Colored fibers, methods for manufacturing colored fibers, and textile products

Abstract

The present invention addresses the problem of providing a colored fiber having excellent heat generation suppression and fastness. The present invention also addresses the problem of providing a method for manufacturing the colored fiber, and a fiber product.　This colored fiber includes fibers and a compound represented by formula (1).

Description

[Technical Field]

[0001] This invention relates to colored fibers, a method for producing colored fibers, and textile products. [Background technology]

[0002] Recently, colored fibers are being used in a variety of fields. For example, Patent Document 1 discloses an acrylic fiber for artificial hair, which is "an acrylic fiber for artificial hair composed of an acrylic polymer, wherein the acrylic polymer contains 29.5 to 79.5% by mass of acrylonitrile, 20 to 70% by mass of vinyl chloride and / or vinylidene chloride, and 0.5 to 5% by mass of a sulfonic acid group-containing vinyl monomer, based on the total mass of the acrylic polymer, and the acrylic fiber for artificial hair contains a condensed phosphate, characterized in that the content of the condensed phosphate in the acrylic fiber for artificial hair is 0.05 to 0.57% by mass." In the above-mentioned Patent Document 1, carbon black is mainly used as a coloring agent. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2017 / 164299 [Overview of the project] [Problems that the invention aims to solve]

[0004] Incidentally, colored fibers containing carbon black (especially black fibers) have a problem where the surface temperature of the fibers rises and becomes hot when exposed to sunlight for a long time. Therefore, when colored fibers containing carbon black are used for hair purposes (such as wigs), the above problem can cause discomfort when worn, and improvement has been desired. In other words, there was a need for colored fibers (especially black fibers) that do not easily become hot even when exposed to sunlight for a long time (hereinafter also referred to as "excellent heat generation suppression"). Furthermore, a basic requirement for colored fibers is that they have excellent colorfastness (hereinafter also referred to as "excellent colorfastness").

[0005] Therefore, the object of the present invention is to provide a colored fiber that is excellent in heat suppression and durability. Furthermore, the present invention also aims to provide a method for producing colored fibers and a textile product. [Means for solving the problem]

[0006] As a result of diligent research into the above problems, the inventors have found that the above problems can be solved by the following configuration.

[0007] [1] A colored fiber comprising a fiber and a compound represented by formula (1) described later. [2] The colored fiber according to [1], wherein the fiber is an acrylic fiber composed of an acrylic polymer. [3] The above acrylic polymer Repeating unit X derived from acrylonitrile monomer, One or more repeating units Y selected from the group consisting of repeating units derived from vinylidene chloride monomers and repeating units derived from vinyl chloride monomers, It contains repeating units Z derived from a sulfonic acid group-containing vinyl monomer, The content of the above repeating unit X is 29.5 to 79.5% by mass relative to the total mass of the above acrylic polymer. The content of the above repeating unit Y is 20 to 70% by mass relative to the total mass of the above acrylic polymer. The colored fiber according to [2], wherein the content of the repeating unit Z is 0.5 to 5% by mass relative to the total mass of the acrylic polymer. [4] In the above equation (1), R 1 and R 2At least one of these represents a substituent containing the substructure represented by formula (1b) above, or R 1 and R 2 and are joined to each other to form a ring, and the ring is the X2 + (Y - A colored fiber according to any one of [1] to [3], which includes a substructure represented by ). [5] The above Y - The colored fiber according to any one of [1] to [4], wherein the anionic counterion represented by is one selected from the group consisting of sulfonimide ion, hexafluorophosphate ion, iodide ion, saccharin ion, and tosylate ion. [6] A method for producing colored fibers as described in any of [1] to [5], A method for producing colored fibers, comprising the step of wet spinning a spinning stock containing the polymer contained in the above-mentioned fiber and the compound represented by formula (1) above. [7] A method for producing colored fibers as described in any of [1] to [5], A method for producing colored fibers, comprising the step of dyeing the fibers using an aqueous solution containing the compound represented by formula (1) above. [8] A textile product containing colored fibers as described in any of [1] to [5]. [9] A textile product described in [8], which is a headwear product.

[10] The textile product according to [9], wherein the head ornament product is selected from the group consisting of hair fiber bundles, weaving, wigs, braids, toupees, hair extensions, and hair accessories. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide colored fibers with excellent heat generation suppression and durability. Furthermore, according to the present invention, a method for producing colored fibers and a textile product can be provided. [Modes for carrying out the invention]

[0009] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, "organic group" means a group containing at least one carbon atom. Furthermore, in this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. The bonding direction of the divalent group as expressed herein is not particularly limited. For example, if L in XLY is -COO-, and the position where it is bonded to the X side is *1 and the position where it is bonded to the Y side is *2, then L may be *1-O-CO-*2 or *1-CO-O-*2. In this specification, (meth)acrylate refers to acrylate and methacrylate, (meth)acrylic refers to acrylic and methacrylic, and (meth)acryloyl refers to acryloyl and methacryloyl. In this specification, the weight-average molecular weight (Mw) and dispersion (also known as molecular weight distribution) (Mw / Mn) of a polymer are defined as polystyrene-equivalent values ​​obtained using a GPC (Gel Permeation Chromatography) apparatus.

[0010] [Colored Fibers] The colored fiber of the present invention comprises a fiber and a compound represented by formula (1) described later (hereinafter also referred to as "specific colorant"). The colored fibers of the present invention, with the above configuration, do not easily experience high surface temperatures even when exposed to sunlight for extended periods (in other words, they exhibit excellent heat generation suppression). Furthermore, they also exhibit excellent fastness of specific colorants to the fibers. Although the detailed mechanism by which the colored fibers of the present invention produce the desired effect is not clear, the inventors speculate as follows. Carbon black, a black coloring agent, has absorption bands in the visible and infrared light regions, so it generates a significant amount of heat when exposed to sunlight for extended periods. On the other hand, certain coloring agents, although black coloring agents, do not have absorption bands in the infrared light region, and therefore generate significantly less heat compared to carbon black. In addition, the specific colorant has a cationic structural site in the molecule, and it is considered that the fixing property to the fiber is ensured due to this structure. According to the studies of the present inventors this time, it has been confirmed that the specific colorant exhibits excellent fixing property particularly to synthetic fibers (especially acrylic fibers such as modacrylic fibers).

[0011] Hereinafter, the colored fiber of the present invention will be described. In the following, that the heat generation inhibitory property of the colored fiber is more excellent and / or that the fastness of the specific colorant to the fiber is more excellent may also be referred to as "the effect of the present invention is more excellent".

[0012] [Compound (specific colorant) represented by formula (1)] The colored fiber of the present invention contains a compound (specific colorant) represented by formula (1).

[0013] [Chemical formula]

[0014] In formula (1), R 1 and R 2 each independently represent a hydrogen atom or a substituent. Further, R 1 and R 2 may be bonded to each other to form a ring. Of the two Xs, one represents a hydrogen atom and the other represents a group represented by the following formula (1a).

[0015] [Chemical formula]

[0016] In formula (1a), R 3 ~R 13 each independently represent a hydrogen atom or a substituent. Further, among R 3 ~R 13 , two adjacent groups may be bonded to each other to form a ring. * represents the bonding position.

[0017] However, the compound represented by formula (1) satisfies at least one of requirements 1 to 3. Requirement 1:R 1 ~R 13 At least one of these represents a substituent containing a substructure represented by the following formula (1b). Formula (1b): *-X1 + Y - In formula (1b), X1 + Y represents a cationic group. - * represents an anionic counterion. * represents the bond position. Requirement 2:R 1 and R 2 and are joined to each other to form a ring, and the above ring is X2 + (Y - Includes a substructure represented by ). X2 + This represents a cationic atom that constitutes a ring member atom of the above ring. - This represents an anionic counterion. Requirement 3:R 3 ~R 13 Of these, two adjacent groups bond to each other to form a ring, and the ring is X3 + (Y - Includes a substructure represented by ). X3 + This represents a cationic atom that constitutes a ring member atom of the above ring. - This represents an anionic counterion.

