CN119213179A

CN119213179A - Modified regenerated collagen fiber, method for producing the same, and headwear product containing the same

Info

Publication number: CN119213179A
Application number: CN202380041060.5A
Authority: CN
Inventors: 古川淳一; 川村光平; 大平和宇
Original assignee: Kao Corp; Kaneka Corp
Current assignee: Kao Corp; Kaneka Corp
Priority date: 2022-05-18
Filing date: 2023-05-15
Publication date: 2024-12-27
Also published as: WO2023224001A1; JP2023171310A; US20250188676A1; EP4528022A1

Abstract

The present invention relates to a modified regenerated collagen fiber which can improve the water resistance and heat resistance, which is a problem of regenerated collagen fiber, can impart thermal shape memory capability, is excellent in stretchability (toughness) and surface touch, and is free from coloring. The modified regenerated collagen fiber of the present invention is produced by adding the following component (a) or a polymer containing the component (a) as a constituent monomer to the regenerated collagen fiber. (A) vinylbenzoic acid or a salt thereof.

Description

Modified regenerated collagen fiber, method for producing same, and head ornament product comprising same

Technical Field

The present invention relates to a regenerated collagen fiber having imparted thereto water resistance, heat resistance and thermal shape memory, and more particularly to a regenerated collagen fiber used for fiber products such as hair wear products including wigs and hair extensions.

Background

Regenerated collagen fibers generally differ from synthetic fibers in that they have a natural hand and appearance from natural raw materials. The regenerated collagen fiber can be obtained by dissolving acid-soluble collagen or insoluble collagen with alkali or enzyme to obtain a spinning solution, spraying the spinning solution into a coagulation bath through a spinning nozzle, and performing fibrillation.

However, regenerated collagen fibers are generally more hydrophilic than synthetic fibers, and therefore have a higher water absorption rate and extremely low mechanical strength in a state of containing a large amount of water. Therefore, mechanical strength is significantly reduced due to high water absorption during cleaning, and breakage or the like occurs during subsequent drying, resulting in a decrease in suitability as a fibrous product such as a head-wear product.

In addition, the regenerated collagen fiber has a problem of low heat resistance, for example, when the heat setting is performed at a high temperature as in the case of human hair in the case of using a hair iron or the like, shrinkage or curling occurs to deteriorate the appearance.

In addition, in the case of synthetic fibers made of plastic, the shape at the time of heat setting by a hair iron or the like is continuously memorized (has a thermal shape memory ability) even after the subsequent washing, but the shape at the time of heat setting by a regenerated collagen fiber by a hair iron or the like is lost (does not have a thermal shape memory ability) after the subsequent washing, and therefore, the degree of freedom in shape setting is inferior to that of the conventional synthetic fibers made of plastic.

The above-mentioned points are the main factors that prevent the popularization of regenerated collagen fibers in fiber products. In particular, the effect of the decrease in water resistance, i.e., mechanical strength upon wetting, is remarkable.

On the other hand, in the field of human hair fibers, there is known a method of applying a specific aldehyde derivative and phenol compound to a human hair fiber which does not have a thermal shape memory capability in itself, in order to newly impart a thermal shape memory capability (patent document 1).

(Patent document 1) Japanese patent application laid-open No. 2019-143281

Disclosure of Invention

The present invention provides a modified regenerated collagen fiber, wherein the regenerated collagen fiber contains the following component (A) or a polymer containing the component (A) as a constituent monomer.

(A) Vinyl benzoic acid or salts thereof

The present invention also provides a method for treating regenerated collagen fibers, comprising the following step (i).

A step (i) of immersing the regenerated collagen fibers in a fiber treating agent which is a single-component fiber treating agent composed of a single composition or a multi-component fiber treating agent composed of a plurality of compositions and contains the following component (A) and component (B) in the total composition,

(A) Vinyl benzoic acid or its salt;

(B) Azo polymerization initiator.

The present invention also provides a method for producing a modified regenerated collagen fiber, comprising the step of treating a regenerated collagen fiber by the above-mentioned regenerated collagen fiber treatment method.

The present invention also provides a method for producing a head gear product, comprising a step of treating regenerated collagen fibers by the method for treating regenerated collagen fibers.

The present invention also provides a head gear product comprising the modified regenerated collagen fiber as a component.

Detailed Description

In the case of producing a fiber product, the fiber may be strongly stretched, and in the technique described in patent document 1, the stretchability (toughness) of the treated fiber may be insufficient. Therefore, in order to prevent breakage during elongation, it is required to improve the stretchability of the treated fiber. In the technique described in patent document 1, fibers may be colored.

Accordingly, the present invention relates to a modified regenerated collagen fiber which can improve the water resistance and heat resistance, which are problems of regenerated collagen fibers, can provide thermal shape memory capability, is excellent in stretchability (toughness) and surface touch, and is free from coloring.

As a result of intensive studies, the present inventors have found that, in a modified regenerated collagen fiber containing vinylbenzoic acid or a salt thereof, a carboxyl group thereof coordinates strongly to a metal (mainly polyvalent metal) in the regenerated collagen fiber along with polymerization of the vinylbenzoic acid or the like, and therefore, the strength and heat resistance of the fiber in water are improved and leakage of vinylbenzoic acid, a salt thereof, or a polymer thereof from the fiber is prevented. As a result, the inventors have found that the modified regenerated collagen fiber has improved water resistance and heat resistance both when dried and when wet, and that the modified regenerated collagen fiber can be provided with a shape by heat setting, and that the flexibility (toughness) is unexpectedly improved to a level close to that of human hair as compared with that before treatment, and that the modified regenerated collagen fiber is not colored with the modification treatment, thereby completing the present invention.

According to the present invention, it is possible to provide a modified regenerated collagen fiber which has improved water resistance and heat resistance, is imparted with thermal shape memory capability, has improved stretchability (toughness) and surface touch, and is free from coloring, which is a problem of regenerated collagen fibers.

[ Fiber to be treated in the present invention ]

The fibers to be treated with the fibers of the present invention are fibers artificially produced from a polymer or oligomer derived from collagen, that is, regenerated collagen fibers produced from collagen.

The regenerated collagen fibers can be produced by known techniques, and the composition need not be 100% collagen, and may contain natural or synthetic polymers or additives for improving quality. In addition, the regenerated collagen fibers may be post-processed. As the form of the regenerated collagen fiber, a filament (filament) is preferable. The filaments are typically taken from a state of being wound or boxed on a bobbin. In addition, filaments obtained from the drying step in the process of producing regenerated collagen fibers may be directly used.

The collagen material used for producing the regenerated collagen fiber is preferably a part of the double skin (SPLIT LEATHER). The double skin can be obtained, for example, from fresh double skin obtained by slaughtering livestock animals such as cattle or salted pelt. Most of these two-layer skins are made of insoluble collagen fibers, but they are usually used after removing the net-like adhering meat portions and removing salts used for preventing spoilage and deterioration.

The insoluble collagen fibers contain impurities such as glycerides, phospholipids, lipids such as free fatty acids, proteins other than collagen such as glycoproteins and albumin. These impurities have a great influence on the quality such as spinning stability, gloss and elongation, and smell when fiberizing. Therefore, for example, it is preferable to remove these impurities in advance by immersing in lime, hydrolyzing the fat component in the insoluble collagen fibers, untangling the collagen fibers, and then subjecting the collagen fibers to leather treatment which has been conventionally generally performed such as acid/alkali treatment, enzyme treatment and solvent treatment.

