group consisting of polyester resin, polyamide resin, polyimide resin, polyamideimide resin, vinyl chloride resin, polycarbonate resin, polyphenylene sulfide resin, and modacrylic resin (a copolymer of acrylonitrile and vinyl chloride). Here, the term "main component" refers to a component whose content in the synthetic fiber is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and even more preferably 90% by mass or more, but not more than 100% by mass. In addition to the above synthetic resins, the synthetic fibers may further contain various additives such as flame retardants, flame retardant auxiliaries, light or heat stabilizers, fluorescent agents, antioxidants, antistatic agents, and ultraviolet absorbers, as long as the effects of the present invention are not impaired.

[0054] The fibers for head accessories to be dyed with the dye composition of the present invention preferably contain the regenerated protein fibers, more preferably regenerated collagen fibers. From the viewpoint of improving the dyeability of the fibers for head accessories and improving compatibility with hair after dyeing, the fibers for head accessories to be dyed with the dye composition of the present invention are more preferably fibers consisting of only regenerated collagen fibers.

[0055] [Dyeing method] The present invention provides a method for dyeing fibers for head accessories, which comprises a step of applying the above-mentioned fiber dye composition for head accessories to the fibers for head accessories. In the following description, the method for dyeing fibers for head accessories will also be simply referred to as the "dyeing method of the present invention." The dye composition, the fiber for head accessories, and the preferred embodiments thereof are the same as those described above.

[0056] The method for applying the dye composition to the fiber for head accessories may be any method that can bring the dye composition into contact with the fiber for head accessories, and examples thereof include a method of applying the composition to the fiber for head accessories in a dry or wet state, and a method of immersing the fiber for head accessories in the composition. Among the above, the method of applying the dye composition to the fiber for head accessories in a dry state or the method of immersing the fiber for head accessories in a dry state in the dye composition is preferred. From the viewpoint of a balance between dyeability, fastness, and economy, the amount of dye composition applied to the fiber for headwear products is preferably such that the bath ratio (dry mass of fiber for headwear products:mass of dye composition) is 1:0.2 to 1:500, when the mass of the fiber after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as the dry mass.

[0057] When the dye composition is applied to the fiber for head accessories, the amount of the dye composition to be applied to the fiber for head accessories is, from the viewpoint of balancing dyeability and economy, preferably 1:0.2 to 1:200, even more preferably 1:0.2 to 1:100, still more preferably 1:0.2 to 1:50, even more preferably 1:0.2 to 1:20, even more preferably 1:0.5 to 1:10, even more preferably 1:0.5 to 1:5, and even more preferably 1:0.8 to 1:3 in terms of the bath ratio (dry mass of fiber for head accessories:mass of dye composition), when the mass of the fiber after conditioning at 20°C and a relative humidity of 65% for 24 hours is taken as the dry mass. Furthermore, when immersing fibers for head accessories in the dye composition, when the mass of the fibers after conditioning for 24 hours at 20°C and a relative humidity of 65% is taken as the dry mass, the bath ratio (dry mass of fibers for head accessories:mass of dye composition) is more preferably 1:2 to 1:500, even more preferably 1:3 to 1:250, still more preferably 1:5 to 1:100, still more preferably 1:10 to 1:50, and even more preferably 1:10 to 1:20.

[0058] When the dye composition is applied to a fiber for a head accessory, the application time is preferably 10 seconds or more, more preferably 20 seconds or more, from the viewpoint of further improving dyeability, and is preferably 10 minutes or less, more preferably 5 minutes or less, from the viewpoint of improving productivity and improving compatibility of the fiber for a head accessory with hair after dyeing. The application time is preferably 10 seconds or more and 10 minutes or less, more preferably 20 seconds or more and 5 minutes or less. After applying the dye composition to the fiber for head accessories, it is preferable to further carry out a step of leaving it to stand. The leaving time in this case is preferably 1 minute or more, more preferably 3 minutes or more, and even more preferably 5 minutes or more, from the viewpoint of further improving dyeability, and is preferably 1 hour or less, more preferably 30 minutes or less, from the viewpoint of improving productivity and improving compatibility of the fiber for head accessories with hair after dyeing. That is, the leaving time is preferably 1 minute or more and 1 hour or less, more preferably 3 minutes or more and 30 minutes or less, and even more preferably 5 minutes or more and 30 minutes or less.