[0018] The compound represented by formula (1) (specific coloring agent) will be described in detail below. In the following, we will first describe substituents that include the substructure represented by formula (1b) as specified in Requirement 1.

[0019] In the above equation (1b), X1 + Examples of cationic groups represented by the formula (N1), the group represented by the formula (P1), the group represented by the formula (CyN1), and the group represented by the formula (CyN2).

[0020] Formula (N1): *-N + (R A)3 Formula (P1): *-P + (R B )3

[0021] In equations (N1) and (P1), R A and R B Each of these independently represents a hydrogen atom or a substituent. R A and R B The substituents represented are not particularly limited, but examples include alkyl groups and aryl groups. The alkyl group is preferably linear or branched. The alkyl group has 1 to 8 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms. The alkyl group may have further substituents. Examples of substituents include hydroxyl groups and cyano groups. The aryl group is preferably a phenyl group. The aryl group may have further substituents. Examples of substituents include alkyl groups (preferably having 1 to 6 carbon atoms), hydroxyl groups, and cyano groups. R A and R B Of these, hydrogen atoms or linear or branched alkyl groups having 1 to 3 carbon atoms are preferred, and hydrogen atoms are more preferred. In equations (N1) and (P1), * indicates a bonding position.

[0022] [ka]

[0023] In the formula (CyN1), R a1 and R a2 Each of these independently represents a hydrogen atom or a substituent. a1 R represents an alicyclic ring containing at least one cationic nitrogen atom as explicitly shown in the formula. The above alicyclic ring is R a1 and R a2 It may have other substituents. * indicates a bond position.

[0024] In the formula (CyN2), R b1 W represents a hydrogen atom or substituent. b1 R represents an aromatic ring containing at least one cationic nitrogen atom as explicitly shown in the formula. The above aromatic ring is R b1 It may have other substituents. * indicates a bond position.

[0025] In equations (CyN1) and (CyN2), R a1 , R a2 , and R b1 The substituents represented by are R in formulas (N1) and (P1) above. A and R B Examples of substituents similar to those represented by can be found, and the preferred embodiments are also the same.

[0026] In equation (CyN1), W a1 This represents an alicyclic ring containing at least one cationic nitrogen atom as explicitly shown in formula (CyN1). The number of ring members in the above-mentioned alicyclic ring is not particularly limited, but is preferably 3 to 10, more preferably 5 to 8, and even more preferably 5 to 6. The above-mentioned alicyclic ring may be a single-ring structure or a fused-ring structure in which two or more rings are fused together, but a single-ring structure is preferred. The atoms constituting the above alicyclic ring (ring member atoms) include the cationic nitrogen atom and carbon atom explicitly shown in formula (CyN1), and other heteroatoms (other heteroatoms) other than the cationic nitrogen atom explicitly shown in formula (CyN1) that may be optionally included. When the above-mentioned alicyclic ring has other heteroatoms as ring member atoms, the number of other heteroatoms is not particularly limited, and for example, 1 to 2 is preferred. Examples of other heteroatoms include sulfur atoms, oxygen atoms, nitrogen atoms, and phosphorus atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. For superior effects of the present invention, it is preferable that the ring member atoms of the alicyclic ring consist only of cationic nitrogen atoms and carbon atoms as explicitly shown in formula (CyN1).

[0027] The above alicyclic ring is R a1 and R a2It may have other substituents. The substituents are not particularly limited and include, for example, hydroxyl groups, cyano groups, alkyl groups, alkylcarbonyloxy groups (preferably with 2 to 8 carbon atoms), alkylaminocarbonyloxy groups (preferably with 2 to 8 carbon atoms), cyano groups, carbamoyl groups, alkylcarbamoyl groups (preferably with 2 to 8 carbon atoms), arylcarbamoyl groups (preferably with 7 to 11 carbon atoms, more preferably with 7 carbon atoms), and aryl groups (preferably with phenyl groups). In terms of having superior effects, the above-mentioned alicyclic ring is R a1 and R a2 It is also preferable that it does not have any substituents other than those mentioned above.

[0028] The bond position represented by * is formed by removing one hydrogen atom from the ring member atom of the alicyclic ring.

[0029] A specific example of formula (CyN1) is the group represented by the following formula (CyN1-1).

[0030] [ka]

[0031] In formula (CyN1-1), R a1 and R a2 This is R in equation (CyN1). a1 and R a2 These terms are synonymous, and the preferred modes are also the same. R a3 R represents a substituent. R may be present on the alicyclic ring as a substituent. a1 and R a2 Other substituents include those described in the section above. m represents an integer between 1 and 3, preferably 1 or 2, and more preferably 2. n represents an integer between 0 and 3, with 0 being preferred. * indicates the connection position.

[0032] Note that the bond positions indicated by * are formed by removing one hydrogen atom from the ring member atom of the alicyclic ring.

[0033] In the formula (CyN2), W b1 This represents an aromatic ring containing at least one cationic nitrogen atom as explicitly stated in the formula. The number of members in the aromatic ring described above is not particularly limited, but 3 to 10 is preferred, 5 to 8 is more preferred, and 5 to 6 is even more preferred. The aromatic ring may be a monoring structure or a fused ring structure in which two or more rings are fused, but a monoring structure is preferred. The above aromatic ring includes the cationic nitrogen atom, carbon atom, and other heteroatoms (other heteroatoms) other than the cationic nitrogen atom specified in formula (CyN2) that may be optionally included. When the above aromatic ring has other heteroatoms as ring member atoms, the number of other heteroatoms is not particularly limited, and for example, 1 to 2 is preferred. Examples of other heteroatoms include sulfur atoms, oxygen atoms, nitrogen atoms, and phosphorus atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. For superior effects of the present invention, it is preferable that the ring member atoms of the aromatic ring consist only of cationic nitrogen atoms and carbon atoms as explicitly shown in formula (CyN2).

[0034] The above aromatic ring is R b1 It may have other substituents. The substituents are not particularly limited and include, for example, hydroxyl groups, cyano groups, alkyl groups, alkylcarbonyloxy groups (preferably with 2 to 8 carbon atoms), alkylaminocarbonyloxy groups (preferably with 2 to 8 carbon atoms), cyano groups, carbamoyl groups, alkylcarbamoyl groups (preferably with 2 to 8 carbon atoms), arylcarbamoyl groups (preferably with 7 to 11 carbon atoms, more preferably with 7 carbon atoms), and aryl groups (preferably with phenyl groups). In terms of having superior effects, the above aromatic ring is R b1 It is also preferable that it does not have any substituents other than those mentioned above.

[0035] The bond position represented by * is formed by removing one hydrogen atom from the ring member atom of the aromatic ring.

[0036] A specific example of the formula (CyN2) is the group represented by the following formula (CyN2-1).

[0037] [ka]

[0038] In formula (CyN2-1), R b1 This is R in equation (CyN2). b1 This is synonymous with the same thing, and the preferred embodiment is also the same. R b2 R represents a substituent. The substituent may be an aromatic ring group. b2 Other substituents include those described in the section above. p represents an integer between 0 and 4, preferably between 0 and 2, and more preferably 0. * indicates the connection position. Note that the bond positions indicated by * are formed by removing one hydrogen atom from the ring member atom of the aromatic ring.

[0039] In the above equation (1b), Y - The anionic counterions represented by are not particularly limited, but examples include sulfonimide ions, perhalogenated Lewis acid anions, halide ions, arylsulfonic acid anions, and saccharin ions. Sulfonimide ions are Rf-SO2-N - This ion is represented by -SO2-Rf, where Rf represents a perfluoroalkyl group having 1 to 8 carbon atoms (preferably 1 to 6). Examples of anions for perhalide Lewis acids include PF6. - SbF6 - BF4 - AsF6 - , and FeCl4 - These are some examples. Examples of halide ions include Cl- , Br - , and I - etc. can be mentioned. As the anion of arylsulfonic acid, p-CH3C6H4SO3 - , and PhSO3 - etc. can be mentioned. In terms of the more excellent effects of the present invention, as the anionic counter ion represented by Y - , sulfonimide ion, hexafluorophosphate ion (PF6 - ), iodide ion (I - ), saccharin ion, and tosylate ion (p-CH3C6H4SO3 - ) are preferably one or more selected from the group consisting of.

