Fiber treatment agent

Abstract

The present invention relates to a fiber treatment agent which improves water resistance and heat resistance, which are problems of naturally-derived fibers, imparts thermal shape memory ability, and also improves stretchability (flexibility) and surface texture without coloring the naturally-derived fibers. This fiber treatment agent contains the following components (A) and (B). (A): a compound which has a hydrogen bond term [delta] H of Hansen solubility parameters of 18.3 MPa1 / 2 or less, has at least one carboxyl group or a salt thereof, and does not have a condensed ring; (B): water.

Description

Technical Field

[0001] The present invention relates to a fiber treatment agent for imparting water resistance, heat resistance and thermal shape memory to natural-origin fibers, and relates to a fiber treatment agent suitable for treating natural-origin fibers used for fiber products such as wigs, hair extensions and other headdresses. Background Art

[0002] Natural fibers are different from synthetic fibers in that they have a natural feel and appearance derived from natural materials. Regenerated protein fibers, such as regenerated collagen fibers, are obtained by dissolving acid-soluble collagen or insoluble collagen with alkali or enzymes to prepare a spinning solution, which is then ejected from a spinning nozzle into a coagulation bath for fiberization.

[0003] However, compared with synthetic fibers, natural fibers are generally more hydrophilic and therefore have a high water absorption rate. When containing a large amount of water, they generally have low mechanical strength, and regenerated protein fibers in particular have extremely low mechanical strength. Therefore, when washed, the mechanical strength is significantly reduced due to the high water absorption rate, and they break during subsequent drying, which reduces their applicability as fiber products.

[0004] In addition, regenerated protein fibers among natural fibers have a problem of low heat resistance. For example, when heat-setting using a hair iron or the like is performed at a high temperature similar to that of human hair, shrinkage or curling may occur, thereby impairing the aesthetics.

[0005] In addition, in the case of synthetic fibers made of plastic, when heat-set using a hair iron, the shape can continue to be remembered even after subsequent washing (having thermal shape memory ability), but in the case of fibers of natural origin, when heat-set using a hair iron, the shape will disappear in the next washing (having no thermal shape memory ability). Therefore, compared with existing synthetic fibers made of plastic, there are some deficiencies in terms of styling freedom.

[0006] The above-mentioned factors have become the main reasons that hinder the popularization of natural-origin fibers, especially regenerated protein fibers, in fiber products such as headwear products. In particular, the influence of the reduction in water resistance, that is, the mechanical strength when wet, is significant.

[0007] On the other hand, in the field of human hair fibers, which are natural fibers, there is known a method of allowing a specific aldehyde derivative to act with a phenol compound in order to impart thermal shape memory capability to human hair fibers that do not originally have thermal shape memory capability (Patent Document 1).

[0008] (Patent Document 1) Japanese Patent Application Publication No. 2019-143281 Summary of the invention

[0009] The present invention provides a fiber treating agent comprising the following components (A) and (B).

[0010] (A): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 The following compounds have at least one carboxyl group or a salt thereof and do not have a condensed ring

[0011] (B) Water DETAILED DESCRIPTION

[0012] When manufacturing fiber products such as headwear products, the fibers are sometimes strongly stretched, and the stretchability (flexibility) of the treated fibers is sometimes insufficient in the technology described in Patent Document 1. Therefore, in order to prevent breakage during stretching, it is required to improve the stretchability of the treated fibers. In addition, in the technology described in Patent Document 1, the fibers are sometimes colored.

[0013] Therefore, the present invention relates to a fiber treatment agent that improves water resistance and heat resistance, which are problematic aspects of natural fibers, imparts thermal shape memory capability, and also improves stretchability (flexibility) and surface feel without coloring natural fibers.

[0014] The inventors of the present invention have conducted intensive studies and have found that by treating natural fibers with a composition containing a compound having a carboxyl group and a hydrogen bonding term of a Hansen solubility parameter of a certain value or less, the carboxyl group of the compound that has penetrated into the fiber is strongly coordinated with the metal (mainly a polyvalent metal) in the natural fiber, thereby making the fiber interior hydrophobic and preventing the compound from leaking out of the fiber. As a result, it was found that the water resistance and heat resistance of the natural fiber in both dry and wet conditions are improved, and not only can the natural fiber be given a shape by heat setting, but the elasticity (flexibility) of the natural fiber is unexpectedly improved compared to before the treatment, and can be improved to a level close to that of human hair, and no coloring occurs, thereby completing the present invention.

[0015] The present invention can provide a fiber treatment agent that can improve water resistance and heat resistance, which are problems of natural fibers, can impart thermal shape memory, and can improve stretchability (flexibility) and surface feel without coloring natural fibers.

[0016] [Fibers to be treated in the present invention]

[0017] The fiber of the treatment object of the fiber treatment agent of the present invention preferably contains metal fiber, preferably natural fiber containing metal or synthetic fiber containing metal, wherein, preferably natural fiber containing metal. Natural fiber refers to fiber obtained from natural animals and plants, or artificial fiber made of polymers or oligomers such as proteins or polysaccharides from keratin, collagen, casein, soybean, peanut, corn, silk scraps, silk protein (such as silk protein), etc. as raw materials. Among these, preferably artificial fiber made of polymers or oligomers such as proteins or polysaccharides from keratin, collagen, casein, soybean, peanut, corn, silk scraps, silk protein (such as silk protein), etc., more preferably regenerated protein fiber made of protein from keratin, collagen, casein, soybean protein, peanut protein, corn protein, silk protein (such as silk protein), etc., more preferably regenerated collagen fiber made of collagen, regenerated protein fiber such as regenerated silk fiber made of silk protein, and further preferably regenerated collagen fiber.

[0018] Regenerated collagen fibers can be manufactured using known techniques, and the composition does not have to be 100% collagen, and may contain natural or synthetic polymers or additives for quality improvement. It may also be a material obtained by post-processing the regenerated collagen fibers. As the form of the regenerated collagen fibers, filaments are preferred. The filaments are usually taken out from a reel or boxed state. In addition, the filaments obtained by the drying process in the manufacturing process of the regenerated collagen fibers can also be directly used.

[0019] The synthetic fiber containing metal may be a synthetic fiber treated with metal. The natural fiber containing metal also includes a fiber that originally contains metal, such as a fiber obtained from natural animals and plants. In this case, it is not necessary to make it contain metal again. For example, it may be a fiber treated with a metal salt, such as a fiber treated with aluminum salt for water resistance as described in Japanese Patent Publication No. 2003-027318.

[0020] [Component (A): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 The following compounds having at least one carboxyl group or a salt thereof and having no condensed ring]

[0021] Component (A) is the hydrogen bonding term of the Hansen solubility parameter δH is 18.3 MPa 1 / 2The following are compounds having at least one carboxyl group or a salt thereof and having no condensed ring. In the present invention, the hydrogen bonding term of the Hansen solubility parameter refers to δH (MPa) calculated at 25°C using the software package HSPiP 4th Edition 4.1.07 based on Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton FL, 2007 in the DIY program. 1 / 2 ) (Energy term generated by hydrogen bonds between molecules). Examples of the component (A) in the form of a salt include alkali metal salts such as sodium salts and potassium salts.

[0022] Examples of the compound of the component (A) include the following (A1) and (A2).

[0023] (A1) The hydrogen bonding term of the Hansen solubility parameter δH is 18.3 MPa 1 / 2 The following aromatic compounds having at least one carboxyl group or a salt thereof and having no condensed ring

[0024] (A2) The hydrogen bonding term of the Hansen solubility parameter δH is 11.0 MPa 1 / 2 Above 18.3MPa 1 / 2 The following compounds having at least one carboxyl group or its salt and having no condensed ring (excluding aromatic compounds)

[0025] Examples of the aromatic compound of the component (A1) include compounds represented by the following general formula (1) or (2) or salts thereof.

[0026]

[0027] [In the formula, =X represents a methylene group or an oxo group, R 1 represents a hydrogen atom, a hydroxyl group, or an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an aralkyloxy group which may have a substituent, and R 2 represents an o-phenylene group, an m-phenylene group, a p-phenylene group, a benzylidene group, or an alkylene group which may have a substituent. 2 When there is no aromatic group, R 1 is aryl, aryloxy or aralkyloxy.

[0028]

[0029] 〔In the formula, A 1 ~A 5 Each independently represents 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.]

[0030] In the component (A1), the aromatic compound represented by the general formula (1) includes compounds represented by the following general formulas (1A), (1B) or (1C).

[0031]

[0032] 〔In the formula, B 1 ~B 4 Each independently represents 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 hydroxyl group or a group represented by the following general formula (1A)-a or (1A)-b.]

[0033]

[0034] 〔In the formula, B 5 ~B 9 Indicates the same as above B 1 ~B 4 The same meaning, R 4 represents a hydrogen atom or a methyl group, and n represents an integer from 0 to 2. ]

[0035]

[0036] 〔Wherein, D 1 ~D 4 Each independently represents 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 E 1 ~E 5 Respectively and independently represent 1 ~D 4 The same group or the group represented by the general formula (1B)-a. 〕

[0037]

[0038] [In the formula, m represents an integer of 0 to 4.]

[0039]

[0040] 〔In the formula, R 6 represents a hydrogen atom or a group represented by the general formula (1C)-a, G 1 and G 2 Each independently represents a hydrogen atom, an acetyl group, a halogen atom, an aryl group which may have a substituent, an aralkyl group or an arylalkenyl group having 7 to 12 carbon atoms, or a linear or branched alkyl group, alkenyl group, alkoxy group, alkenyloxy group or aroyloxy group having 1 to 6 carbon atoms. 6 When G is a hydrogen atom, 1 and G 2At least one of them is an aryl group which may have a substituent, an aralkyl group having 7 to 12 carbon atoms, an arylalkenyl group or an aroyloxy group.]

