Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/2035—Aromatic acids
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
  • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/70—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/10—Animal fibres
  • D06M2101/12—Keratin fibres or silk
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/10—Animal fibres
  • D06M2101/14—Collagen fibres
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

• the present invention relates to a fiber-treating agent for imparting water resistance, heat resistance and heat shape memory ability to naturally derived fibers, and preferably relates to a fiber-treating agent for naturally derived fibers used in fiber products such as headdress products such as wigs and extensions.
• naturally derived fibers generally have natural texture and appearance originating from a natural material.
• regenerated protein fibers for example, regenerated collagen fibers, are obtained by solubilizing acid-soluble collagen or by solubilizing acid-insoluble collagen with an alkali or an enzyme to obtain a spinning stock solution, and discharging the spinning stock solution into a coagulation bath through a spinning nozzle to form fibers.
• Naturally derived fibers generally have higher hydrophilicity and hence higher water absorption as compared to synthetic fibers, and the fibers have generally low mechanical strength when they contain a large amount of water, and in particular, regenerated protein fibers have extremely low mechanical strength. This leads to deterioration of suitability as a fiber product such that during washing, mechanical strength significantly deteriorates because of the higher water absorption, and during subsequent drying, rupture occurs.
• regenerated protein fibers also have a problem of low heat resistance, so that, for example, if a heat set using a hair iron or the like is performed at a temperature as high as that for human hair, shrinkage or crimping occurs, resulting in impairment of visual quality.
• plastic synthetic fibers the shape in a heat set with an iron or the like is continuously memorized even after subsequent washing (there is heat shape memory ability), whereas in naturally derived fibers, the shape in a heat set with an iron or the like is lost through subsequent one time washing (there is no heat shape memory ability). Therefore, naturally derived fibers may be inferior to conventional plastic synthetic fibers in terms of degree of freedom of shape set.
• Patent Literature 1 a method is known in which to human hair fibers having essentially no heat shape memory ability, a specific aldehyde derivative and phenolic compound are applied for newly imparting heat shape memory ability.
• Patent Literature 1 JP-A-2019-143281
• the present invention provides a fiber-treating agent comprising the following components (A) and (B):
• the present invention relates to a fiber-treating agent which improves water resistance and heat resistance problematic in naturally derived fibers, imparts heat shape memory ability, improves stretchability (tenacity) and the feel of the surfaces, and causes no coloring of naturally derived fibers.
• the present inventors have conducted intensive studies and as a result, found that by treating naturally derived fibers with a composition containing a compound having a carboxy group and a hydrogen bond term in Hansen solubility parameter of a certain value or less, the carboxy group of the compound penetrated into the fibers is strongly coordinated with a metal (mainly polyvalent metal) in the naturally derived fibers, so that the inside of the fibers is hydrophobized and the leakage of the compound from the fibers is prevented.
• a metal mainly polyvalent metal
• the present inventors found that not only water resistance, and heat resistance in both dry state and wet state in the naturally derived fibers are improved, so that the shape can be imparted by a heat set, but also surprisingly, the stretchability (tenacity) of the naturally derived fibers is improved as compared to that before treatment and can be enhanced to a level close to that of human hair, and further, no coloring is caused, leading to completion of the present invention.
• a fiber-treating agent which improves water resistance and heat resistance problematic in naturally derived fibers, can impart heat shape memory ability, improves stretchability (tenacity) and the feel of the surfaces, and further, causes no coloring of naturally derived fibers.
• Fibers to be treated with the fiber-treating agent of the present invention are preferably metal-containing fibers, preferably naturally derived metal-containing fibers or synthetic metal-containing fibers, and among them, naturally derived metal-containing fibers are preferable.
• the naturally derived fiber refers to fibers which are taken from a natural animal or plant, or artificially produced fibers using a polymer or an oligomer, such as protein derived from keratin, collagen, casein, soybeans, peanuts, corn, silk flocks, silk protein (for example, silk fibroin) or the like or a polysaccharide, as a raw material.
• artificially produced fibers using a polymer or an oligomer such as protein derived from keratin, collagen, casein, soybeans, peanuts, corn, silk flocks, silk protein (for example, silk fibroin) or the like or a polysaccharide, as a raw material are preferable, regenerated protein fibers using protein derived from keratin, collagen, casein, soybean protein, peanut protein, corn protein, silk protein (for example, silk fibroin) or the like as a raw material are more preferable, regenerated protein fibers such as regenerated collagen fibers made from collagen as a raw material or regenerated silk fibers made from silk fibroin as a raw material are more preferable, and regenerated collagen fibers are further more preferable.
• a polymer or an oligomer such as protein derived from keratin, collagen, casein, soybeans, peanuts, corn, silk flocks, silk protein (for example, silk fibroin) or the like or a polysaccharide, as a
• Regenerated collagen fibers can be produced by a known technique, are not required to have a composition of collagen 100%, and may contain a natural or synthetic polymer and additives for improvement of quality.
• Regenerated collagen fibers are preferably in the form of filaments. Filaments are generally taken from fibers wound around a bobbin or packed in a box. It is also possible to directly use filaments coming out from a drying step in a production process of regenerated collagen fibers.
• Synthetic metal-containing fibers may be metal-treated synthetic fibers.
• Naturally derived metal-containing fibers include those originally containing a metal such as fibers taken from a natural animal or plant. In this case, those originally containing a metal are not required to contain additional metal, but may be treated with a metal salt, as fibers treated with an aluminum salt to achieve water resistance as described in, for example, JP-A-2003-027318 , and the like.
• Component (A) compound having hydrogen bond term ⁇ H in Hansen solubility parameter of 18.3 MPa 1/2 or less, at least one of carboxy group or salt thereof, and no fused ring]
• the component (A) is a compound having a hydrogen bond term ⁇ H in Hansen solubility parameter of 18.3 MPa 1/2 or less, and having at least one of a carboxy group or a salt thereof, and no fused ring.