[0040] As an example of the substituent containing the partial structure represented by formula (1b) in the above requirement 1, for example, the substituent represented by the following formula (T1) can be mentioned. Formula (T1): *-L T1 -X1 + Y - In formula (T1), X1 + and Y - are respectively synonymous with X1 + and Y - in formula (1b), and the preferred embodiments are also the same. L T1 represents a single bond or a divalent linking group. L T1 The divalent linking group represented by is not particularly limited, for example, -CO-, -O-, -S-, -SO-, -SO2-, -NR X- Examples include alkylene groups (which may be linear, branched, or cyclic; preferably having 1 to 15 carbon atoms, and more preferably 1 to 6 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one nitrogen, oxygen, or sulfur atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent arylene groups (preferably 6 to 10-membered rings, and more preferably 6-membered rings), divalent heteroarylene groups (preferably 5 to 10-membered rings having at least one nitrogen, oxygen, or sulfur atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), and divalent linking groups formed by combining several of these. The above R X Examples include a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. Furthermore, the alkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent arylene group, and the divalent heteroarylene group may have substituents.

[0041] L T1 Of these, single bonds are preferred.

[0042] Next, we will elaborate on equation (1). In formula (1), R 1 and R 2 The substituents represented by are not particularly limited, but examples include substituents and alkyl groups that include the substructure represented by formula (1b) above.

[0043] R 1 and R 2 The alkyl group represented by may be linear, branched, or cyclic. R 1 and R 2 The number of carbon atoms in the linear and branched alkyl groups represented by is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 5. Also, R 1 and R 2The cyclic alkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms is preferably 5 to 12, more preferably 5 or 6, and even more preferably 6.

[0044] R 1 and R 2 The alkyl group represented by may have further substituents. Examples of substituents include a hydroxyl group, a cyano group, a carbamoyl group, an aryl group (preferably an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group), and substituents including the substructure represented by the above formula (1b).

[0045] R 1 and R 2 Examples of alkyl groups represented by include -CH3, -C2H5, -(CH2)2CH3, -CH(CH3)2, -(CH2)3CH3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, (CH2)4CH3, -(CH2)2CH(CH3)2, (CH2)5CH3, -(CH2)7CH3, -(CH2)9CH3, and -(CH2) 11 Examples include linear or branched alkyl groups such as CH3, -CH2OCOCH3, -CH2OCOCH(CH3)2, -CH2OCOCH(C2H5)CH2CH2CH2CH3, -CH2OCONHCH(CH3)2, -CH2OH, -CH2CN, -CH2CONH2, -CH2CONHPh, and -CH2Ph ​​(where Ph represents a phenyl group).

[0046] Also, R 1 and R 2 These elements may be joined together to form a ring. R 1 and R 2 The ring formed by the bonding of these elements is not particularly limited and may be an alicyclic ring or an aromatic ring, but an alicyclic ring is preferred. Also, R 1 and R 2 The ring formed by the bonding of these elements may be a single ring structure or a fused ring structure in which two or more rings are fused together, but a single ring structure is preferred.

[0047] R 1 and R 2 The ring formed by the bonding of these two elements is X2 + (Y - It is also preferable that it includes a substructure represented by ). Here, X2 + Y represents a cationic atom that constitutes a ring member atom of the above ring. - This represents an anionic counterion.

[0048] X2 + Examples of cationic atoms represented by this include cationic nitrogen atoms (N + ) and cationic phosphorus atoms (P + Examples include cationic nitrogen atoms (N + ) is preferable. R 1 and R 2 In a ring formed by the bonding of these elements, a cationic nitrogen atom (N + ) is *-N + (R C )(R D )-*, and *-N + (R E It is preferable that the cationic phosphorus atom (P) is in one of the following forms: + ) is *-P + (R F )2-*, and *-P + (R G It is preferable that the form is )=*. C , R D , R E , R F , and R G Each of these independently represents a hydrogen atom or a substituent. C , R D , R E , R F , and R G The substituents represented by are R in formulas (N1) and (P1) mentioned above. A and R B Examples of substituents similar to those represented by are shown. * indicates the bond position. Note that *-P + (R FIn )2-*, two R F These may be the same or different. Y - The anionic counterion represented by is the Y possessed by the substituent containing the substructure represented by formula (1b) above. - Examples include those similar to the anionic counterions represented by .

[0049] R 1 and R 2 The number of ring members in the ring formed by the bonding of these elements is not particularly limited, but is preferably 3 to 10, more preferably 5 to 8, and even more preferably 5 to 6. Note, R 1 and R 2 The ring formed by the bonding of these two is X2 + (Y - If the substructure is represented by ), then at least one of the ring member atoms is the same as X2 described above. + The cationic atom represented by [this symbol] is the one in question. R 1 and R 2 The ring member atoms of the ring formed by the bonding of these two atoms are X2. + (Y - If it includes a substructure represented by ), then the above X2 + A cationic atom, a carbon atom, and the aforementioned X2 which may optionally be included. + Examples include heteroatoms other than cationic atoms represented by . R 1 and R 2 When the ring formed by the bonding of these atoms has other heteroatoms as ring member atoms, the number of other heteroatoms is not particularly limited, and for example, 1 to 2 is preferred. Examples of other heteroatoms include sulfur atoms, oxygen atoms, nitrogen atoms, and phosphorus atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. Also, R 1 and R 2 The ring formed by the bonding of these elements to each other may have substituents on the cationic atom (for example, the above R C , R D , R E , R F , and RG It may have substituents other than ). The substituents are not particularly limited and include, for example, hydroxyl groups, cyano groups, alkyl groups, alkylcarbonyloxy groups (preferably with 2 to 8 carbon atoms), alkylaminocarbonyloxy groups (preferably with 2 to 8 carbon atoms), cyano groups, carbamoyl groups, alkylcarbamoyl groups (preferably with 2 to 8 carbon atoms), arylcarbamoyl groups (preferably with 7 to 11 carbon atoms, more preferably with 7 carbon atoms), and aryl groups (preferably with phenyl groups).

[0050] R 1 and R 2 The ring member atoms of the ring formed by the bonding of these two atoms are X2. + (Y - If the substructure represented by ) is not included, there are no particular limitations, but it may consist of only carbon atoms, or carbon atoms and heteroatoms. Examples of heteroatoms include sulfur atoms, oxygen atoms, nitrogen atoms, and phosphorus atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. The number of heteroatoms in the ring is not particularly limited, for example, 1 to 2 is preferred. Furthermore, the above ring may have substituents. The substituents are not particularly limited and include, for example, a hydroxyl group, a cyano group, an alkyl group, an alkylcarbonyloxy group (preferably having 2 to 8 carbon atoms), an alkylaminocarbonyloxy group (preferably having 2 to 8 carbon atoms), a cyano group, a carbamoyl group, an alkylcarbamoyl group (preferably having 2 to 8 carbon atoms), an arylcarbamoyl group (preferably having 7 to 11 carbon atoms, more preferably 7 carbon atoms), an aryl group (preferably a phenyl group), and the like.

[0051] In terms of having superior effects, R 1 and R 2 When these elements bond to each other to form a ring, the compound represented by formula (1) is preferably the compound represented by the following formula (1A).

[0052] [ka]

[0053] In equation (1A), X is the same as X in equation (1). The above R C and R D Each of these independently represents a hydrogen atom or a substituent. C and R D The substituents represented by are R in formulas (N1) and (P1) mentioned above. A and R B Examples of substituents similar to those represented by include The above R y1 represents a substituent. The substituent is R in formula (CyN1-1). a3 This is synonymous with the substituent represented by , and the preferred embodiment is the same. q represents an integer between 1 and 3, preferably 1 or 2, and more preferably 2. s represents an integer between 1 and 3, preferably 1 or 2, and more preferably 2. r represents an integer between 0 and 3, with 0 being preferred.