[0059] When regenerated collagen fibers are immersed in the dye composition, the immersion time is preferably 10 seconds or more, more preferably 30 seconds or more, from the viewpoint of further improving dyeability, and is preferably 3 hours or less, more preferably 2 hours or less, and even more preferably 1 hour or less, from the viewpoint of improving productivity and improving compatibility of the dyed head accessory fiber with the hair. That is, the immersion time is preferably 10 seconds or more and 3 hours or less, more preferably 30 seconds or more and 2 hours or less, and even more preferably 30 seconds or more and 1 hour or less.

[0060] The temperature at which the dye composition is applied to the fiber for head accessories is not particularly limited, but from the viewpoint of improving the handleability of the dye composition and improving the compatibility of the fiber for head accessories with the hair after dyeing, it is preferably 40°C or lower, more preferably 35°C or lower. Furthermore, from the viewpoint of further improving dyeability, it is preferably 5°C or higher, more preferably 10°C or higher. That is, the temperature is preferably 5°C or higher and 40°C or lower, more preferably 10°C or higher and 35°C or lower.

[0061] The dyeing method of the present invention preferably includes a step of rinsing the dye composition applied to the headwear fiber after applying the dye composition to the headwear fiber (hereinafter also referred to simply as the "rinsing step"). The rinsing step is carried out, for example, by rinsing the dye composition applied to the headwear fiber with water. The temperature of the water is not particularly limited, but warm water of 35 to 45°C is preferred.

[0062] The dyeing method of the present invention preferably includes a step of drying the fiber for head ornament products (hereinafter also simply referred to as a "drying step") after applying the dye composition to the regenerated collagen fibers, or after the rinsing step, if any. The step of drying the fiber for head ornament products is a step of reducing the moisture content of the fiber for head ornament products, and includes, for example, towel drying, drying with a dryer (cold air or hot air), air drying, and a combination of two or more of these drying treatments to actively reduce the moisture content of the fiber for head ornament products.

[0063] [Colored fibers for headdress products, headdress products] The present invention further provides a colored fiber for head accessories dyed with the fiber dye composition for head accessories, and a head accessory comprising the colored fiber for head accessories. The colored fiber for headwear is the fiber for headwear colored with the anionic direct dye (A), and is preferably obtained by applying the dye composition to the fiber for headwear using the dyeing method of the present invention. The colored fiber for head accessories can be suitably used for head accessories. The head accessories may contain the colored fiber for head accessories at least in part, and may contain the colored fiber for head accessories and human hair.

[0064] With respect to the above-mentioned embodiments, the present invention discloses the following.

[0065] <1> A fiber dye composition for headwear products, comprising an anionic direct dye (A) and water, and having a total content of lactic acid, citric acid and salts thereof of 4.5 mass % or less.

[0066] <2> A method for dyeing fibers for head accessories, comprising a step of applying a fiber dye composition for head accessories, which contains an anionic direct dye (A) and water, and has a total content of lactic acid, citric acid and salts thereof of 4.5 mass% or less, to the fibers for head accessories.

[0067] <3> The anionic direct dye (A) comprises one or more anionic direct dyes selected from the group consisting of the following components (A1) and (A2): <1> The fiber dye composition for head accessories described above, or <2> The dyeing method described. (A1) An anionic direct dye having a sulfonic acid group and satisfying at least one of the following (1) and (2): (1) Molecular weight of 500 or more (2) When the molecular weight is Mw, the difference (ab) between the number of sulfonic acid groups (a) and the number of cationic sites (b) divided by Mw [(ab) / Mw] is 0.0010 or more. (A2) One or more selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16 <4> The molecular weight of the component (A1) (1) is 500 or more and 1500 or less, The [(ab) / Mw] of the component (A1) in (2) is 0.0010 or more and 0.0050 or less. The aforementioned <3> The fiber dye composition for head accessories described above, or <3> The dyeing method described. <5> The molecular weight of the component (A1) (1) is 520 or more and 700 or less, The [(ab) / Mw] of the component (A1) in (2) is 0.0015 or more and 0.003 or less. The aforementioned <3> or <4> The fiber dye composition for head accessories described above, or <3> or <4> The dyeing method described.