• the hydrogen bond term in Hansen solubility parameter refers to ⁇ H (MPa 1/2 ) (the energy term by the hydrogen bond between molecules) calculated at 25°C in the DIY program using Software Package HSPiP 4th Edition 4.1.07 based on Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton FL, 2007 .
• the component (A) is a salt
• examples of the salt include alkaline metal salts such as sodium salts and potassium salts.
• Examples of the compound of the component (A) include the following (A1) and (A2):
• examples of the aromatic compound of formula (1) include a compound of the following formula (1A), (1B), or (1C): wherein B 1 to B 4 each independently represent a hydrogen atom, an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group, or alkenyloxy group having 1 to 6 carbon atoms, and R 3 represents a hydroxy group or a group of the following formula (1A)-a or (1A)-b: wherein B 5 to B 9 represent the same meaning as the B 1 to B 4 , R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 2; wherein D 1 to D 4 each independently represent a hydrogen atom, an acetyl group, a halogen atom, or a linear or branched alkyl group, alkenyl group, alkoxy group, or alkenyloxy group having 1 to 6 carbon atoms, and
• examples of the compound in which R 3 is a hydroxy group include 2-carboxy benzoic acid (phthalic acid) (hydrogen bond term ⁇ H in Hansen solubility parameter: 13.4 MPa 1/2 ) (hereinafter, a numerical value in parenthesis described after each compound name indicates the hydrogen bond term ⁇ H calculated by the above method) .
• examples of the compound in which R 3 is a group of formula (1A)-a include 2-(((4-vinylbenzyl)oxy)carbonyl)benzoic acid (7.0 MPa 1/2 ).
• examples of the compound in which R 3 is a group of formula (1A)-b include 2-((2-(acryloyloxy)ethoxy)carbonyl)benzoic acid (9.1 MPa 1/2 ) and 2-((2-(methacryloyloxy)ethoxy)carbonyl)benzoic acid (8.4 MPa 1/2 ).
• Examples of the compound of formula (1B) include 2-benzoylbenzoic acid (7.5 MPa 1/2 ), 2-(2-methylbenzoyl)benzoic acid (6.9 MPa 1/2 ), 2-(3-methylbenzoyl)benzoic acid (6.6 MPa 1/2 ), 2-(4-methylbenzoyl)benzoic acid (7.2 MPa 1/2 ), 2-(2-chlorobenzoyl)benzoic acid (7.1 MPa 1/2 ), 2-(3-chlorobenzoyl)benzoic acid (6.9 MPa 1/2 ), 2-(4-chlorobenzoyl)benzoic acid (7.5 MPa 1/2 ), and 2-(4-(2-(2-(acryloyloxy)ethoxy)ethoxy)benzoyl)benzoic acid (8.7 Mpa 1/2 ).
• examples of the compound in which R 6 is a hydrogen atom include phenylsuccinic acid (15.8 MPa 1/2 ), 2,3-diphenylsuccinic acid (11.9 MPa 1/2 ), and (+)-di-p-toluoyl-D-tartaric acid (10.2 MPa 1/2 ).
• examples of the compound in which R 6 is a group of formula (1C)-a include 4-oxo-4-((4-vinylbenzyl)oxy)butanoic acid (10.1 MPa 1/2 ).
• examples of the compound which is included in formula (1) but is not included in any of formula (1A), (1B), and (1C) include 3-carboxybenzoic acid (isophthalic acid) (12.9 MPa 1/2 ), 4-carboxybenzoic acid (terephthalic acid) (13.7 MPa 1/2 ), 3-benzoylbenzoic acid (7.2 MPa 1/2 ), and 4-benzoylbenzoic acid (7.9 MPa 1/2 ).
• the numerical value in parenthesis described after each compound name is the hydrogen bond term ⁇ H calculated by the above method.
• aromatic compound of formula (2) examples include benzoic acid (9.5 MPa 1/2 ), 2-methylbenzoic acid (8.4 MPa 1/2 ), 3-methylbenzoic acid (8.0 MPa 1/2 ), 4-methylbenzoic acid (8.8 MPa 1/2 ), 2-ethylbenzoic acid (7.7 MPa 1/2 ), 3-ethylbenzoic acid (7.4 MPa 1/2 ), 4-ethylbenzoic acid (8.1 MPa 1/2 ), 2-propylbenzoic acid (7.0 MPa 1/2 ), 3-propylbenzoic acid (6.7 MPa 1/2 ), 4-propylbenzoic acid (7.4 MPa 1/2 ), 2-isopropylbenzoic acid (6.7 MPa 1/2 ), 3-isopropylbenzoic acid (6.5 MPa 1/2 ), 4-isopropylbenzoic acid (7.1 MPa 1/2 ), 2-n-butylbenzoic acid (6.8 MPa 1/2 ), 3-n-butylbenzoic acid (6.5 MPa 1/2 ), 4-n-but
• examples of the compound other than the compounds of formulas (1) and (2) include phenylbutanoic acid.
• Examples of the compound of the component (A2) include potassium 2,4-hexadienoate (12.5 MPa 1/2 ).
• the hydrogen bond term ⁇ H of the aromatic compound of the component (A1) is preferably 16.0 MPa 1/2 or less, more preferably 13.5 MPa 1/2 or less, further more preferably 12.0 MPa 1/2 or less, further more preferably 10.0 MPa 1/2 or less, and preferably 3.0 MPa 1/2 or more, more preferably 4.0 MPa 1/2 or more, further more preferably 5.0 MPa 1/2 or more, from the viewpoint of moderately hydrophobizing the inside of fibers.
• the hydrogen bond term ⁇ H of the compound of the component (A2) is preferably 16.0 MPa 1/2 or less, more preferably 15.0 MPa 1/2 or less, further more preferably 14.0 MPa 1/2 or less, further more preferably 13.0 MPa 1/2 or less, and preferably 11.0 MPa 1/2 or more, more preferably 11.5 MPa 1/2 or more, further more preferably 12.0 MPa 1/2 or more, from the viewpoint of moderately hydrophobizing the inside of fibers.
• the preferred content of the component (A) is described in accordance with the kind of the component (A).