[0041]

[0042] 〔Where J 1 ~J 5 Each independently represents 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.]

[0043] In the compound represented by the general formula (1A), R 3 The compound of hydroxyl group includes 2-carboxybenzoic acid (phthalic acid) (Hansen solubility parameter hydrogen bonding term δH: 13.4 MPa) 1 / 2 ) (hereinafter, the numerical value in the brackets after each compound name represents the hydrogen bonding term δH calculated by the above-mentioned method).

[0044] In the compound represented by the general formula (1A), R 3 The compound represented by the general formula (1A)-a includes 2-(((4-vinylbenzyl)oxy)carbonyl)benzoic acid (7.0 MPa 1 / 2 ).

[0045] In the compound represented by the general formula (1A), R 3 The compound represented by the general formula (1A)-b includes 2-((2-(acryloyloxy)ethoxy)carbonyl)benzoic acid (9.1 MPa 1 / 2 )、2-((2-(methacryloyloxy)ethoxy)carbonyl)benzoic acid (8.4MPa 1 / 2 ).

[0046] Examples of the compound represented by the general formula (1B) include 2-benzoylbenzoic acid (7.5 MPa 1 / 2 )、2-(2-methylbenzoyl)benzoic acid (6.9MPa 1 / 2 )、2-(3-methylbenzoyl)benzoic acid (6.6MPa 1 / 2 )、2-(4-methylbenzoyl)benzoic acid (7.2MPa 1 / 2 )、2-(2-chlorobenzoyl)benzoic acid (7.1MPa 1 / 2 )、2-(3-chlorobenzoyl)benzoic acid (6.9MPa 1 / 2 )、2-(4-chlorobenzoyl)benzoic acid (7.5MPa 1 / 2 ), 2-(4-(2-(2-(acryloyloxy)ethoxy)ethoxy)benzoyl)benzoic acid (8.7MPa 1 / 2 ).

[0047] In the compound represented by the general formula (1C), R 6 The compounds with hydrogen atoms include phenyl succinic acid (15.8 MPa 1 / 2 ), 2,3-diphenylsuccinic acid (11.9MPa 1 / 2 )、(+)-di-p-toluoyl-D-tartaric acid (10.2MPa 1 / 2 ).

[0048] In the compound represented by the general formula (1C), R 6 The compound represented by the general formula (1C)-a includes 4-oxo-4-((4-vinylbenzyl)oxy)butanoic acid (10.1 MPa 1 / 2 ).

[0049] In addition, although the general formula (1A), (1B) and (1C) do not include the compound, as the compound included in the general formula (1), 3-carboxybenzoic acid (isophthalic acid) (12.9 MPa 1 / 2 )、4-carboxybenzoic acid (terephthalic acid) (13.7MPa 1 / 2 )、3-Benzoylbenzoic acid (7.2MPa 1 / 2 )、4-Benzoylbenzoic acid (7.9MPa 1 / 2 The numerical value in the brackets after each compound name is the hydrogen bond term δH calculated using the above method.

[0050] Specific examples of the aromatic compound represented by the general formula (2) in the component (A1) include benzoic acid (9.5 MPa 1 / 2 )、2-methylbenzoic acid (8.4MPa 1 / 2 )、3-Methylbenzoic acid (8.0MPa 1 / 2 )、4-Methylbenzoic acid (8.8MPa 1 / 2 )、2-ethylbenzoic acid (7.7MPa 1 / 2 )、3-ethylbenzoic acid (7.4MPa 1 / 2 )、4-ethylbenzoic acid (8.1MPa 1 / 2 )、2-propylbenzoic acid (7.0MPa 1 / 2 )、3-propylbenzoic acid (6.7MPa 1 / 2 )、4-propylbenzoic acid (7.4MPa 1 / 2 )、2-isopropylbenzoic acid (6.7MPa 1 / 2 )、3-isopropylbenzoic acid (6.5MPa 1 / 2 )、4-isopropylbenzoic acid (7.1MPa 1 / 2 )、2-n-butylbenzoic acid (6.8MPa1 / 2 )、3-n-butylbenzoic acid (6.5MPa 1 / 2 )、4-n-butylbenzoic acid (7.2MPa 1 / 2 ), 2-tert-butylbenzoic acid (6.1MPa 1 / 2 ), 3-tert-butylbenzoic acid (5.9MPa 1 / 2 )、4-tert-butylbenzoic acid (6.5MPa 1 / 2 )、2-vinylbenzoic acid (8.0MPa 1 / 2 )、3-vinylbenzoic acid (7.7MPa 1 / 2 )、4-vinylbenzoic acid (8.5MPa 1 / 2 )、2-acetylbenzoic acid (8.6MPa 1 / 2 )、3-acetylbenzoic acid (8.2MPa 1 / 2 )、4-acetylbenzoic acid (8.9MPa 1 / 2 )、2-methoxybenzoic acid (9.7MPa 1 / 2 )、3-methoxybenzoic acid (9.3MPa 1 / 2 )、4-methoxybenzoic acid (10.1MPa 1 / 2 )、2-chlorobenzoic acid (8.7MPa 1 / 2 )、3-chlorobenzoic acid (8.4MPa 1 / 2 )、4-chlorobenzoic acid (9.2MPa 1 / 2 )、2-bromobenzoic acid (9.1MPa 1 / 2 )、3-bromobenzoic acid (8.8MPa 1 / 2 )、4-bromobenzoic acid (10.1MPa 1 / 2 ) etc. Among them, 4-ethylbenzoic acid, 4-vinylbenzoic acid and benzoic acid are preferred.

[0051] Examples of the compounds other than the compounds of the general formulae (1) and (2) of the component (A1) include phenylbutyric acid.

[0052] Examples of the compound of component (A2) include potassium 2,4-hexadienoate (12.5 MPa 1 / 2 ).

[0053] From the viewpoint of making the fiber interior appropriately hydrophobic, the hydrogen bonding term δH of the aromatic compound of component (A1) is preferably 16.0 MPa. 1 / 2 Below, more preferably 13.5MPa 1 / 2 Below, more preferably 12.0 MPa 1 / 2 Below, more preferably 10.0 MPa 1 / 2 Below, and preferably 3.0 MPa 1 / 2 More preferably 4.0 MPa 1 / 2More preferably, 5.0 MPa 1 / 2 above.

[0054] From the viewpoint of appropriately hydrophobizing the inside of the fiber, the hydrogen bonding term δH of the compound of component (A2) is preferably 16.0 MPa. 1 / 2 Below, more preferably 15.0 MPa 1 / 2 Below, more preferably 14.0 MPa 1 / 2 Below, more preferably 13.0 MPa 1 / 2 Below, and preferably 11.0 MPa 1 / 2 More preferably 11.5 MPa 1 / 2 More preferably, 12.0 MPa 1 / 2 above.

[0055] In addition to the type of component (A), the preferred content of component (A) is described below. In the present invention, the content of component (A) refers to the content of the acid form corresponding to the component (A) in the form of a salt. The content of component (A) varies depending on the pH range of the fiber treatment agent, and is preferably in the range shown below.

[0056] Regarding benzoic acid or a salt thereof (hereinafter sometimes referred to as "component (A1-1)") as component (A) in particular, when the pH of the fiber-treating agent is 2.0 or more and less than 6.5, from the viewpoint of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the natural-origin fiber after the treatment, the content of component (A1-1) in the fiber-treating agent is preferably 0.8% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, further preferably 10% by mass or more, further more preferably 15% by mass or more, further more preferably 20% by mass or more, in terms of benzoic acid (acid form), and from the viewpoint of improving the touch of the fiber surface, it is preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, further more preferably 40% by mass or less, further more preferably 35% by mass or less.

[0057] That is, when component (A) is (A1-1) benzoic acid or a salt thereof and the pH of the fiber treatment agent is 2.0 or more and less than 6.5, from the above viewpoints, the content of component (A1-1) in the fiber treatment agent of the present invention is preferably 0.8 to 90% by mass, more preferably 3.0 to 80% by mass, even more preferably 5.0 to 70% by mass, further preferably 10 to 50% by mass, further more preferably 15 to 40% by mass, and further more preferably 20 to 35% by mass in terms of benzoic acid (acid type).

[0058] When the component (A) is (A1-1) benzoic acid or a salt thereof and the pH of the fiber-treating agent is 6.5 or more and 11.0 or less, the content of the component (A1-1) in the fiber-treating agent is preferably 0.8% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, and even more preferably 10% by mass or more, in terms of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the natural-origin fiber after the treatment. The content is more preferably 15% by mass or more, further preferably 20% by mass or more, further preferably 25% by mass or more, further preferably 26% by mass or more, further preferably 28% by mass or more, further preferably 30% by mass or more, and from the viewpoint of improving the feel of the fiber surface, it is preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, further more preferably 45% by mass or less, further more preferably 40% by mass or less.