[0054] In formula (1), one of the two X's represents a hydrogen atom, and the other represents the group represented by formula (1a) above. The group represented by formula (1a) will be described in detail below.

[0055] In formula (1a), R 3 ~R 7 Substituents represented by the formula (1b) above include, for example, substituents containing the substructure represented by the formula (1b), halogen atoms, -CN, -CO-OR X1 ,-O-CO-R X2 ,-CO-R X3 Examples include , and -NO2.

[0056] R X1 and R X2 Each of these independently represents an alkyl group. X3 This represents an alkyl group or an aryl group. R X1 , R X2 , and R X3The alkyl group represented may be linear, branched, or cyclic, with linear or branched being preferred. R X1 , R X2 , and R X3 The number of carbon atoms in the alkyl group represented is preferably 1 to 11, more preferably 1 to 7, and even more preferably 1 to 4. R X3 The aryl group represented is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group.

[0057] R 3 ~R 7 Examples of halogen atoms represented by include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred, and chlorine atoms being more preferred.

[0058] R 3 ~R 7 The substituents represented by the above formula (1b) include substituents containing the substructure, fluorine atoms, chlorine atoms, -CN, -NO2, and -CO-OR X1 (R x1 (where is an alkyl group having 1 to 11 carbon atoms), or -CO-R X3 (R x3 (Is preferably an alkyl group having 1 to 11 carbon atoms, or an aryl group having 6 to 11 carbon atoms), and is a chlorine atom, -CN, -NO2, -CO-OR X1 (R x1 (where is an alkyl group having 1 to 4 carbon atoms), or -CO-R X3 (R x3 (where is an alkyl group having 1 to 4 carbon atoms) is more preferred, and a chlorine atom is even more preferred. In terms of the superior effects of the present invention, in formula (1a), R 3 ~R 7 Preferably, at least one of them represents a substituent, and among them, R 3 R represents a substituent, and 4 ~R 7 It is more preferable that this represents a hydrogen atom.

[0059] In formula (1a), R 8 ~R 13 The substituents represented by are not particularly limited, and examples include substituents containing the substructure represented by formula (1b) above, hydroxyl groups, cyano groups, alkyl groups, alkylcarbonyloxy groups (preferably having 2 to 8 carbon atoms), alkylaminocarbonyloxy groups (preferably having 2 to 8 carbon atoms), cyano groups, carbamoyl groups, alkylcarbamoyl groups (preferably having 2 to 8 carbon atoms), arylcarbamoyl groups (preferably having 7 to 11 carbon atoms, more preferably 7 carbon atoms), aryl groups (preferably phenyl groups), and the like. In terms of the superior effects of the present invention, in formula (1a), R 8 ~R 13 It is preferable that this represents a hydrogen atom.

[0060] In formula (1a), R 3 ~R 13 Two adjacent groups may bond to each other to form a ring. R 3 ~R 13 The ring formed by the bonding of two adjacent groups is not particularly limited and may be an alicyclic ring or an aromatic ring. Also, R 3 ~R 13 The ring formed by the bonding of two adjacent groups may be a monoring structure or a fused ring structure in which two or more rings are fused together.

[0061] R 3 ~R 13 The ring formed by two adjacent groups bonding to each other is X3 + (Y - It is also preferable that it includes a substructure represented by ). Here, X3 + Y represents a cationic atom that constitutes a ring member atom of the above ring. - This represents an anionic counterion.

[0062] X3 + Examples of cationic atoms represented by this include cationic nitrogen atoms (N + ) and cationic phosphorus atoms (P +Examples include cationic nitrogen atoms (N + ) is preferable. R 3 ~R 13 In a ring formed by the bonding of two adjacent groups, a cationic nitrogen atom (N + ) is *-N + (R H )(R I )-*, and *-N + (R J It is preferable that the cationic phosphorus atom (P) is in one of the following forms: + ) is *-P + (R K )2-*, and *-P + (R L It is preferable that it is in one of the following forms: )=*. H , R I , R J , R K , and R L Each of these independently represents a hydrogen atom or a substituent. H , R I , R J , R K , and R L The substituents represented by are R in formulas (N1) and (P1) mentioned above. A and R B Examples of substituents similar to those represented by are shown. * indicates the bond position. Note that *-P + (R K In )2-*, two R K These may be the same or different. Y - The anionic counterion represented by is the Y possessed by the substituent containing the substructure represented by formula (1b) above. - Examples include those similar to the anionic counterions represented by .

[0063] R 3 ~R 13 The number of ring members in a ring formed by the bonding of two adjacent groups is not particularly limited, but is preferably 3 to 10, more preferably 5 to 8, and even more preferably 5 to 6. Note, R3 ~R 13 The ring formed when two adjacent groups bond to each other is X3 + (Y - If it includes a substructure represented by ), then at least one of the ring member atoms is the X3 described above. + The cationic atom represented by [this symbol] is the one in question. R 3 ~R 13 Among these, the ring member atoms of the ring formed by the bonding of two adjacent groups are X3 + (Y - If it includes a substructure represented by ), then the above X3 + A cationic atom, a carbon atom, and the aforementioned X3 which may optionally be included. + Examples include heteroatoms other than cationic atoms represented by . R 3 ~R 13 When two adjacent groups bond to each other to form a ring, and that ring has other heteroatoms as ring member atoms, the number of other heteroatoms is not particularly limited, and for example, 1 to 2 is preferred. Examples of other heteroatoms include sulfur atoms, oxygen atoms, nitrogen atoms, and phosphorus atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. Also, R 3 ~R 13 The ring formed by the bonding of two adjacent groups is a substituent that the cationic atom may have (for example, the above R H , R I , R J , R K , and R L It may have further substituents other than those other than ). The substituents are not particularly limited and include, for example, hydroxyl groups, cyano groups, alkyl groups, alkylcarbonyloxy groups (preferably with 2 to 8 carbon atoms), alkylaminocarbonyloxy groups (preferably with 2 to 8 carbon atoms), cyano groups, carbamoyl groups, alkylcarbamoyl groups (preferably with 2 to 8 carbon atoms), arylcarbamoyl groups (preferably with 7 to 11 carbon atoms, more preferably with 7 carbon atoms), and aryl groups (preferably with phenyl groups).

[0064] R 3 ~R 13 Among these, the ring member atoms of the ring formed by the bonding of two adjacent groups are X3 + (Y - If the substructure represented by ) is not included, there are no particular limitations, but it may consist of only carbon atoms, or carbon atoms and heteroatoms. Examples of heteroatoms include sulfur atoms, oxygen atoms, nitrogen atoms, and phosphorus atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. The number of heteroatoms in the ring is not particularly limited, for example, 1 to 2 is preferred. Furthermore, the above ring may have substituents. The substituents are not particularly limited and include, for example, a hydroxyl group, a cyano group, an alkyl group, an alkylcarbonyloxy group (preferably having 2 to 8 carbon atoms), an alkylaminocarbonyloxy group (preferably having 2 to 8 carbon atoms), a cyano group, a carbamoyl group, an alkylcarbamoyl group (preferably having 2 to 8 carbon atoms), an arylcarbamoyl group (preferably having 7 to 11 carbon atoms, more preferably 7 carbon atoms), an aryl group (preferably a phenyl group), and the like.

[0065] R 3 ~R 13 Examples of rings formed by the bonding of two adjacent groups include pyridinium rings.

[0066] The specific coloring agent satisfies at least one of the above requirements 1 to 3. In terms of the superior effects of the present invention, in particular, in formula (1) above, R 1 and R 2 At least one of them represents a substituent containing the substructure represented by formula (1b) above, or R 1 and R 2 and are joined to each other to form a ring, and the above ring is the above X2 + (Y - Preferably, it includes a substructure represented by ). In other words, the specific colorant satisfies requirement 1 and R 1 and R 2Preferably, at least one of them represents a substituent containing the substructure represented by formula (1b) above, or satisfies requirement 2. Furthermore, in the compounds of the present invention, it is preferable that, in order to obtain a more superior effect of the present invention, of the two X groups explicitly shown in formula (1), the X at the para position relative to the NH group explicitly shown in formula (1) represents the group represented by formula (1a), and the X at the ortho position relative to the NH group explicitly shown in formula (1) represents a hydrogen atom.