Insoluble collagen subjected to the above-described treatment is subjected to a solubilizing treatment for cleaving the crosslinked peptide portion. As a method of the solubilization treatment, a conventionally used known alkali solubilization method, enzyme solubilization method, or the like can be applied. The above-mentioned alkali-solubilizing method and enzyme-solubilizing method may be used in combination.

In the case of using the above-mentioned alkali-solubilizing method, neutralization is preferably carried out with an acid such as hydrochloric acid. In addition, as a method for improving the conventionally known alkali solubilization method, a method described in Japanese patent publication No. 46-15033 may be used.

The enzyme solubilization method has the advantage of obtaining solubilized collagen having a uniform molecular weight, and is preferably used in the present invention. As the enzyme solubilization method, for example, the methods described in Japanese patent publication No. 43-25829 and Japanese patent publication No. 43-27513 can be used.

When the collagen subjected to the solubilization treatment is subjected to further operations such as pH adjustment, salting-out, washing with water, and solvent treatment, regenerated collagen fibers excellent in quality and the like can be obtained, and therefore, it is preferable to carry out these treatments.

The solubilized collagen thus obtained is dissolved with an acid such as hydrochloric acid, acetic acid, or lactic acid, for example, and is adjusted so that the pH is 2 to 4.5, and the concentration of the collagen is 1 mass% or more, preferably 2 mass% or more, and is 15 mass% or less, preferably 10 mass% or less. The above-mentioned aqueous collagen solution may be filtered, if necessary, for deaeration under stirring under reduced pressure or for removing fine waste as a water-insoluble component. The above collagen aqueous solution may be further blended with an appropriate amount of an additive such as a stabilizer or a water-soluble polymer compound, if necessary, for the purpose of improving mechanical strength, improving water resistance and heat resistance, improving glossiness, improving spinning property, preventing coloring, and preventing corrosion.

The above-mentioned aqueous collagen solution is discharged, for example, through a spinning nozzle or a slit, and immersed in an inorganic salt aqueous solution, thereby forming regenerated collagen fibers. As the aqueous solution of inorganic salt, an aqueous solution of water-soluble inorganic salt such as sodium sulfate, sodium chloride, ammonium sulfate, etc. can be used. The concentration of the inorganic salt in the aqueous solution of the inorganic salt is usually adjusted to 10 to 40 mass%. The pH of the inorganic salt aqueous solution is preferably 2 or more, more preferably 4 or more, and further preferably 13 or less, more preferably 12 or less. For example, metal salts such as sodium borate and sodium acetate, hydrochloric acid, boric acid, acetic acid, sodium hydroxide, and the like can be used for adjusting the pH. If the pH of the inorganic salt aqueous solution is in the above range, the peptide bond of collagen is less susceptible to hydrolysis, and the target fiber is easily obtained. The temperature of the aqueous solution of the inorganic salt is not particularly limited, but is usually preferably 35 ℃ or less, from the viewpoints that the soluble collagen is not denatured, the strength of the fiber obtained by spinning is not lowered, and stable filaments are easily produced. The lower limit of the temperature of the inorganic salt aqueous solution is not particularly limited, but may be generally appropriately adjusted according to the solubility of the inorganic salt.

The regenerated collagen fibers may be immersed in an epoxy compound or a solution thereof, and subjected to a pretreatment (crosslinking treatment). The amount of the epoxy compound is preferably 0.1 equivalent or more, more preferably 0.5 equivalent or more, further preferably 1 equivalent or more, and further preferably 500 equivalents or less, more preferably 100 equivalents or less, further preferably 50 equivalents or less, relative to the amount of the amino groups capable of reacting with the epoxy compound in the regenerated collagen fiber obtained by the amino acid analysis method. The amount of the epoxy compound in the above range is preferable in terms of industrial operability and environment, since a sufficient insolubilization effect against water can be imparted to the regenerated collagen fiber.

The epoxy compound may be used as it is or dissolved in various solvents. Examples of the solvent include water, alcohols such as methanol, ethanol and isopropanol, ethers such as tetrahydrofuran and dioxane, halogen-based organic solvents such as methylene chloride, chloroform and carbon tetrachloride, and neutral organic solvents such as Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO). These solvents may be used alone or in combination of two or more. In the case of using water as a solvent, an aqueous solution of an inorganic salt such as sodium sulfate, sodium chloride, ammonium sulfate, or the like may be used as needed. Generally, the concentration of the inorganic salt in the aqueous solution of the inorganic salt is adjusted to 10 to 40 mass%. The pH of the aqueous solution may be adjusted by, for example, a metal salt such as sodium borate or sodium acetate, or hydrochloric acid, boric acid, acetic acid, sodium hydroxide, or the like. In this case, the pH of the aqueous solution is preferably 6 or more, more preferably 8 or more, from the viewpoint that the reaction between the epoxy group of the epoxy compound and the amino group of the collagen does not slow down and insolubilization of water is sufficient. In addition, since the pH of the aqueous solution of the inorganic salt tends to gradually decrease with time, a buffer may be used as needed.

The treatment temperature of the regenerated collagen fibers using the epoxy compound is preferably 50 ℃ or less, from the viewpoint that the regenerated collagen fibers are not denatured, the strength of the obtained fibers is not lowered, and stable filaments are easily produced.

The regenerated collagen fibers may be washed with water, impregnated with oil, and dried. The water washing can be performed by, for example, washing with running water for 10 minutes to 4 hours. As the oil used for the oiling, for example, an oil composed of an emulsion of amino-modified silicone, epoxy-modified silicone, polyether-modified silicone, or the like, and Pluronic (Pluronic) polyether-based antistatic agent, or the like can be used. The drying temperature is preferably 100 ℃ or less, more preferably 75 ℃ or less.

The regenerated collagen fiber to be treated preferably contains a polyvalent metal or a salt or a complex thereof from the viewpoint of improving water resistance. Examples of the polyvalent metal include calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron, copper, etc., and aluminum, zirconium, titanium, and more preferably aluminum are used from the viewpoints of improving water resistance, reducing coloring of fibers, reducing influence on the environment, and improving economical efficiency. The content of the polyvalent metal or a salt or a complex thereof in the regenerated collagen fiber is preferably 1.0 mass% or more, more preferably 2.0 mass% or more, still more preferably 3.0 mass% or more, still more preferably 5.0 mass% or more, in terms of the amount of the metal element, from the viewpoint of improving the water resistance, and is preferably 40 mass% or less, more preferably 30 mass% or less, still more preferably 20 mass% or less, still more preferably 10 mass% or less, in terms of improving the feel of the fiber surface.

That is, the content of the polyvalent metal or a salt or a complex thereof in the regenerated collagen fiber to be treated is preferably 1.0 to 40% by mass, more preferably 2.0 to 30% by mass, still more preferably 3.0 to 20% by mass, and still more preferably 5.0 to 10% by mass, based on the metal element amount, from the above viewpoint.