[0059] That is, when component (A) is (A1-1) benzoic acid or a salt thereof and the pH of the fiber treatment agent is 6.5 or more and 11.0 or less, from the above viewpoints, the content of component (A1-1) in the fiber treatment agent of the present invention is preferably 0.8 to 90% by mass, more preferably 3.0 to 80% by mass, even more preferably 5.0 to 70% by mass, further preferably 10 to 70% by mass, further more preferably 15 to 50% by mass, further more preferably 20 to 50% by mass, further more preferably 25 to 45% by mass, further more preferably 26 to 45% by mass, further more preferably 28 to 40% by mass, and further more preferably 30 to 40% by mass in terms of benzoic acid (acid form).

[0060] Regarding the component (A1) other than benzoic acid or its salt in the component (A) (hereinafter sometimes referred to as "component (A1-2)"), when the pH of the fiber-treating agent is 2.0 or more and less than 6.5, from the viewpoint of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the natural-origin fiber after the treatment, the content of the component (A1-2) in the fiber-treating agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, and from the viewpoint of improving the touch of the fiber surface, the content of the component (A1-2) in the fiber-treating agent is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and still more preferably 45% by mass or less.

[0061] That is, when component (A) is component (A1) other than (A1-2) benzoic acid or its salt and the pH of the fiber treatment agent is 2.0 or more and less than 6.5, from the above viewpoint, the content of component (A1-2) in the fiber treatment agent of the present invention is preferably 0.1 to 70 mass %, more preferably 0.2 to 60 mass %, further preferably 0.5 to 50 mass %, and further more preferably 1.0 to 45 mass %.

[0062] In addition, when the component (A) is a component (A1) other than (A1-2) benzoic acid or a salt thereof and the pH of the fiber-treating agent is 6.5 or more and 11.0 or less, from the viewpoint of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the treated natural-origin fiber, the content of the component (A1-2) in the fiber-treating agent is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 5.0% by mass or more, and still more preferably 10% by mass or more, and from the viewpoint of improving the touch of the fiber surface, it is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and still more preferably 40% by mass or less.

[0063] That is, when component (A) is component (A1) other than (A1-2) benzoic acid or its salt and the pH of the fiber treatment agent is 6.5 or more and 11.0 or less, from the above viewpoint, the content of component (A1-2) in the fiber treatment agent of the present invention is preferably 1.0 to 70% by mass, more preferably 2.0 to 60% by mass, further preferably 5.0 to 50% by mass, and further more preferably 10 to 40% by mass.

[0064] When component (A) is component (A2) and the pH of the fiber-treating agent is 2.0 or more and less than 6.5, the content of component (A2) in the fiber-treating agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, further more preferably 1.0% by mass or more, from the viewpoint of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the natural-origin fiber after the treatment, and is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 30% by mass or less, from the viewpoint of improving the touch of the fiber surface.

[0065] That is, when component (A) is component (A2) and the pH of the fiber treatment agent is 2.0 or more and less than 6.5, from the above viewpoints, the content of component (A2) in the fiber treatment agent of the present invention is preferably 0.1 to 60% by mass, more preferably 0.2 to 50% by mass, further preferably 0.5 to 40% by mass, and further more preferably 1.0 to 30% by mass.

[0066] When component (A) is component (A2) and the pH of the fiber-treating agent is 6.5 or more and 11.0 or less, the content of component (A2) in the fiber-treating agent is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 5.0% by mass or more, and further preferably 10% by mass or more, from the viewpoint of imparting higher shape retention, water resistance, stretchability (flexibility, i.e., high elongation at break when the fiber is stretched) and heat resistance to the natural-origin fiber after the treatment, and is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and further more preferably 40% by mass or less, from the viewpoint of improving the touch of the fiber surface.

[0067] That is, when component (A) is component (A2) and the pH of the fiber treatment agent is 6.5 or more and 11.0 or less, from the above viewpoint, the content of component (A2) in the fiber treatment agent of the present invention is preferably 1.0 to 70% by mass, more preferably 2.0 to 60% by mass, further preferably 5.0 to 50% by mass, and further more preferably 10 to 40% by mass.

[0068] In addition, when the fiber treatment agent contains two or more compounds as component (A), there is a tendency for the solubility of the component (A) as a whole to increase. Therefore, from the perspective of improving the solubility of the component (A) as a whole, reducing the turbidity of the fiber treatment agent, being able to treat the fiber uniformly, and improving the touch of the fiber surface after such treatment, it is preferred that the fiber treatment agent contains two or more compounds as component (A). When the fiber treatment agent contains two or more compounds as component (A), at least one of them is preferably an aromatic compound represented by the general formula (2), and more preferably benzoic acid or a salt thereof. When the component (A) contains an aromatic compound represented by the general formula (2), it is preferred that the content of the compound in the component (A) is the highest, and when benzoic acid or a salt thereof is contained, it is more preferred that the content of the compound in the component (A) is the highest.

[0069] When the pH of the fiber-treating agent is 2.0 or more and less than 6.5 and the fiber-treating agent contains two or more compounds as the component (A), the content of the component (A) remaining after removing the compound with the highest concentration among all the components (A) in the fiber-treating agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, and is also preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5.0% by mass or less, from the viewpoint of improving the solubility of the entire component (A), reducing the turbidity of the fiber-treating agent, being able to treat the fibers uniformly, and improving the touch of the fiber surface after such treatment.

[0070] Furthermore, when the pH of the fiber-treating agent is 6.5 or more and 11.0 or less and the fiber-treating agent contains two or more compounds as the component (A), the content of the component (A) remaining after removing the compound with the highest concentration among all the components (A) in the fiber-treating agent is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 2.0% by mass or more, and is further preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less, from the viewpoint of improving the solubility of the entire component (A), reducing the turbidity of the fiber-treating agent, being able to treat the fibers uniformly, and improving the touch of the fiber surface after the treatment.

[0071] Even when the pH of the fiber-treating agent is any, when the fiber-treating agent contains two or more compounds as the component (A), from the viewpoints of improving the solubility of the entire component (A), reducing the turbidity of the fiber-treating agent, being able to treat the fibers uniformly, and improving the touch of the fiber surface after such treatment, the mass ratio of the component (A) remaining after removing the compound with the highest concentration among all the components (A) in the fiber-treating agent to the compound (mass of the component (A) remaining after removing the compound with the highest concentration among all the components (A)) / (mass of the compound with the highest concentration among the component (A)) is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.10 or more, and is further preferably 1.0 or less, more preferably 0.5 or less, and further preferably 0.25 or less.

[0072] [Ingredient (B): Water]

[0073] The fiber treatment agent of the present invention uses water as a medium. The content of component (B) in the fiber treatment agent of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further more preferably 40% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, further more preferably 85% by mass or less.

[0074] That is, the content of component (B) in the fiber treatment agent of the present invention is preferably 10 to 99% by mass, more preferably 20 to 95% by mass, further preferably 30 to 90% by mass, and further more preferably 40 to 85% by mass.

[0075] [Cationic surfactant]

[0076] The fiber treatment agent of the present invention may contain a cationic surfactant within a range that does not impair the effects of the present invention. The cationic surfactant is preferably a monolong chain alkyl quaternary ammonium salt having one alkyl group having 8 to 24 carbon atoms and three alkyl groups having 1 to 4 carbon atoms.

[0077] It is preferred that at least one mono-long chain alkyl quaternary ammonium surfactant is selected from the compounds represented by the following general formula (3).

[0078]

[0079] 〔In the formula, R 7 represents a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms, R 11 -CO-NH-(CH2) m - or R 11 -CO-O-(CH2) m -(R 11 represents a saturated or unsaturated linear or branched alkyl chain having 7 to 21 carbon atoms, p represents an integer of 1 to 4), R 8 , R 9 and R 10 An independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, - represents chloride ion, bromide ion, methylsulfate ion or ethylsulfate ion. 】

[0080] Preferred cationic surfactants include long-chain quaternary ammonium compounds such as cetyltrimethylammonium chloride, myristyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetyltrimethylammonium bromide, and stearamidopropyltrimethylammonium chloride. These may be used alone or in the form of a mixture thereof.

[0081] From the viewpoint of improving the touch of the surface of the natural-origin fiber after treatment and further enhancing the effect of the present invention, the content of the cationic surfactant in the fiber treatment agent of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and is preferably 10% by mass or less, more preferably 5.0% by mass or less.

[0082] 〔Silicone〕

[0083] The fiber treatment agent of the present invention may contain silicone from the viewpoint of improving the touch of the treated natural fiber surface and improving combing properties. The silicone is preferably at least one selected from dimethylpolysiloxane and amino-modified silicone.

[0084] As the dimethylpolysiloxane, any cyclic or non-cyclic dimethylpolysiloxane polymer may 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, FZ-4188 (all from Dow Corning Toray Corporation), KF-9088, KM-900 series, MK-15H, and MK-88 (all from Shin-Etsu Chemical Co., Ltd.).

[0085] As the amino-modified silicone, any silicone having an amino group or an ammonium group can be used, and examples thereof include amino-modified silicone oils in which all or part of the terminal hydroxyl groups are blocked with methyl groups or the like, and unblocked amino-terminated polydimethylsiloxanes. From the viewpoint of improving the touch of the surface of the treated natural fiber and improving the combing properties, preferred amino-modified silicones include, for example, compounds represented by the following formula.

[0086]

[0087] [wherein, R' represents a hydrogen atom, a hydroxyl group or R X , R X represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and J represents R X 、R"-(NHCH2CH2) a NH2、OR X or hydroxyl, R" represents a divalent hydrocarbon group having 1 to 8 carbon atoms, a represents a number from 0 to 3, and b and c represent a number 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, and further preferably 40 or more and less than 800 in number average.]