[0067] The following are some specific examples of colorants, but are not limited to these.

[0068] [ka] JPEG0007871374000008.jpg83118

[0069] The specific colorants can be synthesized according to known methods. One example of a method for synthesizing the specific colorants is the following method, which includes steps 1 to 4, similar to the method described in International Publication No. 2020 / 067063. The reagents and solvents used in steps 1 to 4 can be the same as those described in International Publication No. 2020 / 067063. Step 1: A step to obtain a condensate by condensing a ketone compound with 1,8-diaminonaphthalene. Step 2: A process in which o-substituted aniline is converted to a diazonium salt using a diazotizing agent, and then coupled with 1-naphthylamine to obtain a monoazo compound. Step 3: The monoazo compound obtained in Step 2 is converted to a diazonium salt using a diazoting agent, and then coupled with the condensate obtained in Step 1 to obtain a disazo compound. Step 4: Adding the disazo compound obtained in Step 3 to a solution (e.g., acetone solution) containing a salt (e.g., alkali metal salts and organic salts, etc.) that can release one anionic ion selected from the group consisting of sulfonimide ions, hexafluorophosphate ions, iodide ions, saccharin ions, and tosylate ions, thereby introducing an ion pair moiety into the disazo compound to obtain a specific colorant.

[0070] Step 4 may also be a step in which the disazo compound obtained in Step 3 is added to a solution containing a salt capable of releasing anionic ions, an ion pair site is introduced into the disazo compound, and then the counter-anionic species in the compound obtained by the above procedure is converted to other counter-anionic species by salt exchange to obtain a specific coloring agent.

[0071] In the colored fibers, the content of the specific coloring agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, per 100 parts by mass of fiber.

[0072] 〔fiber〕 The colored fiber of the present invention includes fibers. The fiber is not particularly limited, but it is preferably a synthetic fiber, and more preferably an acrylic fiber composed of an acrylic polymer. Examples of acrylic polymers include homopolymers of repeating units derived from acrylonitrile monomers and copolymers containing repeating units derived from acrylonitrile monomers. The copolymer containing repeating units derived from acrylonitrile monomers may be a block copolymer, a random copolymer, or an alternating copolymer. Among acrylic polymers, copolymers containing repeating units derived from acrylonitrile monomers are preferred.

[0073] The acrylic polymer is preferably one that contains repeating units derived from acrylonitrile monomers and repeating units derived from other monomers different from acrylonitrile monomers, and the content of repeating units derived from acrylonitrile monomers is less than 95% by mass of the total mass of the acrylic polymer. For superior suitability as an acrylic fiber for artificial hair, it is more preferable that the content of repeating units derived from acrylonitrile monomers in the above acrylic polymer is less than 80% by mass of the total mass of the acrylic polymer. There is no particular lower limit, but for example, it is 20% by mass or more. Examples of repeating units derived from monomers other than acrylonitrile monomers include repeating units derived from halogen-containing vinylidene monomers and repeating units derived from halogen-containing vinyl monomers. Furthermore, examples of repeating units derived from vinyl monomers other than acrylonitrile monomers, halogen-containing vinylidene monomers, and halogen-containing vinyl monomers include repeating units derived from sulfonic acid group-containing vinyl monomers.

[0074] One specific embodiment of the acrylic polymer is an embodiment that includes repeating units X derived from an acrylonitrile monomer, one or more repeating units Y selected from the group consisting of repeating units derived from halogen-containing vinylidene monomers and repeating units derived from halogen-containing vinyl monomers, and repeating units Z derived from vinyl monomers other than acrylonitrile monomers, halogen-containing vinylidene monomers, and halogen-containing vinyl monomers, wherein the content of the repeating units X is 29.5 to 79.5% by mass (preferably 34.5 to 74.5% by mass) of the total mass of the acrylic polymer, the content of the repeating units Y is 20 to 70% by mass (preferably 25 to 65% by mass) of the total mass of the acrylic polymer, and the content of the repeating units Z is 0.5 to 5% by mass (preferably 0.6 to 3% by mass) of the total mass of the acrylic polymer. The effects of the present invention are better when the repeating unit X is within the above numerical range. Furthermore, the flame retardancy is better when the repeating unit Y is within the above numerical range. In addition, the hydrophilicity is better when the other repeating units derived from vinyl monomers are repeating units derived from sulfonic acid group-containing vinyl monomers, as described later.

[0075] In halogen-containing vinyl monomers and halogen-containing vinylidene monomers, chlorine atoms are preferred as the halogen atoms. In other words, chlorine atom-containing vinyl monomers and chlorine atom-containing vinylidene monomers are preferred as halogen-containing vinyl monomers and halogen-containing vinylidene monomers.

[0076] Other vinyl monomers are preferably vinyl monomers containing sulfonic acid groups. The sulfonic acid group-containing vinyl monomer is not particularly limited as long as it is a vinyl monomer having one or more sulfonic acid groups. Examples include allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid, as well as their metal salts (e.g., alkali metal salts) and amine salts. In the acrylic polymer, the repeating units derived from the sulfonic acid group-containing vinyl monomer may be one type or two or more types.

[0077] Among the acrylic polymers, those that exhibit superior effects of the present invention are preferable, which include repeating units X derived from acrylonitrile monomer, one or more repeating units Y selected from the group consisting of repeating units derived from vinylidene chloride monomer and repeating units derived from vinyl chloride monomer, and repeating units Z derived from sulfonic acid group-containing vinyl monomer, wherein the content of the repeating units X is 29.5 to 79.5% by mass (preferably 34.5 to 74.5% by mass) of the total mass of the acrylic polymer, the content of the repeating units Y is 20 to 70% by mass (preferably 25 to 65% by mass) of the total mass of the acrylic polymer, and the content of the repeating units Z is 0.5 to 5% by mass (preferably 0.6 to 3% by mass) of the total mass of the acrylic polymer.

[0078] Furthermore, the above-mentioned acrylic fiber may also contain polymers other than acrylic polymers. Examples of other polymers include homopolymers of repeating units selected from the group consisting of repeating units derived from halogen-containing vinylidene monomers and repeating units derived from halogen-containing vinyl monomers.

[0079] [Fiber treatment agent] Colored fibers are preferably treated with a fiber treatment agent, as this provides a superior tactile feel. As fiber treatment agents, known oils such as anionic surfactants like phosphate ester salts and sulfate ester salts; cationic surfactants like quaternary ammonium salts and imidazolium salts; nonionic surfactants such as ethylene oxide and / or propylene oxide adducts of oils and fats and polyhydric alcohol partial esters; animal and vegetable oils and fats; mineral oils; fatty acid esters; and silicone-based surfactants such as amino-modified silicones can be used. The fiber treatment agent may be used individually or in combination of two or more types.

[0080] [Other additives] Colored fibers may contain other additives to improve fiber properties as needed. Examples of additives include titanium dioxide; silicon dioxide; gloss modifiers such as esters and ethers of cellulose derivatives including cellulose acetate; colorants such as organic pigments, inorganic pigments, and dyes; stabilizers to improve lightfastness and heat resistance; fiber consolidators such as urethane polymers and cationic ester polymers to improve processability during braiding or twisting; inorganic or organic deodorants to capture isovaleric acid, an odor component emitted from the scalp; and functional agents such as fragrances to impart citrus or other scents to artificial hair fibers. In terms of improving the blackness of the hue of colored fibers, it is also preferable to use a specific coloring agent in combination with a red dye.