• the content of the component (A) refers to the content of the corresponding acid form.
• the content of the component (A) varies different depending on the pH range of the fiber-treating agent, and the following range is preferable.
• the component (A1-1) which is the component (A1) in the component (A)
• the content of the component (A1-1) in the fiber-treating agent is, as benzoic acid (acid form), preferably 0.8 mass% or more, more preferably 3.0 mass% or more, further more preferably 5.0 mass% or more, even more preferably 10 mass% or more, even more preferably 15 mass% or more, even more preferably 20 mass% or more, from the viewpoint of imparting higher shape sustainability, water resistance, stretchability (tenacity, that is, high breaking elongation during fiber tensioning), and heat resistance to treated naturally derived fibers, and preferably 90 mass% or less, more preferably 80 mass% or less, further more preferably 70 mass% or less, even more preferably 50 mass% or less, further more preferably 40 mass% or less, even more preferably 35 mass
• the content of the component (A1-1) in the fiber-treating agent of the present invention is, as benzoic acid (acid form), preferably from 0.8 to 90 mass%, more preferably from 3.0 to 80 mass%, further more preferably from 5.0 to 70 mass%, even more preferably from 10 to 50 mass%, even more preferably from 15 to 40 mass%, even more preferably from 20 to 35 mass%, from the above viewpoint.
• the content of the component (A1-1) in the fiber-treating agent is, as benzoic acid (acid form), preferably 0.8 mass% or more, more preferably 3.0 mass% or more, further more preferably 5.0 mass% or more, even more preferably 10 mass% or more, even more preferably 15 mass% or more, even more preferably 20 mass% or more, even more preferably 25 mass% or more, even more preferably 26 mass% or more, even more preferably 28 mass% or more, even more preferably 30 mass% or more, from the viewpoint of imparting higher shape sustainability, water resistance, stretchability (tenacity, that is, high breaking elongation during fiber tensioning), and heat resistance to treated naturally derived fibers, and preferably 90 mass% or less, more preferably 80 mass% or less, further more preferably 70 mass% or less, even more preferably 50 mass% or less, even
• the content of the component (A1-1) in the fiber-treating agent of the present invention is, as benzoic acid (acid form), preferably from 0.8 to 90 mass%, more preferably from 3.0 to 80 mass%, further more preferably from 5.0 to 70 mass%, even more preferably from 10 to 70 mass%, even more preferably from 15 to 50 mass%, even more preferably from 20 to 50 mass%, even more preferably from 25 to 45 mass%, even more preferably from 26 to 45 mass%, even more preferably from 28 to 40 mass%, even more preferably from 30 to 40 mass%, from the above viewpoint.
• the content of the component (A1-2) in the fiber-treating agent is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further more preferably 0.5 mass% or more, even more preferably 1.0 mass% or more, from the viewpoint of imparting higher shape sustainability, water resistance, stretchability (tenacity, that is, high breaking elongation during fiber tensioning), and heat resistance to treated naturally derived fibers, and preferably 70 mass% or less, more preferably 60 mass% or less, further more preferably 50 mass% or less, even more preferably 45 mass% or less, from the viewpoint of improving the feel of the fiber surfaces.
• the content of the component (A1-2) in the fiber-treating agent of the present invention is preferably from 0.1 to 70 mass%, more preferably from 0.2 to 60 mass%, further more preferably from 0.5 to 50 mass%, even more preferably from 1.0 to 45 mass%, from the above viewpoint.
• the content of the component (A1-2) in the fiber-treating agent is preferably 1.0 mass% or more, more preferably 2.0 mass% or more, further more preferably 5.0 mass% or more, even more preferably 10 mass% or more, from the viewpoint of imparting higher shape sustainability, water resistance, stretchability (tenacity, that is, high breaking elongation during fiber tensioning), and heat resistance to treated naturally derived fibers, and preferably 70 mass% or less, more preferably 60 mass% or less, further more preferably 50 mass% or less, even more preferably 40 mass% or less, from the viewpoint of improving the feel of the fiber surfaces.
• the content of the component (A1-2) in the fiber-treating agent of the present invention is preferably from 1.0 to 70 mass%, more preferably from 2.0 to 60 mass%, further more preferably from 5.0 to 50 mass%, even more preferably from 10 to 40 mass%, from the above viewpoint.
• the content of the component (A2) in the fiber-treating agent is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further more preferably 0.5 mass% or more, even more preferably 1.0 mass% or more, from the viewpoint of imparting higher shape sustainability, water resistance, stretchability (tenacity, that is, high breaking elongation during fiber tensioning), and heat resistance to treated naturally derived fibers, and preferably 60 mass% or less, more preferably 50 mass% or less, further more preferably 40 mass% or less, even more preferably 30 mass% or less, from the viewpoint of improving the feel of the fiber surfaces.
• the content of the component (A2) in the fiber-treating agent of the present invention is preferably from 0.1 to 60 mass%, more preferably from 0.2 to 50 mass%, further more preferably from 0.5 to 40 mass%, even more preferably from 1.0 to 30 mass%, from the above viewpoint.
• the content of the component (A2) in the fiber-treating agent is preferably 1.0 mass% or more, more preferably 2.0 mass% or more, further more preferably 5.0 mass% or more, even more preferably 10 mass% or more, from the viewpoint of imparting higher shape sustainability, water resistance, stretchability (tenacity, that is, high breaking elongation during fiber tensioning), and heat resistance to treated naturally derived fibers, and preferably 70 mass% or less, more preferably 60 mass% or less, further more preferably 50 mass% or less, even more preferably 40 mass% or less, from the viewpoint of improving the feel of the fiber surfaces.
• the content of the component (A2) in the fiber-treating agent is preferably from 1.0 to 70 mass%, more preferably from 2.0 to 60 mass%, further more preferably from 5.0 to 50 mass%, even more preferably from 10 to 40 mass%, from the above viewpoint.
• the fiber-treating agent preferably contains two or more compounds as the component (A), from the viewpoint of improving the solubility of the entire component (A) to reduce the turbidity of the fiber-treating agent, allowing fibers to be uniformly treated, and thereby improving the feel of fiber surfaces after treatment.