[ Fiber treatment method ]

(One-stage treatment and Multi-stage treatment)

The method for treating a fiber according to the present invention comprises a one-stage treatment with a single-component fiber treating agent composed of a single composition, and a multi-stage treatment in which a plurality of components such as a two-component fiber treating agent are used to impregnate a regenerated collagen fiber in the plurality of components in sequence. In addition, the single-unit type fiber treating agent includes a case where a plurality of compositions are mixed to form a single composition at the time of use.

In the present invention, the content in the fiber treating agent means the content in a single composition constituting a single-stage fiber treating agent in the case of one-stage treatment, and the content in each treating agent used in each stage in the case of multi-stage treatment.

(Basic treatment)

The fiber treatment method of the present invention includes the following step (i), and thus can provide a modified regenerated collagen fiber which has improved water resistance and heat resistance, is imparted with thermal shape memory capability, has improved stretchability (toughness) and surface touch, and is free from coloring, which is a problem of regenerated collagen fibers.

A step (i) of immersing the regenerated collagen fibers in a fiber treating agent comprising a single-component fiber treating agent composed of a single composition or a multi-component fiber treating agent composed of a plurality of compositions, wherein the total composition of the fiber treating agent comprises the following components (A) and (B),

(A) Vinyl benzoic acid or its salt;

(B) Azo polymerization initiator.

Examples of the multi-component fiber-treating agent include a two-component fiber-treating agent comprising a1 st component containing component (a) and a2 nd component containing component (B). When such a multi-dose fiber treating agent is used, the step (i) is a multi-stage treatment in which the regenerated collagen fibers are immersed in each dose in sequence. For example, when the two-pack type fiber treatment agent is used, the step (i) is a two-stage treatment in which the regenerated collagen fiber is impregnated in the 1 st pack containing the component (a) and then the 1 st pack treated regenerated collagen fiber is impregnated in the 2 nd pack containing the component (B), or a two-stage treatment in which the regenerated collagen fiber is impregnated in the 2 nd pack containing the component (B) and then the 2 nd pack treated regenerated collagen fiber is impregnated in the 1 st pack containing the component (a).

Component (A) is vinylbenzoic acid or a salt thereof. Examples of the vinylbenzoic acid include 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and a mixture of 2 or 3 kinds selected from these, but from the viewpoint of easiness in obtaining and superiority in the surface touch of the treated fiber, a mixture of 3 kinds is preferable. On the other hand, 4-vinylbenzoic acid is preferable from the viewpoint of imparting water resistance. Examples of the salt of the component (A) include alkali metal salts such as sodium salts and potassium salts.

The content of the component (a) in the fiber-treating agent varies depending on the pH range of the fiber-treating agent, and the following range is preferable. In the case where the fiber-treating agent is multi-stage-treated in a multi-stage manner, the "content of the component (a)" referred to herein means the content of the component (a) -containing composition, and the "pH of the fiber-treating agent" referred to herein means the pH of the treating agent containing the component (a). When there are a plurality of treating agents containing the component (a), a preferable content range is defined according to the pH of each treating agent. In addition, as described above, the case where a plurality of compositions are mixed at the time of use to form a single composition is included in a single-unit type fiber treating agent, and the "pH of the fiber treating agent" means the pH after mixing.

When the pH of the fiber treating agent is 2.0 or more and less than 6.5, the content of the component (a) in the fiber treating agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, in terms of the vinyl benzoic acid monomer, from the viewpoint of imparting high shape persistence, water resistance, stretchability (i.e., high elongation at break upon stretching of the fiber) and heat resistance to the modified regenerated collagen fiber after the treatment.

That is, when the pH of the fiber treating agent is 2.0 or more and less than 6.5, the content of the component (a) in the fiber treating agent is preferably 0.1 to 30 mass%, more preferably 0.2 to 25 mass%, still more preferably 0.5 to 20 mass%, still more preferably 1.0 to 15 mass%, in terms of the vinylbenzoic acid monomer, from the above-mentioned viewpoints.

When the pH of the fiber treating agent is 6.5 or more and 11.0 or less, the content of the component (a) in the fiber treating agent is preferably 1.0 mass% or more, more preferably 2.0 mass% or more, still more preferably 5.0 mass% or more, still more preferably 10 mass% or more, in terms of the vinyl benzoic acid monomer, from the viewpoint of imparting high shape persistence, water resistance, stretchability (toughness, i.e., high elongation at break upon stretching of the fiber) and heat resistance to the modified regenerated collagen fiber after the treatment, and from the viewpoint of improving the touch feeling on the fiber surface, it is preferably 90 mass% or less, more preferably 80 mass% or less, still more preferably 70 mass% or less, still more preferably 60 mass% or less.

That is, when the pH of the fiber-treating agent is 6.5 or more and 11.0 or less, the content of the component (a) in the fiber-treating agent is preferably 1.0 to 90 mass%, more preferably 2.0 to 80 mass%, still more preferably 5.0 to 70 mass%, still more preferably 10 to 60 mass%, in terms of the vinyl benzoic acid monomer, from the above point of view.

The component (B) is an azo polymerization initiator for polymerizing the component (a). The component (B) may be contained in the same composition as the component (a), but the fiber treatment agent to be used may be of a multi-dose type, for example, a 2-dose type, or may be contained in a composition (2 nd dose) different from the composition (1 st dose) containing the component (a).

As the azo polymerization initiator, there may be mentioned: 2,2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane-1-carbonitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2' -azobis (2-methylpropionate), 2' -azobis (2-hydroxymethylpropionitrile), 2,2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 4' -azobis (4-cyanovaleric acid), 2' -azobis [2- (2-imidazolin-2-yl) propane ], 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ], 2' -azobis (2-methylpropionamidine) dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, and the like.

The fiber treating agent for hydrophilic regenerated collagen fibers is preferably an aqueous solution from the viewpoint of promoting penetration of the compound in the solution into the fibers, and therefore, the azo polymerization initiator to be blended in the fiber treating agent is also preferably water-soluble. The water-soluble azo polymerization initiator is preferably 2,2 '-azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 4' -azobis (4-cyanovaleric acid), 2 '-azobis [2- (2-imidazolin-2-yl) propane ], 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ], 2 '-azobis (2-methylpropionamidine) dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, or the like.

The water-soluble azo polymerization initiator is an azo polymerization initiator which is preferably "poorly soluble" to "extremely soluble", more preferably "slightly poorly soluble" to "extremely soluble", further preferably "slightly soluble" to "extremely soluble", further more preferably "easily soluble" to "extremely soluble", and further more preferably "extremely soluble", in terms of the degree of dissolution defined below by the volume (mL) of water required for dissolution within 30 minutes when 1g of the powder of the azo polymerization initiator is put into water and vigorously shaken at 20±5 ℃ every 5 minutes according to the general rule of the JIS K8001 reagent test method.

Water amount required for dissolving azo polymerization initiator 1g

Is very soluble, less than 1mL

Is easy to dissolve, and is more than 1mL and less than 10mL

Is slightly soluble, more than 10mL and less than 30mL

Slightly insoluble, more than 30mL and less than 100mL

Is difficult to dissolve, and is more than 100mL and less than 1000mL

Is extremely insoluble, more than 1000mL and less than 10000mL

Hardly dissolved in 10000mL or more

Further, as the treating agent for regenerated collagen fibers having low heat resistance, an azo polymerization initiator having a low 10-hour half-life temperature, which effectively cleaves to function as a radical initiator even at a low treatment temperature, is more preferably used. Among them, 2 '-azobis [2- (2-imidazolin-2-yl) propane ] (10-hour half-life temperature: 61 ℃), 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] (10-hour half-life temperature: 57 ℃), 2 '-azobis (2-methylpropionamidine) dihydrochloride (10-hour half-life temperature: 56 ℃) and 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride (10-hour half-life temperature: 44 ℃), are preferable.