[0081] [Method for manufacturing colored fibers] [Method for manufacturing colored fibers 1] Colored fibers can be produced by a manufacturing method that includes a step of wet spinning a spinning stock containing a polymer (for example, the acrylic polymer described above) and a specific coloring agent. Preferably, the spinning stock contains a polymer (for example, the acrylic polymer described above), a specific coloring agent, and a solvent. The solvent is not particularly limited, and any suitable solvent for the polymer contained in the fiber (for example, the acrylic polymer mentioned above) can be used as appropriate. Examples of solvents include organic solvents such as dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and acetone. The spinning solution may contain water. In particular, when dimethyl sulfoxide is used as the organic solvent, void formation can be further suppressed. The water content is small, for example, 1.5 to 4.8% by mass. Furthermore, it is preferable that the spinning solution contains an epoxy group-containing compound. When the spinning solution contains an epoxy group-containing compound, odor, discoloration of the fibers due to heat, and devitrification of the fibers due to hot water can be suppressed. In particular, when dimethyl sulfoxide is used as the organic solvent, the generation of malodorous components due to the decomposition of dimethyl sulfoxide when the colored fibers are heated can be suppressed more effectively. The content of the epoxy group-containing compound in the spinning solution is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more, per 100 parts by mass of the polymer contained in the fiber (e.g., the acrylic polymer mentioned above). The upper limit of the epoxy group-containing compound content is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the polymer contained in the fiber (e.g., the acrylic polymer mentioned above), in terms of superior spinnability, fiber quality, and cost.

[0082] Examples of epoxy group-containing compounds that can be used include glycidyl methacrylate-containing polymers, glycidyl acrylate-containing polymers, epoxidized vegetable oils, glycidyl ether-type epoxy resins, glycidyl amine-type epoxy resins, glycidyl ester-type epoxy resins, and cyclic aliphatic-type epoxy resins. In the spinning solution, the epoxy group-containing compound may be used alone or in combination of two or more types.

[0083] The epoxy group-containing compound is preferably one or more selected from the group consisting of glycidyl methacrylate-containing polymers and glycidyl acrylate-containing polymers, and more preferably polyglycidyl methacrylate, in terms of superior epoxy equivalent (mass of resin containing one equivalent of epoxy groups), suppression of fiber discoloration, solubility in organic solvents, and reduction of elution into the spinning bath. The weight-average molecular weight of the epoxy group-containing compound is not particularly limited and can be appropriately determined, for example, by considering its solubility in organic solvents and its elution into the spinning bath. When the epoxy group-containing compound is one or more selected from the group consisting of glycidyl methacrylate-containing polymers and glycidyl acrylate-containing polymers, for example, it is preferable that the weight-average molecular weight is 3,000 or more in terms of superior reduction of elution into the spinning bath, and it is preferable that the weight-average molecular weight is 100,000 or less in terms of superior solubility in organic solvents.

[0084] The spinning solution may contain other additives to improve fiber properties, if necessary. Examples of additives include titanium dioxide; silicon dioxide; gloss modifiers such as esters and ethers of cellulose derivatives including cellulose acetate; colorants such as organic pigments, inorganic pigments, and dyes; and stabilizers to improve lightfastness and heat resistance.

[0085] The process of wet spinning the spinning solution preferably includes at least a coagulation step, a washing step, and a drying step. The process of wet spinning the raw material may also preferably include a bath stretching step before the washing step, or after the washing step but before the drying step. It is also preferable that the process of wet spinning the spinning solution includes an oil application step before the drying step. The process of wet spinning the raw material may also preferably include a stretching process and a heat relaxation process after the drying process.

[0086] First, in the coagulation process, the spinning solution is discharged through a spinning nozzle into a coagulation bath and coagulated to form yarn (also referred to as coagulated yarn). By appropriately adjusting the cross-sectional shape and size of the spinning nozzle, as well as spinning conditions such as the spinning speed and nozzle draft, colored fibers having a predetermined cross-sectional shape and size can be obtained. For the coagulation bath, an aqueous solution of a good solvent, such as acetone, with a concentration of 25-70% by mass can be used. The temperature of the coagulation bath is preferably 5-40°C. If the organic solvent concentration of the coagulation bath is too low, coagulation will occur too quickly, resulting in a coarse coagulation structure and a tendency to form voids inside the fibers.

[0087] Next, in the bath stretching process, it is preferable that the colored fibers (coagulated yarns) be stretched in a stretching bath (also referred to as primary stretching). The stretching bath can be an aqueous solution with a lower concentration of a good solvent such as acetone than that of the coagulation bath. The temperature of the stretching bath is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. There are no particular restrictions on the stretching ratio, but from the viewpoint of increasing the strength and productivity of the fibers, 2 to 8 times is preferred. When primary stretching is performed using a water bath, the bath stretching process may be performed after the water washing process described later, or primary stretching and water washing may be performed simultaneously.

[0088] Next, in the washing process, the colored fibers are washed with hot water at 30°C or higher to remove good solvents such as acetone from the colored fibers. Alternatively, the coagulated yarn may be guided from the coagulation bath to hot water at 30°C or higher, and the bath stretching process and the washing process may be performed simultaneously. In the washing process, for example, using hot water at 70°C or higher makes it easier to remove good solvents such as acetone from the colored fibers.

[0089] In the oil application process, an oil solution is used, which is obtained by dissolving or dispersing a fiber treatment agent in water. Specifically, it is preferable to introduce a predetermined concentration of fiber treatment agent into an oil tank and immerse the yarn that has undergone the water washing process in it to apply the fiber treatment agent to the colored fibers. The temperature of the oil tank is not particularly limited, but for example, it should be 40°C or higher, and preferably 40 to 80°C. The immersion time is not particularly limited, but for example, it should be 1 to 10 seconds, and preferably 1 to 5 seconds. The oil solution may contain other additives to improve the fiber properties, if necessary.

[0090] Next, in the drying process, the colored fibers after being treated with the fiber treatment agent are dried. The drying temperature is not particularly limited, but for example, it is 110 to 190°C. The dried fibers may then be further stretched (secondary stretching) as needed. The stretching temperature for secondary stretching is not particularly limited, but for example, it is 110 to 190°C. The stretching ratio is not particularly limited, but for example, 1 to 4 times is preferred. The total stretching ratio, including bath stretching before drying, is preferably 2 to 12 times.

[0091] The fibers obtained by drying or further stretching after drying are preferably further relaxed in a heat relaxation treatment step. The relaxation rate is not particularly limited, but for example, 5% or more is preferred, and 10 to 30% is more preferred. The heat relaxation treatment is preferably carried out at a high temperature, for example, in a dry heat atmosphere or a superheated steam atmosphere at 150 to 200°C.

[0092] The single fiber fineness of the colored fibers is preferably 10 to 100 dtex, and more preferably 20 to 95 dtex, in terms of suitability for use as artificial hair.

[0093] [Method for manufacturing colored fibers 2] Colored fibers can also be produced by a manufacturing method that includes a step of dyeing the fibers using an aqueous solution containing a specific coloring agent. The concentration of the specific coloring agent is not particularly limited, but is preferably 5.0% by mass or less, and 0.05 to 3.0% by mass, relative to the total mass of the fiber. Furthermore, the temperature of the aqueous solution is not particularly limited, for example, 50 to 100°C, with 70 to 100°C being preferred. The immersion time is not particularly limited, for example, within 180 minutes, with 10 to 120 minutes being preferred.

[0094] It is preferable to carry out a drying step after the dyeing step described above. The drying temperature is not particularly limited, but for example, it is 30 to 200°C, and preferably 50 to 180°C. The dried fibers may then be further stretched (secondary stretching) if necessary.

[0095] The single fiber fineness of the colored fibers is preferably 10 to 100 dtex, and more preferably 20 to 95 dtex, in terms of suitability for use as artificial hair.

[0096] [Uses of colored fibers] There are no particular restrictions on the use of colored fibers, and they can be used in various textile products. Examples of textile products include hair fiber bundles, weaving, wigs, braids, toupees, hair extensions, and other headwear products such as hair accessories. When colored fibers are applied to headwear products, other artificial hair fibers may be included in addition to the colored fibers. Other artificial hair fibers are not particularly limited, but examples include polyvinyl chloride fibers, nylon fibers, polyester fibers, and regenerated collagen fibers. [Examples]

[0097] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0098] [Examples of synthesis of specific colorants: Synthesis of cationic dye 1 and cationic dye 2] Cationic dyes 1 and 2 were synthesized according to the following procedure.