[0088] Specific examples of commercially available products of preferred amino-modified silicones include amino-modified silicone oils such as SF8452C, SS3551 (all from Dow Corning Toray Corporation), KF-8004, KF-867S, and KF-8015 (all from Shin-Etsu Chemical Co., Ltd.), and aminodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671, and FZ4672 (all from Dow Corning Toray Corporation).

[0089] From the viewpoint of improving the feel of the surface of the natural-origin fiber after treatment and further enhancing the effect of the present invention, the content of silicone in the fiber treatment agent of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5.0% by mass or less.

[0090] 〔Cationic polymer〕

[0091] Furthermore, from the viewpoint of improving the touch of the surface of the natural-origin fiber after treatment, the fiber treatment agent of the present invention may contain a cationic polymer.

[0092] Cationic polymer refers to a polymer having a cationic group or a group that can be ionized into a cationic group, and also includes amphoteric polymers that present cationicity as a whole. That is, polymers containing amino or ammonium groups or diallyl quaternary ammonium salts as structural units in the side chains of the polymer chains can be cited, for example, cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salts, quaternized polyvinyl pyrrolidone derivatives, etc. can be cited. Among these, from the perspective of improving the softness, smoothness and easy passing of fingers during rinsing or shampooing, the effects of easy combing and moisture retention during drying and the stability of the preparation, preferably selected from polymers containing diallyl quaternary ammonium salts as structural units, quaternized polyvinyl pyrrolidone derivatives, cationized cellulose derivatives One or more, more preferably selected from polymers or copolymers of diallyl quaternary ammonium salts, cationized cellulose derivatives One or more.

[0093] Specific examples of preferred diallyl quaternary ammonium salt polymers or copolymers include dimethyl diallyl ammonium chloride polymers (polyquaternium-6, such as Merquat 100; Lubrizol Advanced Materials Co., Ltd.), dimethyl diallyl ammonium chloride / acrylic acid copolymers (polyquaternium-22, such as Merquat 280, Merquat 295; Lubrizol Advanced Materials Co., Ltd.), and dimethyl diallyl ammonium chloride / acrylamide copolymers (polyquaternium-7, such as Merquat 550; Lubrizol Advanced Materials Co., Ltd.).

[0094] Specific examples of preferred quaternized polyvinyl pyrrolidone derivatives include polymers obtained by polymerizing a vinyl pyrrolidone copolymer with dimethylaminoethyl methacrylate (polyquaternium salt 11, such as GAFQUAT 734, GAFQUAT 755, and GAFQUAT 755N (all from Ashland)).

[0095] Specific examples of preferred cationized cellulose include polymers obtained by adding glycidyl trimethylammonium chloride to hydroxycellulose (polyquaternium 10, such as LEOGARD G, LEOGARD GP (all from Lion), POLYMER JR-125, POLYMER JR-400, POLYMER JR-30M, POLYMER LR-400, POLYMER LR-30M (all from Amerchol)), hydroxyethylcellulose dimethyl diallylammonium chloride (polyquaternium-4, such as CELQUATH-100, CELQUAT L-200 (all from Akzo Nobel)), and the like.

[0096] From the viewpoint of improving the touch of the surface of the natural-origin fiber after treatment, the content of the cationic polymer in the fiber treatment agent of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less.

[0097] The fiber treatment agent of the present invention may further contain: an antioxidant such as ascorbic acid; a pH adjuster such as sodium hydroxide, potassium hydroxide, phosphoric acid, hydrochloric acid, etc.

[0098] 〔pH〕

[0099] From the viewpoint of suppressing damage to natural-origin fibers and improving durability, the pH of the fiber treatment agent of the present invention is preferably 2.0 or more, more preferably 3.0 or more, further preferably 3.5 or more, further more preferably 4.0 or more, and preferably 11.0 or less, more preferably 10.0 or less, further preferably 9.0 or less. However, the pH of the present invention is a value at 25°C.

[0100] That is, from the viewpoint of suppressing damage to natural fibers and improving durability, the pH of the fiber treatment agent of the present invention is preferably 2.0 to 11.0, more preferably 3.0 to 10.0, further preferably 3.5 to 9.0, and further more preferably 4.0 to 9.0.

[0101] [Storage of fiber treatment agents]

[0102] When the fiber treatment agent produced as described above is transported and stored before being applied to fibers, or when the raw materials before preparing the fiber treatment agent are transported and stored, in order to prevent unintentional reaction or recrystallization in the transported component (A), the storage temperature may be set to a low or high temperature, or nitrogen may be filled into the void portion in the storage container.

[0103] The storage temperature of the fiber treatment agent is preferably 1°C or higher, more preferably 2°C or higher, and further preferably 5°C or higher from the viewpoint of preventing freezing or recrystallization, and is preferably 25°C or lower, more preferably 20°C or lower, and further preferably 15°C or lower from the viewpoint of preventing oxidative coloration or unintentional reaction.

[0104] In addition, the storage temperature of the fiber treatment agent is preferably 20°C or higher, more preferably 30°C or higher, and further preferably 40°C or higher from the viewpoint of preventing recrystallization of a high concentration solution, and is preferably 80°C or lower, more preferably 70°C or lower, and further preferably 60°C or lower from the viewpoint of preventing oxidative coloration or unintentional reaction.

[0105] 〔Fiber processing method〕

[0106] (Basic processing)

[0107] By using the fiber treatment agent of the present invention, by treating natural-origin fibers using a method including the following step (i), water resistance and heat resistance, which are problematic points of natural-origin fibers, can be improved, thermal shape memory can be imparted, and stretchability (flexibility) and surface feel can be improved.

[0108] Step (i) A step of impregnating natural-origin fibers in the fiber-treating agent of the present invention

[0109] In step (i), the natural fiber impregnated with the fiber treatment agent may be dry or wet. The amount of the fiber treatment agent impregnated with the natural fiber is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, further preferably 10 or more, further more preferably 20 or more, and preferably 500 or less, more preferably 250 or less, and further preferably 100 or less in terms of the bath ratio relative to the mass of the natural fiber (mass of the fiber treatment agent / mass of the natural fiber).

[0110] That is, the bath ratio is preferably 2 to 500, more preferably 3 to 250, further preferably 5 to 100, further more preferably 10 to 100, and further more preferably 20 to 100.

[0111] In step (i), the natural fiber may be fixed in advance with a curling iron or the like, and then immersed in the fiber treatment agent of the present invention under heating. By doing so, the natural fiber can be given a desired shape in addition to thermal shape memory and high durability.

[0112] The immersion of the natural fiber in the fiber treatment agent in step (i) is preferably carried out under heating, and the heating is carried out by heating the fiber treatment agent. In addition, the heating can also be carried out by immersing the natural fiber in the fiber treatment agent in a heated state, and can also be carried out by immersing the natural fiber in the fiber treatment agent at a low temperature and then heating it. Regarding the temperature of the fiber treatment agent, in order to obtain the effect of the present invention by increasing the interaction between component (A) and the fiber constituent molecules in the natural fiber, such as protein molecules, it is preferably 20°C or more, more preferably 35°C or more, and further preferably 45°C or more. In addition, in order to prevent the natural fiber from being modified and deteriorated due to heat, it is preferably less than 100°C, more preferably 80°C or less, further preferably 70°C or less, and further preferably 60°C or less.

[0113] The immersion time in step (i) can be appropriately adjusted according to the heating temperature. For example, from the viewpoint of improving the stretchability of natural fibers, the immersion time is preferably 15 minutes or more, more preferably 30 minutes or more, and even more preferably 1 hour or more. In order to suppress damage to natural fibers, the immersion time is preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 12 hours or less.

[0114] Step (i) is preferably performed under an environment where water evaporation is suppressed. A specific method for suppressing water evaporation is to cover the container impregnated with the fiber treatment agent for natural fibers with a film-like material, a cap, a cover, etc. made of a material that does not permeate water vapor.

[0115] After step (i), the natural fiber may or may not be rinsed. However, rinsing is preferred from the viewpoint of preventing the excess component (A) from deteriorating the texture of the natural fiber surface.

[0116] It is considered that by these treatments, the component (A) permeates into the natural fibers and strongly coordinates with metals, for example, polyvalent metals, in the fibers, thereby producing various effects.

[0117] [Additional processing is possible]

[0118] In addition to the above-mentioned step (i), one or more treatments selected from the group consisting of bleaching, dyeing, surface treatment for imparting hydrophobicity and reducing friction, and heat treatment for further improving the stretchability (flexibility) of the fiber may be additionally performed.

[0119] At this time, each treatment of bleaching and dyeing can be carried out before the aforementioned step (i), or it can be carried out afterwards. In addition, it is also possible to combine and add a plurality of treatments. When adding both bleaching and dyeing, except that it is necessary to bleach before dyeing, any treatment can be carried out first, and other treatments can also be carried out between bleaching and dyeing.

[0120] On the other hand, the surface treatment for imparting hydrophobicity and low friction and the heat treatment for further improving the elasticity (flexibility) of the fiber need to be performed after the aforementioned step (i), but the order of the treatments with bleaching and dyeing is not particularly limited. In addition, the surface treatment for imparting hydrophobicity and low friction and the heat treatment for further improving the elasticity (flexibility) of the fiber may be performed first.

[0121] (Decolorization)

[0122] Decolorization is performed by dipping the natural fiber in a decolorizing agent composition containing an alkali agent, an oxidant, and water. The decolorizing agent composition is usually a two-component form, with the first component containing an alkali agent and water and the second component containing an oxidant and water. The two components are usually kept separately and mixed before dipping the natural fiber.