Here, the 10-hour half-life temperature of the azo polymerization initiator means a temperature at which 50% of the azo polymerization initiator is decomposed after 10 hours. The 10-hour half-life temperature of the azo polymerization initiator is preferably 80 ℃ or less, more preferably 70 ℃ or less, still more preferably 60 ℃ or less, still more preferably 50 ℃ or less, from the viewpoint of effectively reacting at a low temperature without damaging the regenerated collagen fiber having weak resistance to high temperature, and is preferably 0 ℃ or more, more preferably 10 ℃ or more, still more preferably 20 ℃ or more, from the viewpoint of exhibiting no excessive reactivity during storage at normal temperature and being advantageous for storage and transportation.

The component (B) may be used alone or in combination of 2 or more. The content of the component (B) in the fiber treatment agent is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, still more preferably 0.1 mass% or more, still more preferably 0.5 mass% or more in terms of a non-dissociable form in the case of a salt or a complex, from the viewpoint of effectively performing a reaction and imparting high shape persistence, water resistance, stretchability (toughness, i.e., high elongation at break upon stretching of the fiber) and heat resistance to the treated modified regenerated collagen fiber, and is preferably 80 mass% or less, more preferably 60 mass% or less, still more preferably 40 mass% or less, still more preferably 20 mass% or less from the viewpoint of preventing the molecular weight of the polymer produced due to excessive concentration from becoming too small. In the case where the fiber-treating agent is multi-stage-treated in a multi-stage manner, the "content of the component (B)" as referred to herein means the content in the composition containing the component (B).

The mass ratio (B)/(a) of the component (B) to the component (a) in the fiber treating agent is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 200 or less, more preferably 50 or less, from the viewpoint of effectively performing a reaction and imparting high shape persistence, water resistance, stretchability (i.e., high elongation at break upon fiber stretching) and heat resistance to the treated modified regenerated collagen fiber. In the case of a multi-dose fiber treating agent in which the component (a) and the component (B) are contained in different treating agents, the mass ratio (B)/(a) in the mixed solution obtained by virtually mixing the two doses may be within the above-described range.

The fiber treating agent used in the step (i) is water as a medium. The content of water in the fiber treating agent is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, still more preferably 40 mass% or more, and further preferably 95 mass% or less, still more preferably 90 mass% or less, still more preferably 85 mass% or less.

That is, the content of water in the fiber treating agent is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, still more preferably 30 to 85% by mass, and still more preferably 40 to 85% by mass.

The pH of the fiber treatment agent used in the step (i) is preferably 2.0 or more, more preferably 3.0 or more, still more preferably 3.5 or more, still more preferably 4.0 or more, and is preferably 11.0 or less, still more preferably 10.0 or less, still more preferably 9.0 or less, from the viewpoints of suppression of damage to the regenerated collagen fibers and improvement of durability. Further, the pH in the present invention is a value at 25 ℃.

That is, the pH of the fiber treatment agent is preferably 2.0 to 11.0, more preferably 3.0 to 10.0, still more preferably 3.5 to 9.0, and still more preferably 4.0 to 9.0, from the viewpoints of suppression of damage to regenerated collagen fibers and improvement of durability.

In the case of the multi-dose fiber treating agent, the above-described conditions are applied to the pH of each agent. However, the closer the pH of each agent is, the better, specifically, the difference between the pH of the agent having the highest pH and the pH of the agent having the lowest pH is preferably 3.0 or less, more preferably 2.0 or less, further preferably 1.0 or less, further more preferably 0.5 or less. In addition, as described above, in the case of using a plurality of compositions mixed at the time of use to form a single composition, included in the single-unit type fiber treating agent, the "pH of the fiber treating agent" means the pH after mixing.

In the step (i), the regenerated collagen fibers to be subjected to the fiber treatment may be dried or may be wet. For example, the direct treatment may be performed in a state before drying at the time of producing the regenerated collagen fiber. The amount of the fiber-treating agent impregnating the regenerated collagen fibers is preferably 2.0 or more, more preferably 3.0 or more, still more preferably 5.0 or more, still more preferably 10 or more, still more preferably 20 or more, and further preferably 500 or less, still more preferably 250 or less, still more preferably 100 or less, in terms of the bath ratio (mass of the fiber-treating agent/mass of the regenerated collagen fibers) relative to the mass of the regenerated collagen fibers.

That is, the bath ratio is preferably 2.0 to 500, more preferably 3.0 to 250, further preferably 5.0 to 100, further more preferably 10 to 100, further more preferably 20 to 100.

In the step (i), the regenerated collagen fibers may be preliminarily fixed by a curler or the like, and then subjected to the fiber treatment of the present invention under heating. By doing so, it is possible to impart a thermal shape memory ability and high durability to the regenerated collagen fibers, while imparting a desired shape.

The impregnation of the regenerated collagen fibers in the fiber treatment agent in the step (i) is preferably performed under heating by heating the fiber treatment agent. The heating may be performed by immersing the regenerated collagen fibers in the fiber treatment agent in a heated state, but may be performed by immersing the regenerated collagen fibers in a low-temperature fiber treatment agent and then heating. The effect of the present invention is obtained by increasing the interaction between the component (a) or the polymer containing the component (a) as a constituent monomer and the fiber-constituting molecules in the regenerated collagen fiber, for example, protein molecules, and therefore, the temperature of the fiber-treating agent is preferably 20 ℃ or higher, more preferably 35 ℃ or higher, further preferably 45 ℃ or higher, and in order to prevent the regenerated collagen fiber from being denatured and degraded by heat, the temperature of the fiber-treating agent is preferably less than 100 ℃, more preferably 80 ℃ or lower, further preferably 70 ℃ or lower, further preferably 60 ℃ or lower.

The soaking time in the step (i) is appropriately adjusted according to the heating temperature, and is preferably 15 minutes or longer, more preferably 30 minutes or longer, still more preferably 1 hour or longer, for example, from the viewpoint of exhibiting an effect of improving the stretchability of the regenerated collagen fibers, and is preferably 48 hours or shorter, more preferably 24 hours or shorter, still more preferably 12 hours or shorter, in order to suppress the damage of the regenerated collagen fibers.

The step (i) is preferably performed in an environment in which evaporation of water is suppressed. Specific means for suppressing the evaporation of water include a method of covering a container impregnated with a fiber treatment agent for regenerated collagen fibers with a film-like substance made of a material impermeable to water vapor, a cap, a cover, or the like.

In the case of multi-stage treatment using a multi-agent fiber treating agent, the above-described bath ratio, temperature, impregnation time, and other conditions may be applied in each stage. In the case of the multistage treatment, washing, drying, and the like may be performed between the stages.

After the step (i), the regenerated collagen fibers may be rinsed, or may not be rinsed, but rinsing is preferably performed from the viewpoint of preventing deterioration of the touch feeling of the regenerated collagen fiber surface due to the remaining component (a) or the polymer containing the component (a) as a constituent monomer.

