JP2010024586A - Regenerated collagen-based artificial hair fiber - Google Patents

Regenerated collagen-based artificial hair fiber Download PDF

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JP2010024586A
JP2010024586A JP2008188427A JP2008188427A JP2010024586A JP 2010024586 A JP2010024586 A JP 2010024586A JP 2008188427 A JP2008188427 A JP 2008188427A JP 2008188427 A JP2008188427 A JP 2008188427A JP 2010024586 A JP2010024586 A JP 2010024586A
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regenerated collagen
fiber
shape
artificial hair
cross
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Yoshitomo Matsumoto
良友 松本
Makoto Shudo
真 首藤
Mitsuru Furukawa
満 古川
Kazuaki Fujiwara
一晃 藤原
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Kaneka Corp
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Kaneka Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain regenerated collagen-based artificial hair fiber suppressed in gloss and excellent in volume without spoiling touch feeling of the regenerated collagen fiber which is extremely close to that of human hair. <P>SOLUTION: The regenerated collagen-based artificial hair fiber has at least one of a cross sectional shape selected from the group consisting of a Y-shape, an S-shape, a C-shape, a cocoon shape, quadri-lobal to octo-lobal shapes, and a shape of ≠, wherein regenerated collagen-based fiber contains a monofunctional epoxy compound and a metal aluminum salt. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、人毛に近い自然な光沢を有し、ボリューム感に優れた再生コラーゲン系人工毛髪繊維に関する。   The present invention relates to a regenerated collagen-based artificial hair fiber having natural luster close to human hair and excellent in volume.

再生コラーゲン繊維は、蛋白繊維の中では絹と同様に高強度を発現することから、従来から様々な分野に応用されている。特に、再生コラーゲン繊維は、コラーゲン由来の特徴的な分子構造を保持した蛋白繊維であることから、天然の蛋白繊維でありきわめて複雑な微細構造を有している人毛と風合い及び触感が近似している。そのため、頭髪や、毛皮用などの獣毛調繊維に用いる試みがなされている(例えば、特許文献1、2)。一般に人毛の断面形状は短軸と長軸の比が1:1〜1:1.75の楕円形であるが、再生コラーゲンからなり人毛と同様な断面形状を有する繊維は、人毛と異なり光沢が強く自然な外観を呈しているとは言えないのが現状である。   Regenerated collagen fibers have been applied to various fields in the past because protein fibers exhibit high strength like silk. In particular, the regenerated collagen fiber is a protein fiber that retains a characteristic molecular structure derived from collagen. ing. For this reason, attempts have been made to use animal hair-like fibers for hair and fur (for example, Patent Documents 1 and 2). In general, the cross-sectional shape of human hair is an ellipse with a ratio of the short axis to the long axis of 1: 1 to 1: 1.75. However, fibers made of regenerated collagen and having a cross-sectional shape similar to human hair are human hair. Unlike the current situation, it cannot be said that it has a strong gloss and a natural appearance.

また、天然原料を使用した蛋白系繊維において、淡色の繊維を得るためには原料の純度を向上したり、着色しない架橋剤を用いて繊維を製造する必要があるが、このような方法で作製した繊維は人毛と比較して透明感が強く、光沢が強過ぎる傾向にある(特許文献3)。   In addition, in order to obtain light-colored fibers in protein-based fibers using natural raw materials, it is necessary to improve the purity of the raw materials or to produce fibers using a non-colored crosslinking agent. The resulting fibers have a strong transparency compared to human hair and tend to be too glossy (Patent Document 3).

光沢を抑制するために艶消し操作を施す場合には、金属化合物等の艶消し剤の添加が一般的に行われるが、反応基を多数有する蛋白質素材において金属化合物の艶消し剤の添加は紡糸原液中で蛋白質分子間の架橋反応が起こり、紡糸原液がゲル化して繊維化できなくなるという問題点がある。
特開平10−168628号 特開平10−168629号 WO01/006045
When a matting operation is performed in order to suppress gloss, addition of a matting agent such as a metal compound is generally performed. However, addition of a matting agent of a metal compound in a protein material having many reactive groups is performed by spinning. There is a problem that a cross-linking reaction between protein molecules occurs in the undiluted solution, and the spinning undiluted solution gels and cannot be fibrillated.
JP-A-10-168628 JP-A-10-168629 WO01 / 006045

本発明は、従来の再生コラーゲン繊維で課題であった、光沢及びボリューム感の優れた人工毛髪を提供することである。   An object of the present invention is to provide artificial hair with excellent gloss and volume, which has been a problem with conventional regenerated collagen fibers.