[0123] Preferred alkali agents include, for example, ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkylenediamines (1,3-propylenediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof, but are not limited to these.

[0124] The content of the alkaline agent in the decolorizing agent composition (a mixture of the first agent and the second agent in the case of a two-part composition) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1.0% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less.

[0125] Preferred oxidizing agents include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate. Among these oxidizing agents, hydrogen peroxide is preferred.

[0126] The content of the oxidizing agent in the decolorizing agent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 9% by mass or less.

[0127] When the first and second agents are stored separately, the pH of the second agent at 25°C is preferably 2.0 or more, more preferably 2.5 or more, and preferably 6.0 or less, and more preferably 4.0 or less. The pH can be adjusted using an appropriate buffer. The pH of the decolorizing agent composition at 25°C is preferably 6 or more, more preferably 6.5 or more, and further preferably 6.8 or more, and preferably 11.0 or less, more preferably 10.5 or less, and further preferably 10.0 or less.

[0128] (dyeing)

[0129] Dyeing is performed by immersing the natural fiber in a dye composition. The dye composition contains a dye and may optionally contain an alkali agent, an acid, an oxidizing agent, etc. Examples of the dye include direct dyes, oxidation dyes, and combinations thereof.

[0130] The type of direct dye is not particularly limited, and any direct dye suitable for dyeing can be used. As examples of direct dyes, anionic dyes, nitro dyes, disperse dyes, cationic dyes, and dyes with azophenol structure selected from the following HC Red 18, HC Blue 18 and HC Yellow 16, and their salts, and their mixtures can be cited.

[0131]

[0132] As the cationic dye, for example, 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 and basic yellow 87 and mixtures thereof can be listed, but are not limited to these. Particularly preferred are basic red 51, basic orange 31, basic yellow 87 and mixtures thereof.

[0133] Examples of the anionic dye include 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, and 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.27, D&C Red No.33, D&C Violet 2, D&C Yellow No.7, D&C Yellow No.8, D&C Yellow No.10, FD&C Red 2, FD&C Red 40, FD&C Red No.4, FD&C Yellow No.6, FD&C Blue 1, Food Black 1, Food Black 2, and alkali metal salts (sodium salt, potassium salt, etc.) thereof and mixtures thereof, but are not limited to these.

[0134] Among these, 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 and acid yellow 10, and salts thereof. More preferred anionic dyes are acid red 52, acid violet 2, acid red 33, acid orange 4 and acid yellow 10, and salts thereof and mixtures thereof.

[0135] Examples of the nitro dye include 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. 14, HC Purple BS, HC Purple No. 1, HC Purple 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-nitrobenzene, 1,4-diamino-2-nitrobenzene, 3-nitro-4-aminophenol, 1-hydroxy-2-amino-3-nitrobenzene and 2-hydroxyethylpicramic acid and mixtures thereof, but are not limited thereto.

[0136] Examples of the disperse dye include Disperse Blue 1, Disperse Black 9, Disperse Violet 1, and mixtures thereof, but the present invention is not limited to these.

[0137] These direct dyes may be used alone or in combination of two or more, and direct dyes having different ionicity may be used in combination.

[0138] The content of the direct dye in the dye composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more from the viewpoint of obtaining sufficient dyeing properties, and is preferably 10% by mass or less, more preferably 7.5% by mass or less, further preferably 5.0% by mass or less, and further preferably 3.0% by mass or less from the viewpoint of compatibility.

[0139] When the dye composition contains only a direct dye as a dye, an oxidizing agent is not required for dyeing natural fibers. However, when the color of natural fibers is to be brightened, an oxidizing agent may be contained in the composition.

[0140] When the dye composition contains an oxidation dye, it is usually prepared in two parts, the first part contains an oxidation dye intermediate (precursor and coupler) and an alkali agent, and the second part contains an oxidizing agent such as hydrogen peroxide. The two parts are usually kept separately and mixed before impregnation of natural fibers.

[0141] The oxidation dye intermediate is not particularly limited, and any known precursors and couplers commonly used in dyeing products can be appropriately used.

[0142] Examples of the precursor include p-phenylenediamine, toluene-2,5-diamine, 2-chloro-p-phenylenediamine, N-methoxyethyl-p-phenylenediamine, N-phenyl-p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,3,2'-p-phenylenediamine, p-aminophenol, p-methylaminophenol, 3-methyl-4-aminophenol, Phenol, 2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminomethyl)-4-aminophenol, o-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1-hydroxyethylpyrazole, salts thereof, and mixtures thereof, but are not limited thereto.

[0143] Examples of the coupler include m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenethyl ether, 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, m-aminophenol, 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-m-aminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4-fluoro-5-aminophenol, p-Amino-o-cresol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 3,4-methylenedioxyphenol Oxyaniline, 1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, salts thereof, and mixtures thereof, but are not limited thereto.

[0144] The content of the precursor and the coupler in the dye composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 7.5% by mass or less, and further preferably 5.0% by mass or less.

[0145] When the dye composition contains an oxidative dye, it also contains an alkali agent. Preferred alkali agents include, for example, ammonia and its salts; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, etc.) and their salts; alkanediamines (1,3-propylenediamine, etc.) and their salts; and carbonates (guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.); and mixtures thereof, but are not limited thereto.

[0146] The content of the alkali agent in the dye composition is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, further preferably 1.0 mass % or more, and is preferably 15 mass % or less, more preferably 10 mass % or less, further preferably 7.5 mass % or less.

[0147] When the dye composition contains an oxidation dye, the composition containing the oxidation dye (second agent) is stored separately from the composition containing the oxidation dye (first agent) and mixed before impregnating the natural fiber. Preferred oxidants include, but are not limited to, hydrogen peroxide, urea peroxide, melamine peroxide, and sodium bromate. Among these oxidants, hydrogen peroxide is preferred.

[0148] The content of the oxidizing agent in the dye composition is preferably 1% by mass or more, more preferably 2% by mass or more, and is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 9% by mass or less.

[0149] When the first and second agents are stored separately, the pH of the second agent at 25°C is preferably 2 or more, more preferably 2.5 or more, and preferably 6 or less, and more preferably 4 or less. The pH can be adjusted using a suitable buffer. The pH of the dye composition formed by mixing the first and second agents at 25°C is preferably 6 or more, more preferably 6.5 or more, and further preferably 6.8 or more, and further preferably 11 or less, more preferably 10.5 or less, and further preferably 10 or less.

[0150] When the dye composition contains an oxidation dye, it may further contain the direct dye exemplified above.

[0151] The dye composition may preferably further contain a surfactant, conditioning component, etc. as shown below, and may preferably be in the form of a solution, emulsion, cream, paste, or mousse.

[0152] From the viewpoint of allowing the dye composition to efficiently penetrate and diffuse into the interior of the natural-origin fiber and further improving the dyeing effect, the temperature of the dye composition is preferably above 0°C, more preferably above 10°C, further preferably above 20°C, and preferably below 90°C, more preferably below 80°C.

[0153] (Post-heating: heating treatment to further improve the elasticity (flexibility) of the fiber)

[0154] From the viewpoint of further effectively improving the elasticity of natural fibers, the natural fibers can be heated while being stretched by applying tension. In this heating, when the natural fibers are in a small amount, it is preferred to use a hair iron, and when the natural fibers are in a large amount, the same result can be obtained by applying tension using a winder while heating with warm air.

[0155] Regarding the fiber elongation during heating, from the viewpoint of more effectively improving the elasticity of the fiber, it is preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.5% or more. From the viewpoint of suppressing damage to the fiber, it is preferably 10% or less, more preferably 5.0% or less, and further preferably 2.0% or less.

[0156] Regarding the heating temperature, from the viewpoint of more effectively improving the stretchability of the fiber, it is preferably above 120°C, more preferably above 140°C, and further preferably above 160°C. From the viewpoint of suppressing damage to the fiber, it is preferably below 240°C, more preferably below 220°C, and further preferably below 200°C.

[0157] Regarding the heating time, from the viewpoint of more effectively improving the elasticity of the fiber, it is preferably more than 1 second, more preferably more than 3 seconds, and further preferably more than 5 seconds. From the viewpoint of suppressing damage to the fiber, it is preferably less than 60 seconds, more preferably less than 30 seconds, and further preferably less than 20 seconds.

[0158] After heating, from the viewpoint of more effectively improving the stretchability of the fiber, the natural fiber may be left to stand in water while tension is applied to stretch it.

[0159] Regarding the elongation at this time, from the viewpoint of more effectively improving the stretchability of the fiber, it is preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.5% or more. From the viewpoint of suppressing damage to the fiber, it is preferably 10% or less, more preferably 5.0% or less, and further preferably 2.0% or less.

[0160] Regarding the water temperature, from the viewpoint of more effectively improving the stretchability of the fiber, it is preferably above 5°C, more preferably above 20°C, and further preferably above 30°C. From the viewpoint of suppressing damage to the fiber, it is preferably below 80°C, more preferably below 60°C, and further preferably below 50°C.

[0161] Regarding the standing time in water, from the viewpoint of more effectively improving the elasticity of the fiber, it is preferably more than 1 minute, more preferably more than 5 minutes, and further preferably more than 30 minutes. From the viewpoint of suppressing damage to the fiber, it is preferably less than 48 hours, more preferably less than 24 hours, and further preferably less than 3 hours.

[0162] By this operation, depending on the treatment conditions in step (i), the fibers can achieve elasticity equivalent to that of human hair when dried.