By the treatment in the step (i), it is considered that the components (a) and (B) in the regenerated collagen fiber are impregnated, and the component (a) is polymerized as a constituent monomer, and strongly coordinated with a metal in the fiber, for example, a polyvalent metal, to thereby exert various effects. That is, by the regenerated collagen fiber treatment method including the step (i), a modified regenerated collagen fiber containing the component (a) in the fiber can be produced, and the obtained modified regenerated collagen fiber can be given a shape by heat setting, and becomes a fiber having excellent water resistance, heat resistance, and tensile elastic modulus, and the stretchability (toughness) of the regenerated collagen fiber is highly improved.

[ Modified regenerated collagen fiber ]

The modified regenerated collagen fiber of the present invention obtained by the above method will be described below.

Component (A) vinylbenzoic acid or a salt thereof

The modified regenerated collagen fiber of the present invention contains vinylbenzoic acid or a salt thereof of the component (a) or a polymer containing the component (a) as a constituent monomer. Examples of the vinylbenzoic acid include 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and a mixture of 2 or 3 kinds selected from these, but from the viewpoint of obtaining easiness and superiority of the surface touch of the treated fiber, a mixture of 3 kinds is preferable. On the other hand, 4-vinylbenzoic acid is preferable from the viewpoint of water resistance. Examples of the salt of the component (A) include alkali metal salts such as sodium salts and potassium salts.

The content of the component (a) and the polymer containing the component (a) as the constituent monomer in the modified regenerated collagen fiber of the present invention is preferably 1.0 mass% or more, more preferably 5.0 mass% or more, still more preferably 10 mass% or more, still more preferably 15 mass% or more, still more preferably 20 mass% or more, in terms of the vinylbenzoic acid monomer, from the viewpoint of producing a modified regenerated collagen fiber having high shape persistence, water resistance and heat resistance, and is preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, still more preferably 40 mass% or less, from the viewpoint of improving the touch feeling on the fiber surface.

That is, from the above point of view, the content of the component (a) and the polymer containing the component (a) as the constituent monomer in the modified regenerated collagen fiber of the present invention is preferably 1.0 to 70 mass%, more preferably 5.0 to 60 mass%, still more preferably 10 to 50 mass%, still more preferably 15 to 40 mass%, still more preferably 20 to 40 mass%, in terms of the vinylbenzoic acid monomer.

(Component (C)) polyvalent metal or salt or complex thereof

The modified regenerated collagen fiber of the present invention preferably contains (C) a polyvalent metal or a salt or a complex thereof from the viewpoint of improving water resistance. Examples of the polyvalent metal include calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron, copper, etc., and aluminum, zirconium, titanium, and more preferably aluminum are used from the viewpoints of improving water resistance, reducing coloring of fibers, reducing influence on the environment, and improving economical efficiency. These may be used alone, or in combination of 2 or more.

The content of the component (C) in the modified regenerated collagen fiber of the present invention is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1.0 mass% or more, still more preferably 2.0 mass% or more, in terms of the amount of the metal element, from the viewpoint of improving the water resistance, and is preferably 40 mass% or less, more preferably 30 mass% or less, still more preferably 20 mass% or less, still more preferably 10 mass% or less, in terms of improving the touch on the fiber surface.

That is, the content of the component (C) in the modified regenerated collagen fiber of the present invention is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, still more preferably 1.0 to 20% by mass, and still more preferably 2.0 to 10% by mass, based on the metal element.

The modified regenerated collagen fiber of the present invention is a fiber which can be given a shape by heat setting, is excellent in water resistance, heat resistance and tensile elastic modulus, and has highly improved stretchability (toughness) of the regenerated collagen fiber. Accordingly, the modified regenerated collagen fiber of the present invention can be suitably used as a fiber for a head gear product, and various head gear products can be produced using the fiber.

Examples of the hair accessory product preferable in the present invention include wigs, hair-dyeing, hair extension, hair braids, hair accessories, and doll hair.

The modified regenerated collagen fiber of the invention can be used as a head ornament product alone or can be mixed with other fibers to prepare the head ornament product. The other fibers are not particularly limited as long as they can be used in a head-wear product. Examples of the other fibers include polyester-based fibers, human hair, animal hair, polyvinyl chloride-based fibers, modacrylic fibers (modacrylic fiber), polyamide-based fibers, and polyolefin-based fibers, and among these, polyester-based fibers are preferable, and flame-retardant polyester-based fibers are more preferable from the viewpoint of excellent heat resistance, flame retardance, and curl retention.

The flame-retardant polyester fiber is not particularly limited, and from the viewpoint of flame retardancy, it is preferable that the flame-retardant polyester fiber contains 5 to 40 parts by mass of a brominated epoxy flame retardant per 100 parts by mass of one or more polyester resins selected from the group consisting of polyalkylene terephthalates and copolyesters mainly composed of polyalkylene terephthalates. In the present invention, "a main component" means a copolymer containing 50 mol% or more, and "a copolymer mainly composed of a polyalkylene terephthalate" means a copolymer containing 50 mol% or more of a polyalkylene terephthalate. The "copolyester mainly composed of a polyalkylene terephthalate" preferably contains 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more of a polyalkylene terephthalate. The flame retardant polyester fiber preferably further contains 0 to 5 parts by mass of an antimony compound per 100 parts by mass of the polyester resin. By containing the antimony compound, the flame retardancy of the polyester fiber is improved.

With respect to the above-described embodiments, preferred modes of the present invention are further disclosed below.

<1>

A modified regenerated collagen fiber comprising the following component (A) or a polymer containing the component (A) as a constituent monomer,

(A) Vinyl benzoic acid or a salt thereof.

<2>

The modified regenerated collagen fiber according to <1>, wherein the content of the component (A) is preferably 1.0 mass% or more, more preferably 5.0 mass% or more, still more preferably 10 mass% or more, still more preferably 15 mass% or more, still more preferably 20 mass% or more, and further preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, still more preferably 40 mass% or less, in terms of the vinyl benzoic acid monomer.

<3>

The modified regenerated collagen fiber according to claim 1 or 2, wherein the modified regenerated collagen fiber further preferably contains the following component (C),

(C) A polyvalent metal or a salt or complex thereof.

<4>

The modified regenerated collagen fiber according to <3>, wherein the component (C) is preferably at least 1 kind of polyvalent metal or a salt or a complex thereof selected from the group consisting of calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron and copper, more preferably at least 1 kind of polyvalent metal or a salt or a complex thereof selected from the group consisting of aluminum, zirconium and titanium, still more preferably aluminum or a salt or a complex thereof.

<5>

The modified regenerated collagen fiber according to <3> or <4>, wherein the content of the component (C) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1.0 mass% or more, further more preferably 2.0 mass% or more, and further preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, further more preferably 10 mass% or less, based on the amount of the metal element.

<6>

A method for treating regenerated collagen fibers, comprising the following step (i),

(A) Vinyl benzoic acid or its salt;

(B) Azo polymerization initiator.