[0099] [ka]

[0100] [Synthesis of intermediate (C)] In a 2 L three-necked flask, 79.1 g (500 mmol) of 1,8-naphthalenediamine (A in the synthesis diagram, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 500 mL of ethanol were added. Then, under ice cooling, 7.9 g (81 mmol) of concentrated sulfuric acid (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added dropwise while maintaining the internal temperature below 40°C. To this suspension, 56.6 g (500 mmol) of 1-methyl-4-piperidone (B in the synthesis diagram, manufactured by Fujifilm Wako Chemical Co., Ltd.) was injected, and the mixture was reacted at an internal temperature of 85°C for 2 hours. The reaction mixture was cooled to room temperature (25°C), and 500 mL of ethyl acetate and 324 mL of 0.5 mol / L aqueous sodium hydroxide solution were slowly added dropwise. After stirring at room temperature for 15 minutes, the aqueous layer was removed. Next, 300 ml of water was added, and the mixture was stirred at room temperature for 15 minutes to remove the aqueous layer. The same procedure was repeated once more. 50 g of sodium sulfate was added to the resulting organic layer and allowed to stand at room temperature for 15 minutes. After removing the sodium sulfate, the solvent was removed by distillation to obtain the intermediate (C in the synthesis diagram), which was a brownish solid (yield 122 g, yield 95%).

[0101] [Synthesis of pigments] <Preparation of diazonium salt solution> In a 500 ml three-necked flask, 20.4 g (64 mmol) of the hydrochloride salt of the monoazo compound (D in the synthesis diagram), 74 mL of water, and 147 mL of acetic acid (Fujifilm Wako Pure Chemical Industries, reagent grade) were added, and the internal temperature was cooled to 5°C. Carefully, 14.8 mL (213 mmol) of 85% aqueous phosphoric acid solution (Fujifilm Wako Pure Chemical Industries, reagent grade) was added dropwise at an internal temperature of 10°C or below, and then an aqueous solution of 4.9 g (71 mmol) of sodium nitrite (Fujifilm Wako Pure Chemical Industries, reagent grade) dissolved in 10 mL of water was slowly added dropwise while maintaining the internal temperature at 0-5°C. After reacting at 0-5°C for 1 hour, 0.68 g (7 mmol) of sulfuric acid amidosulfate (Fujifilm Wako Pure Chemical Industries) was carefully added, and the mixture was stirred for 15 minutes.

[0102] <Preparation of pigment precursors> Separately, 18.5 g (71 mmol) of the previously prepared intermediate (C in the synthesis diagram) was added to 210 mL of acetone (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in a 1 L three-necked flask, and the internal temperature was cooled to 5 °C. Then, while maintaining the internal temperature at 5-10 °C, the previously prepared diazonium salt solution was slowly added dropwise, and the reaction was carried out at 0-10 °C for 30 minutes, followed by a reaction at 15-20 °C for 30 minutes. 580 mL of acetone was then added dropwise, and the precipitated crystals were filtered off by suction filtration and washed with acetone. The resulting wet cake was purified by column chromatography using an ethyl acetate / methanol solvent system to obtain a dark green, glossy crystalline pigment precursor (E in the synthesis diagram) (yield 9.6 g, yield 27%).

[0103] Pigment precursor: 1 H-NMR (DMSO-d6): 1.83 (brs, 4H), 2.35 (s, 3H), 6.70 (d×2, 2H), 6.83 (s, 1H), 7.42 (t, 1H), 7.58 (m, 2H), 7 .78(d, 1H), 7.82(m, 2H), 7.96(d, 1H), 8.05(d, 3H), 8.15(d, 1H), 8.21(d, 1H), 9.04(d, 1H), 9.09(d, 1H)

[0104] [Synthesis of cation dye 1] 25.0 g (45.8 mmol) of the previously prepared dye precursor (E in the synthesis diagram) and 250 ml of acetone were added to a 500 ml three-necked flask. Then, 10.7 g (68.7 mmol) of iodoethane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise to the resulting solution. The mixture was then heated to 50°C and reacted for 8 hours. After the reaction was complete, the mixture was cooled to room temperature and filtered. The resulting solid was washed with acetone to obtain cationic dye 1 (F in the synthesis diagram) (yield 30.0 g, yield 93%).

[0105] [Synthesis of cation dye 2] 10.0 g (14.2 mmol) of the previously prepared cationic dye 1 (F in the synthesis diagram) and 50 ml of ethyl acetate were added to a 200 ml three-necked flask. To the resulting solution, 50 ml of water in which 5.2 g (28.2 mmol) of potassium hexafluorophosphate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved was added. The resulting reaction mixture was stirred at room temperature for 2 hours, and the aqueous layer was removed. Next, 50 ml of water was added to the obtained organic layer (ethyl acetate layer) and stirred for 5 minutes, and the aqueous layer was removed. The same procedure was repeated once more, and sodium sulfate was added to the obtained organic layer (ethyl acetate layer) and allowed to stand for 15 minutes. Next, the sodium sulfate was filtered, and the solvent was removed using a rotary evaporator to obtain cationic dye 2 (G in the synthesis diagram) (yield 5.9 g, yield 58%).

[0106] NMR data of cation dye 1 and cation dye 2: 1 H-NMR (DMSO-d6): 1.30 (t, 3H), 2.20 (brs, 4H), 3.05 (s, 3H), 3.50 (t, 2H), 3.60 (brs, 4H), 6.80 (d×2, 2H), 6.94 (brs, 1H) , 7.50(t, 1H), 7.60(m, 2H), 7.68(d, 1H), 7.85(m, 2H), 7.98(d, 2H), 8.05(q, 2H), 8.25(d, 2H), 9.05(d, 1H), 9.11(d, 1H)

[0107] [Synthesis of colored fibers (Example 1)] An acrylic polymer consisting of 49% by mass of repeating units derived from acrylonitrile, 50% by mass of repeating units derived from vinyl chloride, and 1% by mass of repeating units derived from sodium styrene sulfonate was dissolved in acetone to prepare a resin solution with a resin concentration of 28.0% by mass. Next, the previously prepared cationic dye 2 and red dye (CI Basic Red 46) were added to the resin solution as colorants, in amounts of 2.5 parts by mass and 0.075 parts by mass, respectively, per 100 parts by mass of the acrylic polymer. Furthermore, polyglycidyl methacrylate (weight-average molecular weight 12,000) was added at an amount of 0.9% by mass relative to 100% by mass of the acrylic polymer to prepare a spinning stock. The spinning stock was extruded using a spinning nozzle into a coagulation bath of 40% by mass aqueous acetone solution at 25°C and coagulated to form fibers. Subsequently, desolventing and stretching were carried out in hot water at 75°C. Next, the primary stretched yarn, after being washed with water, was immersed in an oil bath containing a fiber oil (the main components of the oil bath were fatty acid ester-based oil, polyoxyethylene-based surfactant, and water) to impregnate it with the fiber oil. After drying, stretching, and heat treatment, an acrylic fiber with a single fiber fineness of approximately 46 dtex and colored black was obtained.

[0108] [Synthesis of colored fibers (Comparative Example 1)] An acrylic polymer consisting of 49% by mass of repeating units derived from acrylonitrile, 50% by mass of repeating units derived from vinyl chloride, and 1% by mass of repeating units derived from sodium styrene sulfonate was dissolved in acetone to prepare a resin solution with a resin concentration of 28.0% by mass. Next, carbon black was added to the resin solution as a coloring agent in an amount of 2.0 parts by mass per 100 parts by mass of the acrylic polymer. Furthermore, polyglycidyl methacrylate (weight-average molecular weight 12,000) was added at an amount of 0.9% by mass relative to 100% by mass of the acrylic polymer to prepare a spinning stock. The spinning stock was extruded using a spinning nozzle into a coagulation bath of 40% by mass aqueous acetone solution at 25°C and coagulated to form fibers. Subsequently, desolventing and stretching were carried out in hot water at 75°C. Next, the primary stretched yarn, after being washed with water, was immersed in an oil bath containing a fiber oil (the main components of the oil bath were fatty acid ester-based oil, polyoxyethylene-based surfactant, and water) to impregnate it with the fiber oil. After drying, stretching, and heat treatment, acrylic fibers with a single fiber fineness of approximately 46 dtex and colored black were obtained.