[0163] The fibers subjected to the above-mentioned various treatments can also be improved in texture by a common fiber post-treatment, for example, treatment with a fiber treatment agent such as a softener or treatment with a hair care agent such as a conditioner or a hair treatment agent.

[0164] By treating the natural source fiber using the above fiber processing method and containing component (A) in the fiber, it is possible to give a shape by heat setting, and it is possible to produce fibers with excellent water resistance, heat resistance, and tensile elastic modulus, and fibers with highly improved stretchability (flexibility) of natural source fibers, which are suitable for producing fibers for headwear products, etc. In addition, the fibers can be used to produce various fiber products, which are suitable for producing headwear products, etc.

[0165] In the present invention, preferred headwear products include, for example, hair wigs, fake hair, weaving, hair extensions, braid hair, hair accessories, and doll hair.

[0166] With regard to the above-described embodiments, preferred aspects of the present invention will be further disclosed below.

[0167] <1> A fiber treating agent comprising the following components (A) and (B).

[0168] (A): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 The following compounds have at least one carboxyl group or a salt thereof and do not have a condensed ring

[0169] (B) Water

[0170] <2> The fiber treating agent according to <1>, wherein the component (A) is preferably one or more compounds selected from the following components (A1) and (A2).

[0171] (A1) The hydrogen bonding term of the Hansen solubility parameter δH is 18.3 MPa 1 / 2 The following aromatic compounds having at least one carboxyl group or a salt thereof and having no condensed ring

[0172] (A2) The hydrogen bonding term of the Hansen solubility parameter δH is 11.0 MPa 1 / 2 Above 18.3MPa 1 / 2 The following compounds having at least one carboxyl group or its salt and having no condensed ring (excluding aromatic compounds)

[0173] <3> The fiber treating agent according to <2>, wherein the component (A1) is a compound represented by the following general formula (1) or (2) or a salt thereof, or phenylbutyric acid.

[0174]

[0175] [In the formula, =X represents a methylene group or an oxo group, R 1 represents a hydrogen atom, a hydroxyl group, or an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an aralkyloxy group which may have a substituent, and R 2 represents an o-phenylene group, an m-phenylene group, a p-phenylene group, a benzylene group, or an alkylene group which may have a substituent. 2 When there is no aromatic group, R 1 is aryl, aryloxy or aralkyloxy.

[0176]

[0177] 〔In the formula, A 1 ~A 5 Each independently represents 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.]

[0178] <4> The fiber treatment agent as described in <3>, wherein the compound represented by the general formula (1) is a compound represented by the general formula (1A), (1B) or (1C) shown below, 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3-benzoylbenzoic acid or 4-benzoylbenzoic acid.

[0179]

[0180] 〔In the formula, B 1 ~B 4 Each independently represents 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 hydroxyl group, or a group represented by the following general formula (1A)-a or (1A)-b.]

[0181]

[0182] 〔In the formula, B 5 ~B 9 Indicates the same as above B 1 ~B 4 The same meaning, R 4 represents a hydrogen atom or a methyl group, and n represents an integer from 0 to 2. ]

[0183]

[0184] 〔Wherein, D 1 ~D 4Each independently represents 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, 1 ~E 5 Respectively and independently represent 1 ~D 4 The same group or the group represented by the general formula (1B)-a. 〕

[0185]

[0186] [In the formula, m represents an integer from 0 to 4.]

[0187]

[0188] 〔In the formula, R 6 represents a hydrogen atom or a group represented by the general formula (1C)-a, G 1 and G 2 Each independently represents a hydrogen atom, an acetyl group, a halogen atom, an aryl group which may have a substituent, an aralkyl group or an arylalkenyl group having 7 to 12 carbon atoms, or a linear or branched alkyl group, alkenyl group, alkoxy group, alkenyloxy group or aroyloxy group having 1 to 6 carbon atoms. 6 When it is a hydrogen atom, G 1 and G 2 At least one of them is an aryl group which may have a substituent, an aralkyl group having 7 to 12 carbon atoms, an arylalkenyl group or an aroyloxy group.

[0189]

[0190] 〔Where J 1 ~J 5 Each independently represents 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.]

[0191] <5> The fiber treating agent as described in <4>, wherein the compound represented by the general formula (1A) is preferably 2-carboxybenzoic acid (phthalic acid), 2-(((4-vinylbenzyl)oxy)carbonyl)benzoic acid, 2-((2-(acryloyloxy)ethoxy)carbonyl)benzoic acid, or 2-((2-(methacryloyloxy)ethoxy)carbonyl)benzoic acid.

[0192] <6> A fiber treating agent as described in <4>, wherein the compound represented by general formula (1B) is preferably 2-benzoylbenzoic acid, 2-(2-methylbenzoyl)benzoic acid, 2-(3-methylbenzoyl)benzoic acid, 2-(4-methylbenzoyl)benzoic acid, 2-(2-chlorobenzoyl)benzoic acid, 2-(3-chlorobenzoyl)benzoic acid, 2-(4-chlorobenzoyl)benzoic acid, or 2-(4-(2-(2-(acryloyloxy)ethoxy)ethoxy)benzoyl)benzoic acid.

[0193] <7> The fiber treating agent according to <4>, wherein the compound represented by the general formula (1C) is preferably phenylsuccinic acid, 2,3-diphenylsuccinic acid, (+)-di-p-toluoyl-D-tartaric acid or 4-oxo-4-((4-vinylbenzyl)oxy)butanoic acid.

[0194] <8> The fiber treating agent according to <3>, wherein the compound represented by the general formula (2) is benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2-propylbenzoic acid, 3-propylbenzoic acid, 4-propylbenzoic acid, 2-isopropylbenzoic acid, 3-isopropylbenzoic acid, 4-isopropylbenzoic acid, 2-n-butylbenzoic acid, 3-n-butylbenzoic acid, 4-n-butylbenzoic acid, 2-tert-butylbenzoic acid, The invention can be benzoic acid, 3-tert-butylbenzoic acid, 4-tert-butylbenzoic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2-acetylbenzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2-bromobenzoic acid, 3-bromobenzoic acid or 4-bromobenzoic acid, more preferably 4-ethylbenzoic acid, 4-vinylbenzoic acid or benzoic acid.

[0195] <9> The fiber treating agent according to any one of <2> to <8>, wherein the hydrogen bonding term δH of the aromatic compound of component (A1) is preferably 16.0 MPa 1 / 2 Below, more preferably 13.5MPa 1 / 2 Below, more preferably 12.0 MPa 1 / 2 Below, more preferably 10.0 MPa 1 / 2 Below, preferably 3.0 MPa 1 / 2 More preferably 4.0 MPa 1 / 2 More preferably, 5.0 MPa 1 / 2 above.

[0196] <10> The fiber treating agent according to <2>, wherein the component (A2) is potassium 2,4-hexadienoate.

[0197] <11> The fiber treating agent according to <2> or <10>, wherein the hydrogen bonding term δH of the compound of component (A2) is preferably 16.0 MPa 1 / 2 Below, more preferably 15.0 MPa 1 / 2 Below, more preferably 14.0 MPa 1 / 2 Below, more preferably 13.0 MPa 1 / 2 Below, preferably 11.0 MPa 1 / 2 More preferably 11.5 MPa 1 / 2 More preferably, 12.0 MPa 1 / 2 above.

[0198] <12> The fiber treatment agent as described in any one of <1> to <11>, wherein the content of component (B) is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more, further more preferably 40 mass% or more, and is preferably 99 mass% or less, more preferably 95 mass% or less, further preferably 90 mass% or less, further more preferably 85 mass% or less.

[0199] <13> The fiber treatment agent according to any one of <1> to <12>, wherein the pH at 25°C is preferably 2.0 or more, more preferably 3.0 or more, further preferably 3.5 or more, further more preferably 4.0 or more, and is preferably 11.0 or less, more preferably 10.0 or less, further preferably 9.0 or less.

[0200] <14> The fiber treating agent according to any one of <1> to <13>, wherein the component (A) contains (A1-1) benzoic acid or a salt thereof.

[0201] <15> A fiber-treating agent as described in <14>, wherein the pH of the fiber-treating agent is 2.0 or more and less than 6.5, and the content of the component (A1-1) in the fiber-treating agent is preferably 0.8% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, further preferably 10% by mass or more, further more preferably 15% by mass or more, further more preferably 20% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, further more preferably 40% by mass or less, further more preferably 35% by mass or less.

[0202] <16> The fiber-treating agent according to <14>, wherein the pH of the fiber-treating agent is 6.5 or more and 11.0 or less, and the content of the component (A1-1) in the fiber-treating agent is preferably 0.8% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, further preferably 10% by mass or more, further more preferably 15% by mass or more, further more preferably 20% by mass or more, further more preferably 25% by mass or more, further more preferably 26% by mass or more, further more preferably 28% by mass or more, further more preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, further more preferably 45% by mass or less, further more preferably 40% by mass or less.

[0203] <17> The fiber treating agent according to any one of <1> to <13>, wherein the component (A) contains a component (A1-2) other than benzoic acid or a salt thereof.

[0204] <18> A fiber treatment agent as described in <17>, wherein the pH of the fiber treatment agent is 2.0 or more and less than 6.5, and the content of component (A1-2) in the fiber treatment agent is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, even more preferably 0.5 mass % or more, further more preferably 1.0 mass % or more, and is preferably 70 mass % or less, more preferably 60 mass % or less, further preferably 50 mass % or less, further more preferably 45 mass % or less.