本発明者らは、前記問題を解決するため鋭意検討を重ねた結果、繊維断面に明確な凹部を有することで、光沢及びボリューム感を改善できることを見出し、本発明を完成するに至った。   As a result of intensive studies to solve the above problems, the present inventors have found that gloss and volume feeling can be improved by having clear concave portions in the fiber cross section, and have completed the present invention.

すなわち、本発明は、
Y字形、S字形、C字形、繭形、4〜8葉形、キ形よりなる群から選ばれる少なくとも1種の断面形状を有することを特徴とする再生コラーゲン系人工毛髪用繊維に関する(請求項1)、
再生コラーゲン繊維が単官能エポキシ化合物及び金属アルミニウム塩を含むことを特徴とする請求項1に記載の再生コラーゲン系人工毛髪用繊維に関する(請求項2)、
単官能エポキシ化合物が下記一般式(1)で表される単官能エポキシ化合物である請求項2に記載の再生コラーゲン系人工毛髪用繊維に関する(請求項3)、
再生コラーゲン繊維が金属アルミニウム塩で架橋されていることを特徴とする請求項1〜請求項3のいずれかに記載の再生コラーゲン系人工毛髪用繊維に関する(請求項4)、
請求項1〜請求項4のいずれかに記載の再生コラーゲン系人工毛髪用繊維を含む、人工毛髪に関する(請求項5)、
ものである。
That is, the present invention
Regenerated collagen-based artificial hair fibers characterized by having at least one cross-sectional shape selected from the group consisting of Y-shape, S-shape, C-shape, collar shape, 4-8 leaf shape, and key shape. 1),
The regenerated collagen fiber for artificial hair according to claim 1, wherein the regenerated collagen fiber contains a monofunctional epoxy compound and a metal aluminum salt (claim 2),
The monofunctional epoxy compound is a monofunctional epoxy compound represented by the following general formula (1), and relates to a fiber for regenerated collagen-based artificial hair according to claim 2 (claim 3),
The regenerated collagen fiber for artificial hair according to any one of claims 1 to 3, wherein the regenerated collagen fiber is crosslinked with a metal aluminum salt (claim 4),
An artificial hair comprising the regenerated collagen-based artificial hair fiber according to any one of claims 1 to 4 (claim 5),
Is.

本発明によれば、光沢及びボリュームの優れたコラーゲン系人工毛髪用繊維を得ることができる。   ADVANTAGE OF THE INVENTION According to this invention, the fiber for collagen type artificial hair excellent in gloss and volume can be obtained.

本発明の人工毛髪用繊維は、Y字形、S字形、C字形、繭形、4〜8葉形、キ形から選ばれる少なくとも1種の断面形状を有するものである。   The fiber for artificial hair of the present invention has at least one cross-sectional shape selected from a Y shape, an S shape, a C shape, a cocoon shape, a 4-8 leaf shape, and a key shape.

Y字形の代表的なものを図1に示す。図1でq/pの比は特に限定されるものではないが、繊維の触感、強度、紡糸性の観点から通常はq/p=0.3〜8である。また、突起部のなす角度(α、β、γ)についても特に限定されるものではない。   A typical Y-shape is shown in FIG. In FIG. 1, the ratio of q / p is not particularly limited, but is usually q / p = 0.3 to 8 from the viewpoint of the feel of the fiber, strength, and spinnability. Further, the angles (α, β, γ) formed by the protrusions are not particularly limited.

S字形の代表的なものを図2(2−1)、(2−2)、(2−3)に示す。S字状の形状をしていればよく、また図2(2−1)、(2−2)、(2−3)中の太さaについても特に限定されるものではない。   Representative examples of the S shape are shown in FIGS. 2 (2-1), (2-2), and (2-3). What is necessary is just to have an S-shape, and the thickness a in FIGS. 2 (2-1), (2-2), and (2-3) is not particularly limited.

C字形の代表的なものを図3に示す。C字の形状を形成していればよいが、C字形を保持しやすいという理由から、図3の開口部の長さbは大きい方が好ましい。小さくなりすぎると中空の円形状に近づき、光沢抑制の点から好ましくない。図3に示す外径cとbの関係については特に限定されないが、以上の観点から、b/c=0.05〜0.8が好ましい。   A typical C-shape is shown in FIG. Although it is sufficient if the C-shape is formed, it is preferable that the length b of the opening in FIG. 3 is large because the C-shape is easily retained. When it becomes too small, it approaches a hollow circular shape, which is not preferable from the viewpoint of gloss suppression. The relationship between the outer diameters c and b shown in FIG. 3 is not particularly limited, but b / c = 0.05 to 0.8 is preferable from the above viewpoint.