[0068] <6> The anionic direct dye (A) comprises one or more anionic direct dyes selected from the group consisting of the following components (A1) and (A2): <1> , and <3> ~ <5> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <5> The dyeing method according to any one of the above. (A1) Acid Black 52 (Color Index No.15711), Acid Green 1 (Color Index No.10020), Food Black 1 (Color Index No.28440), Food Green 3 (Color Index No.42053), Acid Green 5 (Color Index No.42095), Acid Blue 9 (Color Index No.42090), Acid Blue 5 (Color Index No.42052), Acid Green 3 (Color Index No.42085), Acid Green 25 (Color Index No.61570), Acid Blown 13 (Color Index No.10410), Acid Red 52 (Color Index No.45100), Acid Black 1 (Color Index No.20470), Acid Red 18 (Color Index No.16255), Acid Red 27(Color Index one or more selected from the group consisting of Acid Blue 3 (Color Index No. 16185), Acid Green 50 (Color Index No. 44090), Acid Red 73 (Color Index No. 27290), Acid Blue 1 (Color Index No. 42045), Acid Violet 43 (Color Index No. 60730), Acid Yellow 36 (Color Index No. 13065), Acid Yellow 1 (Color Index No. 10316), Acid Orange 7 (Color Index No. 15510), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102). (A2) One or more selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16

[0069] <7> The anionic direct dye (A) comprises one or more anionic direct dyes selected from the group consisting of the following components (A1) and (A2): <1> , <3> ~ <6> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <6> The dyeing method according to any one of the above. (A1) One or more selected from the group consisting of Acid Blue 9 (Color Index No. 42090), Acid Red 52 (Color Index No. 45100), Acid Violet 43 (Color Index No. 60730), and Acid Orange 7 (Color Index No. 15510) (A2) One or more selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16

[0070] <8> The content of the anionic direct dye (A) in the fiber dye composition for headwear is 0.10% by mass or more and 1.5% by mass or less. <1> , <3> ~ <7> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <7> The dyeing method according to any one of the above. <9> The content of the anionic direct dye (A) in the fiber dye composition for headwear is 0.2% by mass or more and 1.2% by mass or less. <1> , <3> ~ <8> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <8> The dyeing method according to any one of the above.

[0071] <10> The total content of lactic acid, citric acid and salts thereof in the fiber dye composition for headwear products is 2.5 mass% or less. <1> , <3> ~ <9> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <9> The dyeing method according to any one of the above. <11> The total content of lactic acid, citric acid and salts thereof in the fiber dye composition for headwear products is 1.5 mass% or less. <1> , <3> ~ <10> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <10> The dyeing method according to any one of the above. <12> The total content of organic acids and organic acid salts in the fiber dye composition for headwear products is 3% by mass or less. <1> , <3> ~ <11> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <11> The dyeing method according to any one of the above. <13> The total content of organic acids and organic acid salts in the fiber dye composition for headwear products is 2% by mass or less. <1> , <3> ~ <12> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <12> The dyeing method according to any one of the above.

[0072] <14> The fiber dye composition for headwear further contains one or more penetration enhancers selected from alkylene carbonates and aromatic ring-containing alcohols. <1> , <3> ~ <13> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <13> The dyeing method according to any one of the above. <15> The fiber dye composition for headwear further contains one or more penetration enhancers selected from propylene carbonate and benzyl alcohol. <1> , <3> ~ <14> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <14> The dyeing method according to any one of the above. <16> The total content of the penetration enhancer in the fiber dye composition for headwear products is 10% by mass or more and 25% by mass or less. <14> or <15> The fiber dye composition for head accessories described above, or <14> or <15> The dyeing method described. <17> The mass ratio of the penetration enhancer to the anionic direct dye (A) in the dye composition [penetration enhancer / anionic direct dye (A)] is 8 or more and 60 or less. <13> ~ <16> The fiber dye composition for head accessories according to any one of the preceding claims, or <13> ~ <16> The dyeing method according to any one of the above. <18> The mass ratio of the penetration enhancer to the anionic direct dye (A) in the dye composition [penetration enhancer / anionic direct dye (A)] is 8 or more and 30 or less. <13> ~ <17> The fiber dye composition for head accessories according to any one of the preceding claims, or <13> ~ <17> The dyeing method according to any one of the above.

[0073] <19> The pH of the dye composition is 4 or less. <1> , <3> ~ <18> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <18> The dyeing method according to any one of the above. <20> The pH of the dye composition is 2.5 or more and 3.5 or less. <1> , <3> ~ <19> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <19> The dyeing method according to any one of the above.