[0205] <19> A fiber treatment agent as described in <17>, wherein the pH of the fiber treatment agent is 6.5 or more and 11.0 or less, and the content of component (A1-2) in the fiber treatment agent is preferably 1.0 mass % or more, more preferably 2.0 mass % or more, further preferably 5.0 mass % or more, further more preferably 10 mass % or more, and preferably 70 mass % or less, more preferably 60 mass % or less, further preferably 50 mass % or less, further more preferably 40 mass % or less.

[0206] <20> The fiber treating agent according to any one of <1> to <13>, wherein the component (A) contains a component (A2).

[0207] <21> A fiber treatment agent as described in <20>, wherein the pH of the fiber treatment agent is 2.0 or more and less than 6.5, and the content of component (A2) in the fiber treatment agent is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, even more preferably 0.5 mass % or more, further preferably 1.0 mass % or more, further more preferably 60 mass % or less, further more preferably 50 mass % or less, further more preferably 40 mass % or less, further more preferably 30 mass % or less.

[0208] <22> A fiber treatment agent as described in <20>, wherein the pH of the fiber treatment agent is 6.5 or more and 11.0 or less, and the content of component (A2) in the fiber treatment agent is preferably 1.0 mass % or more, more preferably 2.0 mass % or more, further preferably 5.0 mass % or more, further more preferably 10 mass % or more, and preferably 70 mass % or less, more preferably 60 mass % or less, further preferably 50 mass % or less, further more preferably 40 mass % or less.

[0209] <23> The fiber treating agent according to any one of <1> to <22>, comprising two or more compounds as component (A).

[0210] <24> The fiber treating agent according to <23>, wherein at least one of the components (A) is preferably an aromatic compound represented by the general formula (2), and more preferably benzoic acid or a salt thereof.

[0211] <25> The fiber treating agent according to <24>, wherein the content of the aromatic compound represented by the general formula (2) in the component (A) is preferably the highest, and the content of benzoic acid or a salt thereof is more preferably the highest.

[0212] <26> A fiber-treating agent as described in any one of <23> to <25>, wherein the pH of the fiber-treating agent is 2.0 or more and less than 6.5, and the content of the component (A) remaining after removing the compound with the highest concentration in all components (A) in the fiber-treating agent is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1.0 mass% or more, and is preferably 20 mass% or less, more preferably 10 mass% or less, and further preferably 5.0 mass% or less.

[0213] <27> A fiber-treating agent as described in any one of <23> to <25>, wherein the pH of the fiber-treating agent is 6.5 or more and 11.0 or less, and the content of the component (A) remaining after removing the compound with the highest concentration in all components (A) in the fiber-treating agent is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, further preferably 2.0 mass% or more, and is preferably 30 mass% or less, more preferably 20 mass% or less, and further preferably 10 mass% or less.

[0214] <28> A fiber treatment agent as described in any one of <23> to <27>, wherein the mass ratio of the component (A) remaining after removing the compound with the highest concentration among all components (A) in the fiber treatment agent to the compound (mass of the component (A) remaining after removing the compound with the highest concentration among all components (A)) / (mass of the compound with the highest concentration among component (A)) is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.10 or more, and is preferably 1.0 or less, more preferably 0.5 or less, and further preferably 0.25 or less.

[0215] <29> A fiber processing method comprising the following step (i).

[0216] Step (i) A step of impregnating natural-derived fibers in a composition containing the following components (A) and (B)

[0217] (A): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 The following compounds have at least one carboxyl group or a salt thereof and do not have a condensed ring

[0218] (B) Water

[0219] <30> A fiber processing method comprising the following step (i).

[0220] Step (i) A step of impregnating natural-derived fibers in a composition containing the following components (A1-2) and (B)

[0221] (A1-2): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 The following compounds having at least one carboxyl group or its salt and having no condensed ring (excluding benzoic acid and its salt)

[0222] (B) Water

[0223] <31> Use of a composition containing the following components (A) and (B) as a fiber treating agent.

[0224] (A): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2The following compounds have at least one carboxyl group or a salt thereof and do not have a condensed ring

[0225] (B) Water

[0226] <32> Use of a composition containing the following components (A1-2) and (B) as a fiber treating agent.

[0227] (A1-2): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 The following compounds having at least one carboxyl group or its salt and having no condensed ring (excluding benzoic acid and its salt)

[0228] (B) Water

[0229] Example

[0230] Examples 1 to 22, Comparative Examples 1 to 3

[0231] Regenerated collagen fibers were treated and various evaluations were performed according to the following methods using the compositions of the formulations shown in Tables 1 and 2. The pH of each prepared composition was measured directly at room temperature (25° C.) using a pH meter (F-52 manufactured by HORIBA).

[0232] <Handling method>

[0233] 1. Immerse 0.50 g of a 22 cm long bundle of regenerated collagen fiber (※) in a container to which a fiber treatment agent in the amount of bath ratio shown in the table has been added, seal the container mouth, and immerse the container in a water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) at the temperature shown in the table, and heat for the time shown in the table.

[0234] ※: Regenerated collagen fibers manufactured by Kaneka were purchased in the form of commercially available hair extension products, and fibers were cut and divided into bundles for evaluation. In this evaluation, the hair extension products used were white, straight fibers with the Ultima 100% usage mark and color number 30.

[0235] 2. Take the container containing the hair bundle out of the water bath and return it to room temperature.

[0236] 3. The hair bundle was taken out of the container, rinsed with 30°C running tap water for 30 seconds, foamed with the evaluation shampoo for 60 seconds, rinsed with 30°C running tap water for 30 seconds, and the moisture was gently wiped off with a towel. The hair bundle was then blow-dried while being combed with a warm air hair dryer (manufactured by TESCOM, Nobby White NB3000).

[0237] <Evaluation of Shampoo Formulation>

[0238]

[0239] <Increase in average elongation at break when stretching fibers>

[0240] As an index of water resistance and stretchability (flexibility), the average elongation at break when the fiber is stretched, that is, the average value of the fiber when it is stretched by stretching and then breaks after a few percent of the original fiber length, is used when evaluating multiple (10) fibers. The evaluation is performed using the hair bundle just after the treatment using the above-mentioned <treatment method> according to the following steps.

[0241] 1. Cut 10 fibers from the root of the hair bundle. Select a 3 cm fiber piece from the middle between the root and the tip of each fiber, and get a total of 10 3 cm hair pieces.

[0242] 2. Place the fiber sheet in the "MTT690 Fiber Automatic Tensile Tester" manufactured by DIA-STRON Limited. After being immersed in water for 30 minutes, start automatic measurement to find the average breaking elongation of the fiber in the state of being immersed in water. The higher the value, the higher the elasticity, the better the flexibility, and the better the durability.

[0243] According to the following formula, the average breaking elongation (A%) when the fiber is stretched in the original state (untreated; Comparative Example 1) cut from a commercial product is used as a reference, and the degree to which the average breaking elongation (B%) of the treated hair bundle increases from the untreated state (C%) is recorded in the table as the "increase rate of average breaking elongation when the fiber is stretched [%]".

[0244] C(%)=B(%)-A(%)

[0245] <Increase in average breaking load when stretching fibers>

[0246] As an index of water resistance, the average breaking load when the fiber is stretched is used. The evaluation is performed using the hair bundle just after being treated by the above-mentioned <Treatment Method>. In addition, as a numerical value, the average value when evaluating using multiple (10) fibers is used. The evaluation is performed according to the following steps.

[0247] 1. Cut 10 fibers from the root of the hair bundle. Select a 3 cm fiber piece from the middle between the root and the tip of each fiber, and get a total of 10 3 cm hair pieces.

[0248] 2. Place the fiber sheet in the "MTT690 Fiber Automatic Tensile Tester" manufactured by DIA-STRON Limited. After being immersed in water for 30 minutes, start automatic measurement to find the breaking load when the fiber is extended while immersed in water. The higher the value, the more elastic it is, the stronger the extension caused by external force, and the better the durability.

[0249] According to the following formula, the average breaking load (W0(gf)) when the fiber is stretched in the original state (untreated; Comparison Example 1) cut from a commercial product is used as a reference, and the degree to which the average breaking load (W1(gf)) of the treated hair bundle increases from the untreated state (Y(gf)) is recorded in the table as "the increase in the average breaking load when the fiber is stretched [gf]".

[0250] Y(gf)=W1(gf)-W0(gf)

[0251] <Shrinkage rate during high temperature perming>

[0252] As an index of heat resistance, the shrinkage rate during high temperature hair curling was used. The evaluation was performed using the hair bundle just after being treated by the above-mentioned <Treatment Method>. In addition, as a numerical value, the average value when evaluating using multiple (5) fibers was used. The evaluation was performed according to the following procedures.

[0253] 1. Cut 5 fibers from the roots of the hair bundle just treated in the above-mentioned <Treatment Method> and mark them. Measure the lengths of these 5 treated fibers and record the average value (set as length L1). Next, tie these 5 marked treated fibers together by sandwiching them between 2 hair bundles (1 g) of 0.5 g of untreated regenerated collagen fibers prepared separately to make a new hair bundle (hereinafter referred to as a large hair bundle), and apply a hair straightener set to 180°C (manufactured by Miki Electric Industry Co., Ltd. / Model: AHI-938) to the entire large hair bundle 3 times at a speed of 5 cm / sec.

[0254] 2. After the perming operation, take out 5 marked fibers from the large hair bundle, re-measure the length of each of the 5 marked fibers, and record the average value (referred to as length L2).