• the fiber-treating agent contains two or more compounds as the component (A)
• at least one compound is preferably an aromatic compound of formula (2), and more preferably benzoic acid or a salt thereof.
• the content of the above compound is preferably the highest among the components (A), and when benzoic acid or a salt thereof is contained, the content of the above compound is more preferably the highest among the components (A).
• the content of the component (A) left after excluding a compound present at the highest concentration in the entire component (A) in the fiber-treating agent is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further more preferably 1.0 mass% or more, and preferably 20 mass% or less, more preferably 10 mass% or less, further more preferably 5.0 mass% or less, from the viewpoint of improving the solubility of the entire component (A) to reduce the turbidity of the fiber-treating agent, allowing fibers to be uniformly treated, and thereby improving the feel of fiber surfaces after treatment.
• the content of the component (A) left after excluding a compound present at the highest concentration in the entire component (A) in the fiber-treating agent is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, further more preferably 2.0 mass% or more, and preferably 30 mass% or less, more preferably 20 mass% or less, further more preferably 10 mass% or less, from the viewpoint of improving the solubility of the entire component (A) to reduce the turbidity of the fiber-treating agent, allowing fibers to be uniformly treated, and thereby improving the feel of fiber surfaces after treatment.
• a mass ratio of the component (A) left after excluding a compound present at the highest concentration in the entire component (A) to the compound in the fiber-treating agent is preferably 0.01 or more, more preferably 0.05 or more, further more preferably 0.10 or more, and preferably 1.0 or less, more preferably 0.5 or less, further more preferably 0.25 or less, from the viewpoint of improving the solubility of the entire component (A) to reduce the turbidity of the fiber-treating agent, allowing fibers to be uniformly treated, and thereby improving the feel of fiber surfaces after treatment.
• the fiber-treating agent of the present invention contains water as a medium.
• the content of the component (B) in the fiber-treating agent of the present invention is preferably 10 mass% or more, more preferably 20 mass% or more, further more preferably 30 mass% or more, even more preferably 40 mass% or more, and preferably 99 mass% or less, more preferably 95 mass% or less, further more preferably 90 mass% or less, even more preferably 85 mass% or less.
• the content of the component (B) in the fiber-treating agent of the present invention is preferably from 10 to 99 mass%, more preferably from 20 to 95 mass%, further more preferably from 30 to 90 mass%, even more preferably from 40 to 85 mass%.
• the fiber-treating agent of the present invention may contain a cationic surfactant as long as the effects of the present invention are not impaired.
• the cationic surfactant is preferably a long chain monoalkyl quaternary ammonium salt having one alkyl group having 8 to 24 carbon atoms and three alkyl groups having 1 to 4 carbon atoms.
• At least one long chain monoalkyl quaternary ammonium surfactant is selected from the group consisting of compounds of the following formula (3): wherein R 7 is a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms, R 11 -CO-NH-(CH 2 ) m - or R 11 -CO-O-(CH 2 ) m - (R 11 represents a saturated or unsaturated linear or branched alkyl chain having 7 to 21 carbon atoms, and p represents an integer of 1 to 4), R 8 , R 9 and R 10 independently represent an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, and An - represents a chloride ion, a bromide ion, a methosulfate ion or an ethosulfate ion.
• Suitable cationic surfactant examples include long chain quaternary ammonium compounds such as cetyltrimethylammonium chloride, myristyltrimethylammonium chloride, behentrimonium chloride, cetyltrimethylammonium bromide and stearamidopropyltrimonium chloride. One of them may be used alone, or a mixture thereof may be used.
• the content of the cationic surfactant in the fiber-treating agent of the present invention is preferably 0.05 mass% or more, more preferably 0.10 mass% or more, and preferably 10 mass% or less, more preferably 5.0 mass% or less, from the viewpoint of improving the feel of the surfaces of naturally derived fibers after treatment, and further improving the effects of the present invention.
• the fiber-treating agent of the present invention may contain silicone from the viewpoint of improving the feel of the surfaces of naturally derived fibers after treatment, and improving styling ease.
• the silicone is preferably one or more selected from the group consisting of dimethylpolysiloxane and amino-modified silicone.
• any of cyclic or acyclic dimethylsiloxane polymers can be used, and examples thereof include SH200 Series, BY22-019, BY22-020, BY11-026, B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083 and FZ-4188 (each manufactured by Dow Corning Toray), and KF-9088, KM-900 Series, MK-15H and MK-88 (each manufactured by Shin-Etsu Chemical Co., Ltd.).
• SH200 Series BY22-019, BY22-020, BY11-026, B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083 and FZ-4188 (each manufactured by Dow Corning Toray), and KF-9088, KM-900 Series, MK-15H and MK-88 (each manufactured by Shin-Etsu Chemical Co., Ltd.).
• any silicone having an amino group or an ammonium group can be used, and examples thereof include amino-modified silicone oil which is terminal-blocked at all or a part of terminal hydroxyl groups with a methyl group or the like, and amodimethicone which is not terminal-blocked.
• Examples of the amino-modified silicone preferable from the viewpoint of improving the feel of the surfaces of naturally derived fibers after treatment and improving styling ease include compounds of the following formula: wherein R' represents a hydrogen atom, a hydroxy group or R X , where R X represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, J represents R X , R"- (NHCH 2 CH 2 )aNH 2 , OR X or a hydroxy group, R" represents a divalent hydrocarbon group having 1 to 8 carbon atoms, a represents a number of 0 to 3, and b and c represent numbers whose sum is 10 or more and less than 20 000, preferably 20 or more and less than 3 000, more preferably 30 or more and less than 1 000, further more preferably 40 or more and less than 800, in terms of number average.
• amino-modified silicone oils such as SF8452C and SS3551 (each manufactured by Dow Corning Toray) and KF-8004, KF-867S and KF-8015 (each manufactured by Shin-Etsu Chemical Co., Ltd.), and amodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671 and FZ4672 (each manufactured by Dow Corning Toray).