<7>

The method for treating regenerated collagen fibers according to claim 6, wherein the fiber treating agent in the step (i) is a multi-agent fiber treating agent comprising the 1 st agent containing the component (A) and the 2 nd agent containing the component (B),

The step (i) includes a step of immersing the regenerated collagen fibers in the 1 st agent and immersing the regenerated collagen fibers treated in the 1 st agent in the 2 nd agent, or a step of immersing the regenerated collagen fibers treated in the 2 nd agent and immersing the regenerated collagen fibers treated in the 2 nd agent.

<8>

The method for treating regenerated collagen fibers according to <6> or <7>, wherein the method comprises, prior to the step (i), a step of preparing regenerated collagen fibers by subjecting insoluble collagen fibers prepared from two skins of livestock animals to a solubilizing treatment, discharging the obtained solubilized collagen aqueous solution through a spinning nozzle or slit, and immersing the treated insoluble collagen fibers in an inorganic salt aqueous solution.

<9>

The method for treating regenerated collagen fibers according to <8>, wherein the method preferably comprises a crosslinking treatment step of immersing the regenerated collagen fibers in an epoxy compound or a solution thereof after the regenerated collagen fiber production step.

<10>

The method for treating regenerated collagen fiber according to any one of <6> -9 >, wherein component (B) is preferably a water-soluble azo polymerization initiator, more preferably 1 or more selected from the group consisting of 2,2 '-azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 4' -azobis (4-cyanovaleric acid), 2 '-azobis [2- (2-imidazolin-2-yl) propane ], 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ], 2 '-azobis (2-methylpropionamidine) dihydrochloride, and 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride.

<11>

The method for treating a regenerated collagen fiber according to any one of <6> to <10>, wherein the content of the component (B) in the fiber treating agent (in the case of the multi-agent fiber treating agent, the content of the component (B) in the composition containing the component (B)) is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, still more preferably 0.1 mass% or more, still more preferably 0.5 mass% or more, and further preferably 80 mass% or less, more preferably 60 mass% or less, still more preferably 40 mass% or less, still more preferably 20 mass% or less, in terms of non-dissociable form.

<12>

The method for treating a regenerated collagen fiber according to any one of <6> to <11>, wherein the regenerated collagen fiber contains the following component (C),

(C) A polyvalent metal or a salt or complex thereof.

<13>

The method for treating regenerated collagen fibers according to <12>, wherein the component (C) is preferably at least 1 polyvalent metal or a salt or a complex thereof selected from the group consisting of calcium, magnesium, strontium, barium, zinc, chromium, aluminum, titanium, zirconium, tin, lead, antimony, iron and copper, more preferably at least 1 polyvalent metal or a salt or a complex thereof selected from the group consisting of aluminum, zirconium and titanium, still more preferably aluminum or a salt or a complex thereof.

<14>

The method for treating a regenerated collagen fiber according to any one of <6> to <13>, wherein the fiber treating agent used in the step (i) has a pH of preferably 2.0 or more, more preferably 3.0 or more, still more preferably 3.5 or more, still more preferably 4.0 or more, and further preferably 11.0 or less, more preferably 10.0 or less, still more preferably 9.0 or less at 25 ℃.

<15>

The method for treating a regenerated collagen fiber according to any one of <6> to <14>, wherein the pH of the treating agent containing the component (A) used in the step (i) is 2.0 or more and less than 6.5, and the content of the component (A) in the treating agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, in terms of the vinylbenzoic acid monomer.

<16>

The method for treating a regenerated collagen fiber according to any one of <6> to <14>, wherein the pH of the treating agent containing the component (A) used in the step (i) is 6.5 or more and 11.0 or less, and the content of the component (A) in the treating agent is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, still more preferably 5.0% by mass or more, still more preferably 10% by mass or more, still more preferably 90% by mass or less, still more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, in terms of the vinylbenzoic acid monomer.

<17>

The method for treating a regenerated collagen fiber according to any one of <6> to <16>, wherein the mass ratio (B)/(A) of the component (B) to the component (A) in the fiber treating agent (in the case where the component (A) and the component (B) are contained in different treating agents, the component (A) and the component (B) are contained in a mixture in which the two agents are supposed to be mixed) is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 200 or less, more preferably 50 or less.

<18>

The method for treating a regenerated collagen fiber according to any one of <6> to <17>, wherein the fiber treating agent used in the step (i) is water as a medium, and the content of water in the fiber treating agent is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, still more preferably 40 mass% or more, and further preferably 95 mass% or less, more preferably 90 mass% or less, still more preferably 85 mass% or less.

<19>

The method for treating regenerated collagen fibers according to any one of <6> to <18>, wherein the amount of the fiber treating agent impregnating the regenerated collagen fibers in the step (i) is preferably 2.0 or more, more preferably 3.0 or more, still more preferably 5.0 or more, still more preferably 10 or more, still more preferably 20 or more, and further preferably 500 or less, still more preferably 250 or less, still more preferably 100 or less, in terms of the bath ratio (mass of the fiber treating agent/mass of the regenerated collagen fibers) with respect to the mass of the regenerated collagen fibers.

<20>

The method for treating a regenerated collagen fiber according to any one of <6> to <19>, wherein the temperature of the fiber treating agent for impregnating the regenerated collagen fiber in the step (i) is preferably 20 ℃ or higher, more preferably 35 ℃ or higher, further preferably 45 ℃ or higher, and further preferably less than 100 ℃, more preferably 80 ℃ or lower, further preferably 70 ℃ or lower, further preferably 60 ℃ or lower.

<21>

The method for treating a regenerated collagen fiber according to any one of <6> to <20>, wherein the soaking time in the step (i) is preferably 15 minutes or longer, more preferably 30 minutes or longer, further preferably 1 hour or longer, and further preferably 48 hours or shorter, more preferably 24 hours or shorter, further preferably 12 hours or shorter.

<22>

The method for treating regenerated collagen fiber according to any one of <6> to <21>, wherein the step (i) is preferably performed in an environment in which evaporation of water is suppressed.

<23>

A method for producing a modified regenerated collagen fiber, comprising the step of treating a regenerated collagen fiber by the regenerated collagen fiber treatment method according to any one of <6> to <22 >.

<24>

A method for producing a head gear product, comprising the step of treating regenerated collagen fibers by the method for treating regenerated collagen fibers according to any one of <6> to <22 >.

<25>

A headwear product comprising the modified regenerated collagen fiber according to any one of <1> to <5> as a constituent element.

<26>

The headwear article of <25>, wherein the headwear article is selected from the group consisting of wigs, hair-dyeing, hair extension, hair-braiding, hair accessories, and doll hair.

Examples

Example 1, comparative examples 1 to 3

The regenerated collagen fibers were treated and evaluated in the following manner using the compositions of the formulations shown in table 1. In addition, the pH of each of the prepared compositions was measured directly with a pH meter (manufactured by HORIBA Co., ltd., F-52) at room temperature (25 ℃).

< Treatment method >

1. A strand of regenerated collagen fibers (for example) having a length of 22cm was immersed in a container containing a fiber treatment agent in an amount corresponding to the bath ratio shown in the table, the mouth of the container was closed, and the container was immersed in a water bath (manufacturer: toyo Seiyaku Co., ltd.; model: TBS221 FA) at the temperature shown in the table together with the container, and the time shown in the table was heated.