[0255] 3. Define the shrinkage rate S during high temperature perm setting dry ={1-(L2 / L1)}×100[%]. dry The closer to 0%, the less likely the shrinkage due to dry heat occurs, and the better the heat resistance.

[0256] <Shrinkage ratio when heated with hot water>

[0257] As an index of water resistance and heat resistance, the shrinkage rate when heated with hot water was used. The evaluation was performed using the hair bundle just after being treated by the above-mentioned <Treatment Method>. In addition, as a numerical value, the average value when evaluating using multiple (5) fibers was used. The evaluation was performed according to the following procedures.

[0258] 1. Five fibers were cut from the root of the hair bundle, and the average length of each fiber was recorded (referred to as length L1), and then immersed in a 90°C water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) for 1 minute.

[0259] 2. After the heating operation, take out 5 fibers, gently wipe off the moisture with a towel, dry them at room temperature and humidity for 30 minutes, and then re-record the average length of each fiber (set as length L2).

[0260] 3. Definition of shrinkage rate when heated with hot water Swet = {1-(L2 / L1)}×100 [%] The closer Swet is to 0%, the less likely it is to shrink due to wet heat, and the better the heat resistance.

[0261] <Thermal shape memory capability>

[0262] The thermal shape memory ability was evaluated using the hair bundle immediately after being treated by the above-mentioned <Treatment Method>. If the result value of "I: Shape Imparting (Curl)" was 5% or less, it was considered that there was no effect, and subsequent treatment and evaluation were not performed.

[0263] I: Shape giving (curls)

[0264] 1. A 22 cm long bundle of 0.5 g of regenerated collagen fibers was moistened with 30°C tap water for 30 seconds, and then the moistened bundle was wound around a plastic rod with a diameter of 14 mm and fixed with a clip.

[0265] 2. The entire hair bundle wound around the rod was immersed in a 60° C. water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) and heated for 1 minute.

[0266] 3. Take the hair bundle out of the water bath, immerse it in 25°C water for 1 minute, take it out of the water, and cool it back to room temperature.

[0267] 4. Remove the hair bundle from the rod, comb it 3 times, take it out of the water, and then take photos from the front and side in the hanging state after 3 minutes.

[0268] (Evaluation Criteria)

[0269] The untreated hair bundle length is defined as L0 (22 cm), the treated hair bundle length is defined as L, and the curl ratio = hair bundle length reduction ratio (I) (%) obtained by the following formula is defined as the curl strength of the curled hair.

[0270] I=[(L0-L) / L0]×100

[0271] II: Reshape (straighten)

[0272] 1. The hair bundle evaluated in I was combed into a lock and then slid six times at a speed of 5 cm / sec using a hair straightener (manufactured by Miki Electric Industry Co., Ltd., model: AHI-938) set at 180°C.

[0273] 2. Rinse with 30°C running tap water for 30 seconds, lather with the evaluation shampoo for 60 seconds, rinse with 30°C running tap water for 30 seconds, and dry with a towel.

[0274] 3. Hang it up and dry it naturally at 20°C 65% RH for 12 hours. After combing, visually observe it from the front and side while it is hung up.

[0275] (Evaluation Criteria)

[0276] The untreated hair bundle length is L0 (22 cm), the treated hair bundle length is L, and the straightening rate (ST) (%) obtained by the following formula is defined as the degree of straightening. When ST = 100%, the hair bundle is completely straightened.

[0277] ST=[1-(L0-L) / L0]×100

[0278] III: Reshape (curls)

[0279] 1. The hair bundle evaluated in II was moistened with tap water at 30°C for 30 seconds, and then the moistened hair bundle was wound around a plastic rod having a diameter of 14 mm and fixed with a clip.

[0280] 2. The entire hair bundle wound around the rod was immersed in a 60° C. water bath (manufacturer: Toyo Seisakusho Co., Ltd. / model: TBS221FA) and heated for 1 minute.

[0281] 3. Take the hair bundle out of the water bath, immerse it in 25°C water for 1 minute, take it out of the water, and cool it back to room temperature.

[0282] 4. Remove the hair bundle from the rod, comb it 3 times, take it out of the water, and after 3 minutes, take photos from the front and side while it is hanging.

[0283] (Evaluation Criteria)

[0284] The untreated hair bundle length is defined as L0 (22 cm), the treated hair bundle length is defined as L, and the curl ratio = hair bundle length reduction ratio (I) (%) obtained by the following formula is defined as the curl strength of the curled hair.

[0285] I=[(L0-L) / L0]×100

[0286] <Excellent surface feel>

[0287] Evaluation of Surface Feeling The hair bundles immediately after being treated by the <Treatment Method> were used, and the smoothness of the feel when touched by hand was evaluated by five professional panelists based on the following criteria, and the total value of the five panelists was used as the evaluation result.

[0288] (Evaluation Criteria)

[0289] 5: The texture is very smooth compared with the untreated fiber (Comparative Example 1).

[0290] 4: Smoother feel than the untreated fiber (Comparative Example 1).

[0291] 3: The texture is slightly smoother than that of the untreated fiber (Comparative Example 1).

[0292] 2: There is no difference in feel from the untreated fiber (Comparative Example 1).

[0293] 1: Compared with the untreated fiber (Comparative Example 1), the fiber had a rough and astringent feel and a poor texture.

[0294] <Suppression of fiber coloration>

[0295] 1. For the front and back sides of the hair bundle, measure the color near the root, near the middle, and near the tip of the hair using a colorimeter (CR-400, manufactured by Konica Minolta). The average value of the total of 6 points is taken as the color value (L, a, b).

[0296] 2. The untreated white hair bundle (*) of color number 30 (Comparative Example 1) was used as a reference, and the degree of coloration was evaluated using ΔE*ab. In addition, color measurement was performed on the day of treatment.

[0297] (※) Untreated color 30 white hair

[0298] Regenerated collagen fibers manufactured by Kaneka Co., Ltd. were purchased in the form of commercially available hair extension products, and fibers were cut and divided into bundles for evaluation. In this evaluation, the hair extension products used were white, straight products with the Ultima 100% use mark and color number 30.

[0299] When the measured value of the untreated white hair bundle of color number 30 is set to (L0, a0, b0), and the measured value of the treated hair bundle is set to (L1, a1, b1), [(L1-L0) 2 +(a1-a0) 2 +(b1-b0) 2 〕 1 / 2 ΔE*ab was defined, and the coloration suppressing effect was determined according to the following criteria.

[0300] 5: ΔE*ab≤5.0

[0301] 4: 5.0<ΔE*ab≤10.0

[0302] 3: 10.0<ΔE*ab≤15.0

[0303] 2: 15.0<ΔE*ab≤20.0

[0304] 1:20.0<ΔE*ab

[0305]

[0306]

Claims

1. A fiber treating agent, wherein Containing the following ingredients (A) and (B), (A): The hydrogen bonding term δH of the Hansen solubility parameter is 18.3 MPa 1 / 2 The following compounds have at least one carboxyl group or a salt thereof and do not have a condensed ring; (B): Water.

2. The fiber treating agent according to claim 1, wherein Component (A) is one or more compounds selected from the following components (A1) and (A2), (A1) The hydrogen bonding term of the Hansen solubility parameter δH is 18.3 MPa 1 / 2 The following aromatic compounds having at least one carboxyl group or a salt thereof and having no condensed ring; (A2) The hydrogen bonding term of the Hansen solubility parameter δH is 11.0 MPa 1 / 2 Above 18.3MPa 1 / 2 The following are compounds having at least one carboxyl group or a salt thereof and having no condensed ring, excluding aromatic compounds.

3. The fiber treating agent according to claim 2, wherein Component (A1) is a compound represented by the following general formula (1) or (2) or a salt thereof, In formula (1), =X represents a methylene group or an oxo group, and R 1 represents a hydrogen atom, a hydroxyl group, or an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an aralkyloxy group which may have a substituent, and R 2 represents an o-phenylene group, an m-phenylene group, a p-phenylene group, a benzylidene group, or an alkylene group which may have a substituent, wherein R 2 When there is no aromatic group, R 1 is aryl, aryloxy or aralkyloxy; In formula (2), A 1 ~A 5 Each independently represents 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.

4. The fiber treating agent according to any one of claims 1 to 3, wherein Component (A) contains benzoic acid or a salt thereof.

5. The fiber treating agent according to claim 4, wherein The pH of the fiber treatment agent is 2.0 or more and less than 6.5, and the content of benzoic acid or its salt in the fiber treatment agent is 0.8 mass % or more and 40 mass % or less in terms of benzoic acid, ie, acid form.

6. The fiber treating agent according to claim 4, wherein The pH of the fiber treatment agent is 2.0 or more and less than 6.5, and the content of benzoic acid or its salt in the fiber treatment agent is 5.0 mass % or more and 40 mass % or less in terms of benzoic acid, ie, acid form.

7. The fiber treating agent according to claim 4, wherein The pH of the fiber treatment agent is 6.5 or more and 11.0 or less, and the content of benzoic acid or its salt in the fiber treatment agent is 0.8 mass % or more and 40 mass % or less in terms of benzoic acid, ie, acid form.

8. The fiber treating agent according to claim 4, wherein The pH of the fiber treatment agent is 6.5 or more and 11.0 or less, and the content of benzoic acid or its salt in the fiber treatment agent is 5.0 mass % or more and 40 mass % or less in terms of benzoic acid, ie, acid form.

9. The fiber treating agent according to any one of claims 1 to 8, wherein As the component (A), two or more compounds are contained.

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