• the content of silicone in the fiber-treating agent of the present invention is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further more preferably 0.5 mass% or more, and preferably 20 mass% or less, more preferably 10 mass% or less, further more preferably 5.0 mass% or less, from the viewpoint of improving the feel of the surfaces of naturally derived fibers after treatment, and further improving the effects of the present invention.
• the fiber-treating agent of the present invention may contain a cationic polymer from the viewpoint of improving the feel of the surfaces of naturally derived fibers after treatment.
• the cationic polymer refers to a polymer having a cationic group, or a group capable of being ionized into a cationic group, and also includes an amphoteric polymer which is cationic as a whole. That is, examples of the cationic polymer include those in the form of an aqueous solution, which contain an amino group or an ammonium group on the side chain of the polymer chain or contain a diallyl quaternary ammonium salt as a constituent unit, for example, cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, polymers or copolymers of a diallyl quaternary ammonium salt, and quaternized polyvinylpyrrolidone derivatives.
• one or more selected from the group consisting of a polymer containing a diallyl quaternary ammonium salt as a constituent unit, a quaternized polyvinylpyrrolidone derivative and a cationized cellulose derivative are preferable, and one or more selected from the group consisting of a polymer or copolymer of a diallyl quaternary ammonium salt and a cationized cellulose derivative are more preferable, from the viewpoint of improving the effects of softness in the feel, smoothness and finger-combability during rinsing and shampooing and ease of styling and moisture retainability during drying, and the stability of the agent.
• Suitable polymer or copolymer of a diallyl quaternary ammonium salt include dimethyldiallylammonium chloride polymers (polyquaternium-6, for example, MERQUAT 100; Lubrizol Advanced Materials, Inc.), dimethyldiallylammonium chloride/acrylic acid copolymers (polyquaternium-22, for example, MERQUATs 280 and 295; Lubrizol Advanced Materials, Inc.), and dimethyldiallylammonium chloride/acrylamide copolymers (polyquaternium-7, for example, MERQUAT 550; Lubrizol Advanced Materials, Inc.).
• suitable quaternized polyvinylpyrrolidone derivative include polymers obtained by polymerizing a vinylpyrrolidone copolymer and dimethylaminoethyl methacrylate (polyquaternium 11, for example, GAFQUAT 734, GAFQUAT 755 and GAFQUAT 755N (Ashland Inc.)).
• Suitable cationized cellulose include polymers obtained by adding glycidyltrimethylammonium chloride to hydroxycellulose (polyquaternium 10, for example, LEOGARDs G and GP (Lion Corporation) and POLYMERs JR-125, JR-400, JR-30M, LR-400 and LR-30M (Amerchol Corporation)), and hydroxyethylcellulose dimethyldiallylammonium chloride (polyquaternium-4, for example, CELQUATs H-100 and L-200 (Akzo Nobel N.V.)).
• polyquaternium 10 polymers obtained by adding glycidyltrimethylammonium chloride to hydroxycellulose
• polyquaternium 10 for example, LEOGARDs G and GP (Lion Corporation) and POLYMERs JR-125, JR-400, JR-30M, LR-400 and LR-30M (Amerchol Corporation)
• polyquaternium-4 for example, CELQUATs H-100 and L-200
• the content of the cationic polymer in the fiber-treating agent of the present invention is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further more preferably 0.05 mass% or more, and preferably 20 mass% or less, more preferably 10 mass% or less, from the viewpoint of improving the feel of the surfaces of naturally derived fibers after treatment.
• the fiber-treating agent of the present invention may contain an antioxidant such as ascorbic acid, and a pH adjuster such as sodium hydroxide, potassium hydroxide, phosphoric acid or hydrochloric acid.
• an antioxidant such as ascorbic acid
• a pH adjuster such as sodium hydroxide, potassium hydroxide, phosphoric acid or hydrochloric acid.
• the pH of the fiber-treating agent of the present invention is preferably 2.0 or more, more preferably 3.0 or more, further more preferably 3.5 or more, even more preferably 4.0 or more, and preferably 11.0 or less, more preferably 10.0 or less, further more preferably 9.0 or less, from the viewpoint of suppressing damage to and improving durability of naturally derived fibers.
• the pH in the present invention is a value at 25°C.
• the pH of the fiber-treating agent of the present invention is preferably from 2.0 to 11.0, more preferably from 3.0 to 10.0, further more preferably from 3.5 to 9.0, even more preferably from 4.0 to 9.0, from the viewpoint of suppressing damage to and improving durability of naturally derived fibers.
• the storage temperature can be set to a cool temperature or a high temperature or gap portions in a storage container can be filled with nitrogen for the purpose of preventing progress of an unintentional reaction or recrystallization of the component (A) during transportation .
• the storage temperature of the fiber-treating agent is preferably 1°C or higher, more preferably 2°C or higher, further more preferably 5°C or higher, from the viewpoint of preventing occurrence of freezing and recrystallization, and preferably 25°C or lower, more preferably 20°C or lower, further more preferably 15°C or lower, from the viewpoint of preventing coloring by oxidation and progress of an unintentional reaction.
• the storage temperature of the fiber-treating agent is preferably 20°C or higher, more preferably 30°C or higher, further more preferably 40°C or higher, from the viewpoint of preventing recrystallization of a highly concentrated solution, and preferably 80°C or lower, more preferably 70°C or lower, further more preferably 60°C or lower, from the viewpoint of preventing coloring by oxidation and progress of an unintentional reaction.
• the fiber-treating agent of the present invention By using the fiber-treating agent of the present invention and treating naturally derived fibers with a method comprising the following step (i), it is possible to improve water resistance and heat resistance which are problems of naturally derived fibers, impart heat shape memory ability, and improve stretchability (tenacity) and the feel of the surfaces.
• Step (i) Immersing naturally derived fibers in the fiber-treating agent of the present invention.
• the naturally derived fibers immersed in the fiber-treating agent may be dry or wet.