[0109] [Synthesis of colored fibers (Comparative Example 2)] An acrylic polymer consisting of 49% by mass of repeating units derived from acrylonitrile, 50% by mass of repeating units derived from vinyl chloride, and 1% by mass of repeating units derived from sodium styrene sulfonate was dissolved in acetone to prepare a resin solution with a resin concentration of 28.0% by mass. Next, a black dye (Sudan Black B) and a red dye (CI Basic Red 46) were added to the resin solution as colorants, in amounts of 2.5 parts by mass and 0.075 parts by mass, respectively, per 100 parts by mass of the acrylic polymer. Furthermore, polyglycidyl methacrylate (weight-average molecular weight 12,000) was added at an amount of 0.9% by mass relative to 100% by mass of the acrylic polymer to prepare a spinning stock. The spinning stock was extruded using a spinning nozzle into a coagulation bath of 40% by mass aqueous acetone solution at 25°C and coagulated to form fibers. Subsequently, desolventing and stretching were carried out in hot water at 75°C. Next, the primary stretched yarn, after being washed with water, was immersed in an oil bath containing a fiber oil (the main components of the oil bath were fatty acid ester-based oil, polyoxyethylene-based surfactant, and water) to impregnate it with the fiber oil. After drying, stretching, and heat treatment, an acrylic fiber with a single fiber fineness of approximately 46 dtex and colored black was obtained.

[0110] [Evaluation Results] The heat-reducing properties and fastness in 90°C hot water of the obtained colored fibers in Example 1 and Comparative Examples 1-2 were evaluated, respectively. [Method for evaluating fever suppression] The colored fibers of Example 1 and Comparative Examples 1-2 were prepared as bundled samples measuring 30 mm in length, 30 mm in width, and 10 mm in thickness. Next, the samples were placed in a constant temperature and humidity chamber adjusted to a temperature of 32°C and a humidity of 60%, and exposed to simulated sunlight (light source: spectral matching grade B or higher as defined in JIS C8904-9, and irradiance of 800 ± 100 W / m²). 2 An artificial sunlight lamp capable of irradiating the surface of the test specimen was set at a distance of 200 mm from the sample, and after exposure for 20 minutes, the surface temperature of the colored fiber was measured with a thermocouple.

[0111] [Method for evaluating robustness in 90°C hot water] When 2g each of the colored fibers from Example 1 and Comparative Examples 1-2 were impregnated in a container with 10g of 90°C hot water, the amount of colorant leached from the colored fibers was observed by visually checking the hue of the hot water. The fastness was evaluated based on the observed hue according to the following criteria. (Evaluation Criteria) A: It is colorless, transparent, or has a light hue, and has excellent durability. B: It has a dark hue and poor durability.

[0112] In Example 1 and Comparative Example 2, the difference in surface temperature of the colored fibers before and after exposure to simulated sunlight was 30°C (an increase of 30°C), whereas in Comparative Example 1, the difference in surface temperature of the colored fibers before and after exposure to simulated sunlight was 42°C (an increase of 42°C). Furthermore, in Example 1 and Comparative Example 1, the amount of colorant leached from the colored fibers when impregnated with 90°C hot water was small, indicating good colorfastness. In contrast, in Comparative Example 2, the amount of colorant leached from the colored fibers when impregnated with 90°C hot water was large, resulting in poor colorfastness.

Claims

1. A colored fiber comprising a fiber and a compound represented by the following formula (1). 【Chemistry 1】 In formula (1) above, R １ and R ２ Each of these independently represents a hydrogen atom or a substituent. Also, R １ and R ２ These may be bonded together to form a ring. Of the two X's, one represents a hydrogen atom, and the other represents a group represented by the following formula (1a). 【Chemistry 2】 In formula (1a) above, R ３ ~R １３ Each of these independently represents a hydrogen atom or a substituent. Also, R ３ ~R １３ Two adjacent groups may bond to each other to form a ring. * indicates the bonding position. However, the compound represented by formula (1) satisfies at least one of requirements 1 to 3. Requirement 1: R １ ~R １３ At least one of them represents a substituent containing a partial structure represented by the following formula (1b). Equation (1b): *-X １ ＋ Y － In the above formula (1b), * - X １ ＋ This represents a cationic group selected from the group consisting of the group represented by the following formula (N1), the group represented by the following formula (CyN1), and the group represented by the following formula (CyN2). － * represents an anionic counterion. * represents the bond position. Formula (N1): *-N + (R A ) 3 In formula (N1), R and A each independently represent a hydrogen atom or a substituent. * indicates a bond position. 【Transformation 3】 In formula (CyN1), Ra1 and Ra2 each independently represent a hydrogen atom or a substituent. W a1 represents an alicyclic ring containing at least one cationic nitrogen atom as explicitly shown in the formula, and which may further have substituents other than R a1 and R a2. * indicates a bond position. In formula (CyN2), R b1 represents a hydrogen atom or substituent. W b1 represents an aromatic ring containing at least one cationic nitrogen atom as explicitly shown in the formula, and which may further have substituents other than R b1. * represents a bond position. Requirement 2: R １ and R ２ and are joined to each other to form a ring, and the ring is X ２ ＋ (Y － Includes a substructure represented by ). ２ ＋ This represents a cationic nitrogen atom constituting a ring member atom of the aforementioned ring. － This represents an anionic counterion. Requirement 3: R ３ ~R １３ Of these, two adjacent groups bond to each other to form a ring, and the ring is X ３ ＋ (Y － Includes a substructure represented by ). ３ ＋ This represents a cationic nitrogen atom constituting a ring member atom of the aforementioned ring. － This represents an anionic counterion.

2. The colored fiber according to claim 1, wherein the fiber is an acrylic fiber composed of an acrylic polymer.

3. The aforementioned acrylic polymer Repeating units X derived from acrylonitrile monomers, One or more repeating units Y selected from the group consisting of repeating units derived from vinylidene chloride monomers and repeating units derived from vinyl chloride monomers, It contains repeating units Z derived from a sulfonic acid group-containing vinyl monomer, The content of the repeating unit X is 29.5 to 79.5% by mass relative to the total mass of the acrylic polymer. The content of the repeating unit Y is 20 to 70% by mass relative to the total mass of the acrylic polymer. The colored fiber according to claim 2, wherein the content of the repeating unit Z is 0.5 to 5% by mass with respect to the total mass of the acrylic polymer.

4. In formula (1) above, R １ and R ２ At least one of these represents a substituent including the substructure represented by formula (1b), or R １ and R ２ and are joined to each other to form a ring, and the ring is the X ２ ＋ (Y － A colored fiber according to any one of claims 1 to 3, comprising a substructure represented by ).

5. The aforementioned Y － The colored fiber according to any one of claims 1 to 3, wherein the anionic counterion represented by is one selected from the group consisting of sulfonimide ion, hexafluorophosphate ion, iodide ion, saccharin ion, and tosylate ion.

6. A method for producing colored fibers according to any one of claims 1 to 3, A method for producing colored fibers, comprising the step of wet spinning a spinning stock containing a polymer contained in the fiber and a compound represented by formula (1).

7. A method for producing colored fibers according to any one of claims 1 to 3, A method for producing colored fibers, comprising the step of dyeing the fibers using an aqueous solution containing a compound represented by formula (1) above.

8. A textile product comprising a colored fiber as described in any one of claims 1 to 3.

9. A textile product according to claim 8, which is a headwear product.

10. The textile product according to claim 9, wherein the head ornament product is selected from the group consisting of hair fiber bundles, weaving, wigs, braids, toupees, hair extensions, and hair accessories.

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