The regenerated collagen fiber manufactured by KANEKA company is purchased in the form of a commercially available hair extension product, and the fiber is cut from the commercially available hair extension product and divided into small hair bundles for evaluation. In the evaluation of this time, a product with a white color having a color number of 30 and a straight hair shape, which was marked with a fiber type of Ultima of 100%, was used as the hair extension product.

The regenerated collagen fibers manufactured by KANEKA contain aluminum, and the aluminum content obtained by the following analysis method was 6.8 mass%.

After drying the regenerated collagen fibers in a dryer, 0.1g of the fibers was added to a mixed solution in which 5mL of nitric acid and 15mL of hydrochloric acid were mixed, and heated to dissolve the fibers. After cooling, the solution was diluted with water to 50 times, and the aluminum content in the diluted aqueous solution was measured using an atomic absorption measuring device (model Z-5300) manufactured by Hitachi Corp.

2. The container with the hair tress was removed from the water bath and returned to room temperature.

3. The hair tresses were removed from the container, rinsed with running water at 30 ℃ for 30 seconds, foamed with an evaluation shampoo for 60 seconds, rinsed with running water at 30 ℃ for 30 seconds, gently wiped off with a towel, and dried with a warm air blower (TESCOM, nobby White NB 3000) while combing.

< Formulation of shampoo for evaluation >

< Increase in average elongation at break upon fiber stretching >

As an index of water resistance and stretchability (toughness) at the time of fiber drawing, an average elongation at break, that is, an average value at the time of evaluation with a plurality of (10) fibers was used for how much% the fiber was elongated with respect to the fibril length by drawing. The evaluation was performed by using the hair tress immediately after the treatment by the above < treatment method >, according to the following procedure.

1. From the root of the hair bundle, 10 fibers were cut. From the middle vicinity of the root and the tip of each fiber, 3cm fiber pieces were collected, and 10 pieces of 3cm hair were obtained in total.

2. The fiber sheet was set in an "MTT690 automatic tensile tester" manufactured by DIA-STRON limited. After the fiber was left to stand in a state immersed in water for 30 minutes, automatic measurement was started, and the average elongation at break of the fiber in a state immersed in water was obtained. The higher the numerical value, the higher the stretchability, the more excellent the toughness, and the more excellent the durability.

The degree (C%) by which the average elongation at break (B%) of the treated hair strand was increased from the untreated state is expressed as "increase in average elongation at break [% ] when the fibers were stretched" in the table, based on the average elongation at break (A%) when the fibers were stretched in the state of being cut directly from the commercial product (untreated; comparative example 1), according to the following formula.

C(%)=B(%)-A(%)

< Increase in average breaking load during fiber stretching >

As an index of water resistance at the time of fiber drawing, an average breaking load at the time of fiber drawing was used. The evaluation was performed using the hair tresses immediately after the treatment by the above < treatment method >. Further, as the numerical value, an average value at the time of evaluation using a plurality of (10) fibers was used. The evaluation was performed according to the following procedure.

2. The fiber sheet was set in an "MTT690 automatic tensile tester" manufactured by DIA-STRON limited. After the fiber was left to stand in a state immersed in water for 30 minutes, automatic measurement was started, and the breaking load of the fiber when the fiber was stretched in a state immersed in water was determined. The higher the numerical value, the more elastic and resistant to stretching against external force, and the more excellent the durability.

The degree to which the average breaking load (W ₁ (gf)) of the treated strands was increased from the untreated state (Y (gf)) was expressed as "the increase in the average breaking load during fiber stretching [ gf ]" in the table, based on the average breaking load (W ₀ (gf)) during fiber stretching in the state of being directly sheared from a commercially available product (untreated; comparative example 1), according to the following formula.

Y(gf)=W₁(gf)－W₀(gf)

< Shrinkage at shaping of high temperature Hair iron >

As an index of heat resistance, shrinkage at the time of shaping by a high-temperature hair iron was used. The evaluation was performed using the hair tresses immediately after the treatment by the above < treatment method >. Further, as the numerical value, an average value at the time of evaluation using a plurality of (5) fibers was used. The evaluation was performed according to the following procedure.

1. From the root of the hair bundle just treated by the above < treatment method >, 5 fibers were cut off and marked. The length of 5 fibers after these treatments was measured and the average value was recorded (as length L ₁). Next, these 5 fibers after the treatment with marks were bundled together so as to be sandwiched between 2 hair bundles (1 g) of 0.5g of untreated regenerated collagen fibers prepared separately, and a new hair bundle (hereinafter referred to as a large hair bundle) was produced, and the entire large hair bundle was ironed 3 times at a speed of 5 cm/sec using a hair straightener (model: AHI-938, manufactured by three wood electric industries, ltd.) set at 180 ℃.

2. After the perming operation, the 5 fibers marked with marks were removed from the large hair bundle, and the lengths of the 5 fibers marked with marks were measured again, and the average value (as length L ₂) was recorded.

3. The shrinkage ratio at the time of shaping the high-temperature hair iron was defined as being as 0% or less as S _dry＝{1－(L₂/L₁)}×100[％].S_dry, which means that shrinkage due to dry heat is less likely to occur and heat resistance is more excellent.

< Shrinkage at Hot Water heating >

As an index of water resistance and heat resistance, shrinkage upon hot water heating was used. The evaluation was performed using the hair tresses immediately after the treatment by the above < treatment method >. Further, as the numerical value, an average value at the time of evaluation using a plurality of (5) fibers was used. The evaluation was performed according to the following procedure.

1. From the root of the hair bundle, 5 fibers were cut, the average value of the lengths of the respective fibers was recorded (as a length L ₁), and immersed in a water bath (manufacturer: toyo Co., ltd./model: TBS221 FA) at 90℃and heated for 1 minute.

2. After the heating operation, 5 fibers were taken out, water was gently removed by towel, and after drying at room temperature and normal humidity for 30 minutes, the average value of the lengths of the respective fibers (as length L ₂) was recorded again.

3. The shrinkage ratio at the time of hot water heating is defined as being as closer to 0% at S _wet＝{1－(L₂/L₁)}×100[％].S_wet, which means that shrinkage due to moist heat is less likely to occur and heat resistance is more excellent.

< Thermal shape memory Capacity >

Evaluation of thermal shape memory was performed using the hair tress immediately after treatment by the above < treatment method >. When the value of the result of "I: shape imparting (curling)" is 5% or less, the result is invalid, and no subsequent treatment or evaluation is performed.

Shape imparting (curling)

1. After 0.5g of a hair bundle of length 22cm of regenerated collagen fibers was wetted with tap water at 30℃for 30 seconds, the wetted hair bundle was wound on a plastic rod of diameter 14mm and fixed with a clip.

2. The resultant mixture was immersed in a water bath (manufacturer: toyo Seisakusho Co., ltd./model: TBS221 FA) at 60℃together with the hair strands wound around the rod and heated for 1 minute.

3. The hair tresses were removed from the water bath, immersed in water at 25 ℃ for 1 minute, removed from the water and returned to room temperature.

4. After the hair bundle was removed from the bar and combed three times, a photograph was taken from the front side in a hanging state after being taken out of the water for 3 minutes.

(Evaluation criterion)

The untreated strand length was L ₀ (22 cm), the treated strand length was L, and the curl increase rate=the strand length decrease rate (I) (%) obtained by the following formula was defined as the curl strength of the curls.