• the amount of the fiber-treating agent in which the naturally derived fibers are immersed is preferably 2 or more, more preferably 3 or more, further more preferably 5 or more, even more preferably 10 or more, even more preferably 20 or more, and preferably 500 or less, more preferably 250 or less, further more preferably 100 or less, in terms of bath ratio to the mass of the naturally derived fibers (mass of fiber-treating agent/mass of naturally derived fibers).
• the bath ratio is preferably from 2 to 500, more preferably from 3 to 250, further more preferably from 5 to 100, even more preferably from 10 to 100, even more preferably from 20 to 100.
• the naturally derived fibers may be fixed with a curler or the like, followed by immersion in the fiber-treating agent of the present invention under heating. This enables a desired shape to be imparted to the naturally derived fibers together with heat shape memory ability and high durability.
• the immersion of the naturally derived fibers in the fiber-treating agent in the step (i) be performed under heating, and this heating is performed by heating the fiber-treating agent.
• This heating may be performed by immersing the naturally derived fibers in the fiber-treating agent being heated, or by immersing the naturally derived fibers in the fiber-treating agent at a low temperature, and then performing heating.
• the temperature of the fiber-treating agent is preferably 20°C or higher, more preferably 35°C or higher, further more preferably 45°C or higher for increasing interaction of the component (A) with fiber constituent molecules, for example protein molecules, in the naturally derived fibers to obtain the effects of the present invention, and preferably lower than 100°C, more preferably 80°C or lower, further more preferably 70°C or lower, further more preferably 60°C or lower for preventing the naturally derived fibers from being degenerated by heat and thus degraded.
• the immersion time in the step (i) is appropriately adjusted depending on the heating temperature, and is, for example, preferably 15 minutes or more, more preferably 30 minutes or more, further more preferably 1 hour or more, from the viewpoint of exhibiting a stretchability improving effect on naturally derived fibers, and is preferably 48 hours or less, more preferably 24 hours or less, further more preferably 12 hours or less, for suppressing damage to naturally derived fibers.
• step (i) it is preferable to carry out the step (i) in an environment where evaporation of moisture is suppressed.
• the specific means for suppressing evaporation of moisture include a method in which a container of the fiber-treating agent in which naturally derived fibers are immersed is covered with a film-shaped material, a cap, a lid or the like made of a material impermeable to water vapor.
• naturally derived fibers may be rinsed or may not be rinsed, but are preferably rinsed from the viewpoint of preventing deterioration of the feel of the surfaces of naturally derived fibers by an excess component (A).
• These treatments may allow the component (A) to penetrate into the naturally derived fibers, and to be strongly coordinated with metals in the fibers, for example, polyvalent metals, thereby producing various effects.
• One or more treatments selected from the group consisting of bleaching, dyeing, surface finish for imparting hydrophobicity and reducing friction, and heating treatment for further improving fiber stretchability (tenacity) may be performed in addition to the step (i).
• the treatments of bleaching and dyeing may be performed before or after the step (i).
• a plurality of steps may be combined and added, and when both bleaching and dyeing are added, any of the treatments may be performed first except that it is necessary to perform bleaching before dyeing. It is also possible to perform another treatment between bleaching and dyeing.
• surface finish for imparting hydrophobicity and reducing friction and heating treatment for further improving fiber stretchability (tenacity) need to be performed after the step (i), but their treatment order relation with bleaching and dyeing is not particularly limited.
• One of surface finish for imparting hydrophobicity and reducing friction and heating treatment for further improving fiber stretchability (tenacity) may be performed before or after the other.
• the bleaching is performed by immersing naturally derived fibers in a bleach composition containing an alkali agent, an oxidizing agent and water.
• the bleach composition is typically composed of two-part formulation. The first part contains an alkali agent and water, and the second part contains an oxidizing agent and water. These two parts are typically stored separately, and mixed before immersion of naturally derived fibers.
• alkali agent examples include, but are not limited to, ammonia and salts thereof; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and the like) and salts thereof; alkanediamines (1,3-propanediamine and the like) and salts thereof; carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like); and mixtures thereof.
• alkanolamines monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and the like
• alkanediamines (1,3-propanediamine and the like
• carbonates guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like
• the content of the alkali agent in the bleach composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further more preferably 1.0 mass% or more, and preferably 15 mass% or less, more preferably 10 mass% or less, further more preferably 7.5 mass% or less.
• Suitable oxidizing agent examples include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide and sodium bromate. Among these oxidizing agents, hydrogen peroxide is preferable.
• the content of the oxidizing agent in the bleach composition is preferably 1 mass% or more, more preferably 2 mass% or more, and preferably 15 mass% or less, more preferably 12 mass% or less, further more preferably 9 mass% or less.
• the pH of the second part at 25°C is preferably 2.0 or more, more preferably 2.5 or more, and preferably 6.0 or less, more preferably 4.0 or less.
• the pH can be adjusted by a suitable buffering agent.
• the pH of the bleach composition at 25°C is preferably 6 or more, more preferably 6.5 or more, further more preferably 6.8 or more, and preferably 11.0 or less, more preferably 10.5 or less, further more preferably 10.0 or less.
• the dyeing is performed by immersing naturally derived fibers in a hair dye composition.
• the hair dye composition contains a dye, and optionally contains an alkali agent or an acid, an oxidizing agent or the like.
• the dye include direct dyes, oxidative dyes, and combinations thereof.
• the type of the direct dye is not particularly limited, and any direct dye suitable for dyeing can be used.
• Examples of the direct dye include anionic dyes, nitro dyes, disperse dyes, cationic dyes, and dyes having an azo-phenol structure selected from the group consisting of the following HC Red 18, HC Blue 18 and HC Yellow 16, salts thereof, and mixtures thereof.
• cationic dye examples include, but are not limited to, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Orange 31, Basic Red 2, Basic Red 12, Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic yellow 57, Basic Yellow 87, and mixtures thereof.
• Basic Red 51, Basic Orange 31, Basin Yellow 87 and Mixtures thereof are particularly preferable.