[0074] <21> The fiber for headwear products contains recycled protein fiber. <1> , <3> ~ <20> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <20> The dyeing method according to any one of the above. <22> The fiber for headwear products contains regenerated collagen fiber. <1> , <3> ~ <21> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <21> The dyeing method according to any one of the above. <23> The fiber for head accessories is a fiber consisting of only regenerated collagen fiber. <1> , <3> ~ <22> The fiber dye composition for head accessories according to any one of the preceding claims, or <2> ~ <22> The dyeing method according to any one of the above.

[0075] <24> The aforementioned <1> , <3> ~ <23> A colored fiber for head accessories dyed using the fiber dye composition for head accessories described in any one of the above. <25> The fiber for headwear products contains regenerated collagen fiber. <24> The fiber for colored headwear products described in 1. <26> A headdress product containing the fiber for a colored headdress product described in <24> or <25> above.

Example

[0076] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the scope of the examples. In this example, various measurements and evaluations were carried out by the following methods.

[0077] <pH measurement> Using a pH meter (F-72, manufactured by Horiba, Ltd.), the pH at 25 °C was measured.

[0078] In the evaluation of this example, the regenerated collagen fibers were purchased in the form of a commercially available extension product of regenerated collagen fibers manufactured by Kaneka Corporation, and the fibers were cut therefrom and divided into small bundles of hair for use in the evaluation. In this evaluation, in the extension product, Ultima 100% was indicated as the fiber type, and white with a color number of 30 and a straight shape was used.

[0079] <Preparation of Dye Composition for Regenerated Collagen Fibers> Examples 1 to 6, Comparative Examples 1 to 2 Each component other than sodium hydroxide shown in Table 2 was blended at the blending ratio described in Table 2 and mixed until uniform. Further, the pH was adjusted to 3.0 using sodium hydroxide to prepare a dye composition for regenerated collagen fibers.

[0080] <Evaluation of Dye Composition for Regenerated Collagen Fibers> Examples 7 to 12, Comparative Examples 3 to 4 Using the obtained dye composition, the dyeability of the fibers and the affinity to the hair were evaluated by the following method. The results are shown in Table 2.

[0081] <Dyeability (Color difference ΔE before and after dyeing * ab)> (Dyeing process) A fiber bundle having a length of 10 cm and a mass of 1 g was prepared using the fibers shown in Table 2. The fiber bundle was washed with a plain shampoo having the following composition, then rinsed with warm water at 40°C, and thoroughly dried with a dryer. The hue (L0 * ,a0 * ,b0 * ) was measured using a color difference meter (CR-400, Konica Minolta, Inc.). * ,a0 * ,b0 * The values ​​were measured at six points per fiber bundle and the average value was calculated. Next, 2 g of the dye composition was applied to the fiber bundle, which was then placed in a glass Petri dish. The opening was covered with aluminum foil and the fiber bundle was left floating in a water bath (UCT-1000, AS ONE Corporation) set to 30°C for 30 minutes (the bath ratio (dry mass of fiber:mass of dye composition) was 1:2, where the dry mass was the mass of fiber after conditioning for 24 hours at 20°C and a relative humidity of 65%). After leaving for 30 minutes, the fiber bundle was rinsed with 40°C warm water for 30 seconds to wash away the dye composition, and then the fiber bundle was lathered with a plain shampoo of the following composition for 15 seconds and then rinsed with 40°C warm water for 15 seconds, this operation being repeated twice. Next, a plain conditioner of the following composition was applied for 15 seconds, and the fiber bundle was rinsed with 40°C warm water for 15 seconds, and then thoroughly dried with cold air from a dryer. The dried fiber bundle (dyed fiber bundle) was measured for hue (L1) using a color difference meter in the same manner as above. * ,a1 * ,b1 * The color difference ΔE before and after dyeing of the fiber bundle was calculated using the following formula: * ab was calculated and shown in Table 2. ΔE * A larger ab value means higher staining.