I=[(L₀－L)/L₀]×100

II shape imparting again (Hair straightening)

1. After the hair tress evaluated in I was combed through with a comb, the tress was slip-ironed 6 times at a speed of 5 cm/sec with a hair straightener (AHI-938, manufactured by Sanmu industries Co., ltd.) set at 180 ℃.

2. Rinse with tap water at 30 ℃ for 30 seconds, rinse with tap water at 30 ℃ for 30 seconds after foaming with the evaluation shampoo for 60 seconds, and dry with towel.

3. Lifted, dried naturally at 20 ℃ and 65% RH for 12 hours, combed by a comb and observed from the front side in a lifted state.

(Evaluation criterion)

The untreated hair strand length was L ₀ (22 cm), the treated hair strand length was L, and the hair straightening rate (ST) (%) obtained according to the following formula was defined as the degree of achieving hair straightening. At st=100%, the hair strand is completely straightened.

ST=[1-(L₀－L)/L₀]×100

III shape imparting again (curling)

1. After the hair tresses evaluated in II were wetted with tap water at 30℃for 30 seconds, the wetted hair tresses were wound onto plastic bars having a diameter of 14mm and secured with clips.

4. After removing the hair bundle from the bar and putting through the comb 3 times, the hair bundle was taken out of the water for 3 minutes, and then a photograph was taken from the front side in a hanging state.

(Evaluation criterion)

I=[(L₀－L)/L₀]×100

< Excellent surface touch feeling >

Regarding the evaluation of the touch feeling on the surface, the smoothness of the touch feeling upon touching with the hand was evaluated by 5 professional evaluators using the hair tresses immediately after the treatment with the < treatment method >, and the total value of 5 persons was used as the evaluation result.

(Evaluation criterion)

5-Very smooth hand compared to untreated fiber (comparative example 1)

4-Smooth hand compared to untreated fiber (comparative example 1)

3-Slightly smoother hand than untreated fiber (comparative example 1)

2 Hand feel identical to untreated fiber (comparative example 1)

1 Coarser and coarser than untreated fiber (comparative example 1), poor hand feel

< Inhibition of coloring of fiber >

1. The front and back sides of the hair bundle were each measured for color near the root, near the middle and near the tip by a color meter (color meter CR-400 manufactured by Kenicamantadine, inc.), and the average value of the total 6 points was used as the measured color value (L, a, b).

2. The degree of coloring was evaluated by Δe×ab based on the untreated color number 30 white hair bundle (+b) (comparative example 1). In addition, color measurement was performed on the day of the treatment.

() Color number 30 white hair bundle untreated in the hair

Regenerated collagen fibers manufactured by KANEKA were purchased as commercially available hair extension products, from which the fibers were cut and split into small hair bundles for evaluation. In this evaluation, a white product with a color number of 30 and a straight hair, which was marked with a labeling of Ultima100% as a fiber type, was used as the hair extension product.

The regenerated collagen fibers manufactured by KANEKA contain aluminum, and the aluminum content obtained by the above-described analysis method was 6.8 mass%.

Δe×ab is defined by 〔(L₁－L₀)²+(a₁－a₀)²+(b₁－b₀)²〕^1/2 when the measurement value of the untreated color number 30 white hair bundle is (L ₀,a₀,b₀) and the measurement value of the treated hair bundle is (L ₁,a₁,b₁), and the coloring suppression effect is determined by the following criteria.

5:ΔE*ab≤5.0

4:5.0<ΔE*ab≤10.0

3:10.0<ΔE*ab≤15.0

2:15.0<ΔE*ab≤20.0

1:20.0<ΔE*ab

TABLE 1

* PH adjusting amount

Examples 2 to 6

The regenerated collagen fibers were treated by the following methods using the 1 st and 2 nd agents of the formulations shown in table 2, and various evaluations were performed. Further, the pH of each of the prepared compositions was measured directly with a pH meter (manufactured by HORIBA Co., ltd., F-52) at room temperature (25 ℃).

The concentrations of the components shown in the table are the concentrations in the 1 st and 2 nd preparations, respectively.

< Treatment method >

1. A strand of regenerated collagen fibers (for example) having a length of 22cm was immersed in a container containing the 1 st agent in an amount corresponding to the bath ratio shown in the table, the mouth of the container was closed, and the container was immersed in a water bath (manufacturer: toyo Seiyaku Co., ltd.; model: TBS221 FA) at the temperature shown in the table together with the container, and the time shown in the table was heated.

4. The hair tress was immersed in a container containing the 2 nd agent in an amount to be the bath ratio shown in the table, the mouth of the container was closed, and the container was immersed in a water bath (manufacturer: toyo Co., ltd./model: TBS221 FA) at the temperature shown in the table together with the container, and the time shown in the table was heated.

5. The container with the hair tress was removed from the water bath and returned to room temperature.

6. The hair tresses were removed from the container, rinsed with running water at 30 ℃ for 30 seconds, foamed with an evaluation shampoo for 60 seconds, rinsed with running water at 30 ℃ for 30 seconds, gently wiped off with a towel, and dried with a warm air blower (TESCOM, nobby White NB 3000) while combing. At this point the hair strand is still straight.

TABLE 2

* PH adjusting amount

Comparative example 4

The regenerated collagen fibers were treated according to the following formulation < treatment method > in example 1 and comparative examples 1 to 3. As a result of evaluating the degree of coloring of the treated hair strands in the same manner as described above, brown coloration was observed (evaluation 1)

pH(25°C):5.5

Bath ratio of 40

Heating condition of 50 ℃ for 3h

In addition, the hair bundles treated in the above embodiments can be fixed to the hair by the hair clip or the like, and thus can be used as hair extension as they are, and can exhibit sufficient performance on the head of a person.

Claims

1. A modified regenerated collagen fiber, wherein,

The regenerated collagen fiber contains the following component (A) or a polymer containing the component (A) as a constituent monomer,

(A) Vinyl benzoic acid or a salt thereof.

2. The modified regenerated collagen fiber according to claim 1, wherein,

Further comprises the following component (C),

(C) A polyvalent metal or a salt or complex thereof.

3. The modified regenerated collagen fiber according to claim 2, wherein,

Component (C) is aluminum or a salt or complex thereof.

4. A method for treating regenerated collagen fibers, wherein,

Comprises the following step (i),

(A) Vinyl benzoic acid or its salt;

(B) Azo polymerization initiator.

5. The method for treating regenerated collagen fiber according to claim 4, wherein,

The fiber treating agent in the step (i) is a multi-agent fiber treating agent comprising the 1 st agent containing the component (A) and the 2 nd agent containing the component (B),

6. The method for treating regenerated collagen fiber according to claim 4 or 5, wherein,

The regenerated collagen fiber contains the following component (C),

(C) A polyvalent metal or a salt or complex thereof.

7. The method for treating regenerated collagen fibers according to claim 6, wherein,

Component (C) is aluminum or a salt or complex thereof.

8. A method for producing a modified regenerated collagen fiber, comprising:

the method for treating regenerated collagen fibers according to any one of claims 4 to 7.

9. A method of making a headwear article, comprising:

10. A headwear article, wherein the article comprises a base,

A modified regenerated collagen fiber according to any one of claims 1 to 3 as a constituent element.