• anionic dye examples include, but are not limited to, Acid Black 1, Acid Blue 1, Acid Blue 3, Food Blue 5, Acid Blue 7, Acid Blue 9, Acid Blue 74, Acid Orange 3, Acid Orange 4, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Red 1, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 50, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 155, Acid Red 180, Acid Violet 2, Acid Violet 9, Acid Violet 43, Acid Violet 49, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 3, Food Yellow No. 8, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 21, D&C Red No.
• preferred anionic dyes are Acid Black 1, Acid Red 52, Acid Violet 2, Acid Violet 43, Acid Red 33, Acid Orange 4, Acid Orange 7, Acid Red 27, Acid Yellow 3, Acid Yellow 10, and salts thereof. More preferred anionic dyes are Acid Red 52, Acid Violet 2, Acid red 33, Acid Orange 4, Acid Yellow 10, and salts and mixtures thereof.
• nitro dye examples include, but are not limited to, HC Blue No. 2, HC Blue No. 4, HC Blue No. 5, HC Blue No. 6, HC Blue No. 7, HC Blue No. 8, HC Blue No. 9, HC Blue No. 10, HC Blue No. 11, HC Blue No. 12, HC Blue No. 13, HC Brown No. 1, HC Brown No. 2, HC Green No. 1, HC Orange No. 1, HC Orange No. 2, HC Orange No. 3, HC Orange No. 5, HC Red BN, HC Red No. 1, HC Red No. 3, HC Red No. 7, HC Red No. 8, HC Red No. 9, HC Red No. 10, HC Red No. 11, HC Red No. 13, HC Red No. 54, HC Red No.
• HC Violet BS HC Violet No. 1, HC Violet No. 2, HC Yellow No. 2, HC Yellow No. 4, HC Yellow No. 5, HC Yellow No. 6, HC Yellow No. 7, HC Yellow No. 8, HC Yellow No. 9, HC Yellow No. 10, HC Yellow No. 11, HC Yellow No. 12, HC Yellow No. 13, HC Yellow No. 14, HC Yellow No. 15, 2-amino-6-chloro-4-nitrophenol, picramic acid, 1,2-diamino-4-nitrobenzole, 1,4-diamino-2-nitrobenzole, 3-nitro-4-aminophenol, 1-hydroxy-2-amino-3-nitrobenzole, 2-hydroxyethylpicramic acid, and mixtures thereof.
• disperse dye examples include, but are not limited to, Disperse Blue 1, Disperse Black 9, Disperse Violet 1, and mixtures thereof.
• One of these direct dyes may be used alone, or two or more thereof may be used in combination.
• Direct dyes different in ionicity may be used in combination.
• the content of the direct dye in the hair dye composition is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further more preferably 0.05 the mass% or more, from the viewpoint of obtaining sufficient dyeability, and preferably 10 mass% or less, more preferably 7.5 mass% or less, further more preferably 5.0 mass% or less, further more preferably 3.0 mass% or less, from the viewpoint of compatibility.
• the hair dye composition contains only direct dyes, an oxidizing agent is not necessary for dyeing naturally derived fibers.
• the composition may contain an oxidizing agent.
• the hair dye composition contains an oxidative dye
• the composition is typically of two-part type.
• the first part contains an oxidative dye intermediate (precursor and coupler) and an alkali agent
• the second part contains an oxidizing agent such as hydrogen peroxide.
• the oxidative dye intermediate is not particularly limited, and it is possible to suitably use any known of precursors and couplers which are commonly used for dyed products.
• Examples of the precursor include, but are not limited to, paraphenylenediamine, toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-para-phenylenediamine, N-phenylparaphenylenediamine, N,N-bis(2-hydroxyethyl)-paraphenylenediamine, 2-(2-hydroxyethyl)-paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,3,2'-paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3-methyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminoethyl)-4-
• coupler examples include, but are not limited to, metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenetole, 2,4-diamino-5-(2-hydroxyethoxy)toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino) toluene, 2,4-diamino-5-fluorotoluene, 1,3-bis(2,4-diaminophenoxy)propane, metaaminophenol, 2-methyl-5-aminophenol, 2-methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-metamin
• the content of each of the precursor and the coupler in the hair dye composition is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and preferably 10 mass% or less, more preferably 7.5 mass% or less, further more preferably 5.0 mass% or less.
• the hair dye composition when the hair dye composition contains an oxidative dye, the hair dye composition further contains an alkali agent.
• suitable alkali agent include, but are not limited to, ammonia and salts thereof; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and the like) and salts thereof; alkanediamines (1,3-propanediamine and the like) and salts thereof; carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like); and mixtures thereof.
• the content of the alkali agent in the hair dye composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further more preferably 1.0 mass% or more, and preferably 15 mass% or less, more preferably 10 mass% or less, further more preferably 7.5 mass% or less.
• composition containing an oxidizing agent (second part) when the hair dye composition contains an oxidative dye is stored separately from the composition containing an oxidative dye (first part), and mixed before naturally derived fibers are immersed.
• suitable oxidizing agent include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide and sodium brominate. Among these oxidizing agents, hydrogen peroxide is preferable.
• the content of the oxidizing agent in the hair dye composition is preferably 1 mass% or more, more preferably 2 mass% or more, and preferably 15 mass% or less, more preferably 12 mass% or less, further more preferably 9 mass% or less.
• the pH of the second part at 25°C is preferably 2 or more, more preferably 2.5 or more, and preferably 6 or less, more preferably 4 or less.
• the pH can be adjusted by a suitable buffering agent.
• the pH of the hair dye composition at 25°C obtained by mixing the first part and the second part is preferably 6 or more, more preferably 6.5 or more, further more preferably 6.8 or more, and preferably 11 or less, more preferably 10.5 or less, further more preferably 10 or less.
• the hair dye composition may further contain any of the direct dyes exemplified above.
• the hair dye composition may further contain the following surfactant, conditioning component and the like.
• the hair dye composition can be in the form of solution, emulsion, cream, paste and mousse.