[0082] ΔE * ab=〔(L1 * -L0 * ) 2 +(a1 * -a0 * ) 2 +(b1 * -b0 * ) 2 〕 1 / 2

[0083] (Plain shampoo composition) Ingredients (mass %) Polyoxyethylene (2) lauryl ether sodium sulfate (*1) 15.5 Lauric acid diethanolamide (*2) 1.5 edetic acid tetrasodium salt 0.3 Sodium benzoate 1.43 Refined water residue Total 100.0 *1: 57.4% by mass of Emar 227 (manufactured by Kao Corporation, active ingredient 27% by mass) *2: Aminone L-02 (Kao Corporation)

[0084] (Plain conditioner composition) Ingredients (mass %) Trimethylstearylammonium chloride (*1) 1.01 Distearyldimethylammonium chloride (*2) 2.0 Propylene glycol 5.0 Cetyl alcohol (*3) 2.0 Isopropyl alcohol 0.4 Methyl parahydroxybenzoate(*4) 0.1 Refined water residue Total 100.0 *1: 3.6% by mass of Kotamin 86W (manufactured by Kao Corporation, active ingredient 28% by mass) *2: 2.7% by mass of Kotamin D86P (manufactured by Kao Corporation, active ingredient 75% by mass) *3: Kalcol 6870 (Kao Corporation) *4: Mekkinsu M (manufactured by Ueno Pharmaceutical Co., Ltd.)

[0085] <Fits well with hair> The fiber bundle of regenerated collagen fibers dyed by the method described in the "Dyeability" section above was placed on hair, and five expert monitors performed a sensory evaluation of the compatibility of the regenerated collagen fibers with the hair, including how well the regenerated collagen fibers aligned with the hair and how easily the hair could be combed. The expert monitors scored the compatibility with the hair from 5 to 1, with the number of expert monitors who scored 3 or higher representing the evaluation score. The results are shown in Table 2.

[0086] <Width change rate of fiber bundle (%)> For the fiber bundle of the regenerated collagen fibers (length 10 cm, mass 1 g), the width (W0 (cm)) was measured at a position 5 cm from the base of the fiber bundle toward the tip. Then, for the regenerated collagen fiber bundle dyed by the method described in the "Dyeability" section above, the width [W1 (cm)] was measured at a position 5 cm from the base of the fiber bundle toward the tip, and the width change rate (%) of the fiber bundle was calculated using the following formula. The results are shown in Table 2. A small width change rate of the fiber bundle indicates that the width of the fiber bundle is suppressed even after dyeing, and the alignment of the fibers with the hair is good, resulting in excellent compatibility with the hair.

[0087] Fiber bundle width change rate (%) = (W1-W0) / W0 x 100

[0088] Reference examples 1~4 Instead of regenerated collagen fibers, human hair (manufactured by Bealux Co., Ltd.), silk (Ichifuji Co., Ltd.), or cellulose fiber (Nippon Himobuton Trading Co., Ltd.) was used to prepare hair bundles for evaluation, each 10 cm long and weighing 1 g. Using these hair bundles, various evaluations were carried out in the same manner as described above. The results are shown in Table 2. The blending amounts (% by mass) shown in Table 2 are all amounts of active ingredients. Table 3 shows details of the anionic direct dyes used in Table 2 that correspond to component (A1).

[0089] [Table 2]

[0090] [Table 3]

[0091] Table 2 shows that the dye composition of the present invention exhibits similar dyeability of regenerated collagen fibers and is compatible with hair compared to the dye compositions of Comparative Example 1, which contains 5% by mass or more of lactic acid, and Comparative Example 2, which contains 5% by mass or more of citric acid. As shown in Reference Examples 1 and 2, when the subject of dyeing with a dye composition is human hair, a dye composition containing 5% by mass or more of lactic acid is preferable because it improves dyeability. Furthermore, silk and cellulose fibers are fibers used in clothing and are not normally used as fibers for head accessories, so there is no problem of compatibility with hair. This is also evident from the small width change rate (%) of the fiber bundle as shown in Reference Examples 3 and 4.

[0092] The effects of the present invention can also be achieved by using the dye compositions of Formulation Examples 1 to 6 shown in Table 4.

[0093] [Table 4] [Industrial Applicability]

[0094] According to the present invention, there can be provided a fiber dye composition for head accessories, which contains an anionic direct dye, has excellent dyeability for fibers for head accessories such as regenerated collagen fibers, does not impair ease of combing even after dyeing, and can give colored fibers that blend well with hair.< / ph>

Claims

1. A fiber dye composition for headwear products, comprising an anionic direct dye (A) and water, and having a total content of lactic acid, citric acid and salts thereof of 4.5 mass% or less.

2. 2. The fiber dye composition for headwear products according to claim 1, wherein the anionic direct dye (A) comprises one or more anionic direct dyes selected from the group consisting of the following components (A1) and (A2): (A1) An anionic direct dye having a sulfonic acid group and satisfying at least one of the following (1) and (2): (1) Molecular weight of 500 or more (2) When the molecular weight is Mw, the difference (a-b) between the number of sulfonic acid groups (a) and the number of cationic sites (b) divided by Mw [(a-b) / Mw] is 0.0010 or more. (A2) One or more selected from the group consisting of HC Blue 18, HC Red 18, and HC Yellow 16

3. The component (A1) is Acid Black 52 (Color Index No.15711), Acid Green 1 (Color Index No.10020), Food Black 1 (Color Index No.28440), Food Green 3 (Color Index No.42053), Acid Green 5 (Color Index No.42095), Acid Blue 9 (Color Index No.42090), Acid Blue 5 (Color Index No.42052), Acid Green 3 (Color Index No.42085), Acid Green 25 (Color Index No.61570), Acid Blown 13 (Color Index No.10410), Acid Red 52 (Color Index No.45100), Acid Black 1 (Color Index No.20470), Acid Red 18 (Color Index No.16255), Acid Red 27 (Color Index No.16185), Acid Blue 3 (Color Index No.42051), Acid Green 50 (Color Index No.44090), Acid Red 73 (Color Index No.27290), Acid Blue 1 (Color Index No.42045), Acid Red 184 (Color Index No.15685), Solv.Green 7 (Color Index No. 59040), Acid Red 35 (Color Index No.18065), Acid Red 14 (Color Index No.14720), Food Red 6 (Color Index No.16155), Acid Red 26 (Color Index No. 16150), Food Red 1 (Color Index No. 14700), Acid Yellow 3 (Color Index No. 47005), Acid Red 33 (Color Index No. 17200), Acid Blue 74 (Color Index No.73015)、Acid Orange 3(Color Index No.10385)、Food Yellow 3(Color Index No. 15985)、Acid Orange 24(Color Index No.20170)、Acid Violet 43(Color Index No.60730)、Acid Blue 62(Color Index No.62045)、Acid Red 88(Color Index No.15620)、Acid Yellow 11(Color Index No.18820)、Acid Yellow 36(Color Index No.13065)、Acid Yellow 1(Color Index No.10316)、Acid Orange 7(Color Index No.15510)、Acid Orange 20(Color Index No.14600)、Acid Yellow 9(Color Index No. 13015)、Acid Orange 6(Color Index No.14270)、Food Red 17(Color Index No.16035)、Acid Red 41(Color Index No.16290)、Acid Red 1(Color Index No.18050)、Acid Red 155(Color Index No.18130)、Acid Red 180(Color Index No.18736)、Acid Yellow 17(Color Index No.18965)、Acid Yellow 23(Color Index No.19140)、Acid Red 163(Color Index No.24790)、Food Black 2(Color Index No.27755)、Direct Orange 39(Color Index No.40215)、Acid Blue 7(Color Index No.42080)、Acid Green 9(Color Index No.42100)、Acid Green 22(Color Index No.42170)、Acid Blue 104(Color Index No.42735), Acid Violet 9 (Color Index No. 45190), Acid Red 50 (Color Index No. 45220), Acid Violet 50 (Color Index No. 50325), Acid Black 2 (Color Index No. 50420), Acid Blue 80 (Color Index No. 61585), Acid Blue 87 (Color Index No. 74180), Acid Red 195 (Color Index No. 18760), Acid Red 249 (Color Index No. 18134), Acid Red 131, and Acid Red 337 (Color Index No. 17102).

4. 2. The fiber dye composition for head accessories according to claim 1, wherein the total content of the organic acid and the organic acid salt in the dye composition is 4.5% by mass or less.

5. 2. The fiber dye composition for head accessories according to claim 1, wherein the content of the anionic direct dye (A) in the dye composition is 0.001% by mass or more and 3% by mass or less.

6. The fiber dye composition for headwear according to claim 1, wherein the fiber for headwear comprises recycled protein fiber.

7. The fiber dye composition for headwear products according to claim 1, wherein the fiber for headwear products comprises regenerated collagen fiber.

8. A method for dyeing fibers for head accessories, comprising a step of applying the fiber dye composition for head accessories according to any one of claims 1 to 7 to the fibers for head accessories.

9. A colored fiber for head accessories dyed with the fiber dye composition for head accessories according to any one of claims 1 to 7.

10. A headwear product comprising the colored headwear fiber according to claim 9.

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