• the temperature of the hair dye composition is preferably 0°C or higher, more preferably 10°C or higher, further more preferably 20°C or higher, and preferably 90°C or lower, more preferably 80°C or lower, from the viewpoint of efficiently having the hair dye composition penetrated and diffused into naturally derived fibers to enhance the effect of dyeing.
• naturally derived fibers can be heated while being stretched by applying tension to the fibers.
• the naturally derived fibers are small in amount, it is preferable to use a hair iron for the heating, and when the naturally derived fibers are large in amount, an equivalent result can be obtained by, for example, performing hot air heating while tension is applied by a rewinder.
• the fiber elongation percentage during heating is preferably 0.1% or more, more preferably 0.2% or more, further more preferably 0.5% or more, from the viewpoint of more effectively improving the stretchability of the fibers, and preferably 10% or less, more preferably 5.0% or less, further more preferably 2.0% or less, from the viewpoint of suppressing damage to the fibers.
• the heating temperature is preferably 120°C or higher, more preferably 140°C or higher, further more preferably 160°C or higher, from the viewpoint of more effectively improving the stretchability of the fibers, and preferably 240°C or lower, more preferably 220°C or lower, further more preferably 200°C or lower, from the viewpoint of suppressing damage to the fibers.
• the heating time is preferably 1 second or more, more preferably 3 seconds or more, further more preferably 5 seconds or more, from the viewpoint of more effectively improving the stretchability of the fibers, and preferably 60 seconds or less, more preferably 30 seconds or less, further more preferably 20 seconds or less, from the viewpoint of suppressing damage to the fibers.
• the elongation percentage here is preferably 0.1% or more, more preferably 0.2% or more, further more preferably 0.5% or more, from the viewpoint of more effectively improving the stretchability of the fibers, and preferably 10% or less, more preferably 5.0% or less, further more preferably 2.0% or less, from the viewpoint of suppressing damage to the fibers.
• the water temperature is preferably 5°C or higher, more preferably 20°C or higher, further more preferably 30°C, from the viewpoint of more effectively improving the stretchability of the fibers, and preferably 80°C or lower, more preferably 60°C or lower, further more preferably 50°C or lower, from the viewpoint of suppressing damage to the fibers.
• the time for leaving the fibers to stand in water is preferably 1 minute or more, more preferably 5 minutes or more, further more preferably 30 minutes or more, from the viewpoint of more effectively improving the stretchability of the fibers, and preferably 48 hours or less, more preferably 24 hours or less, further more preferably 3 hours or less, from the viewpoint of suppressing damage to the fibers.
• stretchability of the fibers at dry state can achieve the equivalent to that of human hair.
• the fibers When naturally derived fibers are treated by the above method for treating fibers, the fibers contain the component (A), so that it is possible to produce fibers, preferably fibers for headdress products and the like, in which the shape of the fiber is possible to be imparted by a heat set, the fibers are excellent in water resistance, heat resistance, and tensile elastic modulus, and the stretchability (tenacity) of the naturally derived fibers is highly improved, and to produce various fiber products using the fibers, preferably headdress products and the like.
• Suitable headdress products include hair wigs, wigs, weavings, hair extensions, blade hairs, hair accessories, and doll hairs.
• compositions whose formulations are shown in Tables 1 and 2 regenerated collagen fibers were treated by the following method, and various properties were evaluated.
• the pH of each composition was measured with the prepared composition directly applied to a pH meter (F-52 manufactured by HORIBA, Ltd.) at room temperature (25°C).
• an average breaking elongation during fiber tensioning that is, an average value in evaluation on a plurality of fibers (ten fibers) for the percentage by which the fiber was stretched by tensioning with respect to the original fiber length when rupture occurred was used.
• the evaluation was performed in the following procedure using a tress immediately after treatment performed as described in ⁇ Treatment method> above.
• the degree of increase (C%) in average breaking elongation of the treated tress (B%) with respect to an untreated state when the average breaking elongation during fiber tensioning in an intact state (untreated; Comparative Example 1) at the time of being cut from the commercially available product (A%) is used as a reference is determined from the following expression, and shown as "ratio of increase in average breaking elongation during fiber tensioning [%]" in the table.
• C % B % ⁇ A %
• an average breaking load during fiber tensioning was used. Evaluation was performed using a tress immediately after treatment performed as described in ⁇ Treatment method> above. As a numerical value, an average value in evaluation on a plurality of fibers (ten fibers) was used. The evaluation was performed in the following procedure.
• the degree of increase (Y (gf)) in average breaking load of the treated tress (W 1 (gf)) with respect to an untreated state when the average breaking load during fiber tensioning in an intact state (untreated; Comparative Example 1) at the time of being cut from the commercially available product (W 0 (gf)) is used as a reference is determined from the following expression, and shown as "amount of increase in average breaking load during fiber tensioning [gf]" in the table.
• Y gf W 1 gf ⁇ W 0 gf
• a shrinkage ratio during a set with an iron at a high temperature was used.
• the evaluation was performed using a tress immediately after treatment performed as described in ⁇ Treatment method> above.
• a numerical value an average value in evaluation on a plurality of fibers (five fibers) was used. The evaluation was performed in the following procedure.
• the curling-up ratio ratio of decrease in tress length (I) (%) determined from the following expression, where L 0 is an untreated tress length (22 cm) and L is a treated tress length, was defined as curling strength.
• I L 0 ⁇ L / L 0 ⁇ 100
• the curling-up ratio ratio of decrease in tress length (I) (%) determined from the following expression, where L 0 is an untreated tress length (22 cm) and L is a treated tress length, was defined as curling strength.
• I L 0 ⁇ L / L 0 ⁇ 100
• ⁇ E*ab was defined as [(L 1 - L 0 ) 2 + (a 1 - a 0 ) 2 + (b 1 - b 0 ) 2 ] 1/2 , where (L 0 , a 0 , b 0 ) is a measured value for the untreated white tress with a color number of 30 and (L 1 , a 1 , b 1 ) is a measured value for the treated tress, and a coloring suppressing effect was determined on the basis of the following criteria.

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