繭形の代用的なものを図4に示す。繭形形状とは、楕円または卵型形状を連結したものである。図4で繭形状の長さdと窪み部分の長さeの大きさは特に限定されないが、光沢、触感の観点からe/d=0.2〜0.95が好ましい。   A substitute for the saddle shape is shown in FIG. The saddle shape is a concatenation of elliptical or oval shapes. In FIG. 4, the length d of the bowl shape and the length e of the hollow portion are not particularly limited, but e / d = 0.2 to 0.95 is preferable from the viewpoint of gloss and touch.

4〜8葉形の代表的なものを図5(5−1)、(5−2)、(5−3)、(5−4)、(5−5)に示す。触感の観点から、4〜8葉形におけるL/Wは、L/W=0.3〜3であることが好ましい。   Representative examples of 4 to 8 leaf shapes are shown in FIGS. 5 (5-1), (5-2), (5-3), (5-4), and (5-5). From the viewpoint of tactile sensation, L / W in the 4-8 leaf shape is preferably L / W = 0.3-3.

キ形の代表的なものを図6に示す。キ形の形状を形成していればよいが、図6でf(またはg、h、i)がjに対して大きくなりすぎるとがさついた触感になるため、f(またはg、h、i、)/j=3〜0.2にすることが好ましい。   A typical key shape is shown in FIG. However, since f (or g, h, i) is too large with respect to j in FIG. ) / J = 3 to 0.2 is preferable.

本発明に用いるコラーゲンの原料は、例えば牛などの動物から得られるフレッシュな床皮や塩漬けした生皮より得られる床皮の部分を用いるのが好ましい。これら床皮などは、大部分が不溶性コラーゲン繊維からなる。   The collagen raw material used in the present invention is preferably a fresh skin obtained from animals such as cattle or a portion of the skin obtained from salted raw skin. Most of these skins are made of insoluble collagen fibers.

この不溶性コラーゲン繊維には、脂質、糖タンパク質、コラーゲン以外のタンパク質など、不純物が存在しているため、繊維化にあたって紡糸安定性、光沢や強伸度などの品質、臭気などに多大な影響を及ぼすため、例えば石灰漬けにして不溶性コラーゲン繊維中の脂肪分を加水分解し、コラーゲン繊維を解きほぐした後、酸・アルカリ処理、酵素処理、溶剤処理等のような従来より一般に行われている皮革処理を施し、予めこれらの不純物を除去しておくことが好ましい。   This insoluble collagen fiber contains impurities such as lipids, glycoproteins, and proteins other than collagen, so it has a great influence on spinning stability, quality such as gloss and strength, and odor. Therefore, for example, after leaching with lime, the fat content in insoluble collagen fibers is hydrolyzed, the collagen fibers are unraveled, and then conventional leather treatment such as acid / alkali treatment, enzyme treatment, solvent treatment, etc. is performed. It is preferable to remove these impurities in advance.

前記のような処理の施された不溶性コラーゲンは、架橋しているペプチド部を切断するために可溶化処理が施される。かかる可溶化処理の方法としては、一般に採用されている公知のアルカリ可溶化法や酵素可溶化法等を適用することができる。   The insoluble collagen subjected to the treatment as described above is subjected to a solubilization treatment in order to cleave the cross-linked peptide portion. As such a solubilization method, a publicly-known publicly known alkali solubilization method, enzyme solubilization method or the like can be applied.

このように可溶化処理を施したコラーゲンにpHの調整、塩析、水洗や溶剤処理などの操作をさらに施した場合には、品質などの優れた再生コラーゲンを得ることが可能なため、これらの処理を施すことが好ましい。   When the solubilized collagen is further subjected to operations such as pH adjustment, salting out, water washing and solvent treatment, it is possible to obtain regenerated collagen with excellent quality and so on. It is preferable to perform the treatment.

次に、得られた可溶化コラーゲン皮片は、例えば、1〜15重量%程度の所定濃度の原液になるように塩酸、酢酸、乳酸などの酸でpH2〜4.5に調整した酸性溶液を用いて溶解され、コラーゲン水溶液となる。   Next, the obtained solubilized collagen skin is prepared by, for example, using an acid solution adjusted to pH 2 to 4.5 with an acid such as hydrochloric acid, acetic acid, or lactic acid so as to be a stock solution having a predetermined concentration of about 1 to 15% by weight. It is dissolved by using a collagen aqueous solution.

尚、得られる可溶化コラーゲン水溶液には、例えば機械的強度の向上、耐水・耐熱性の向上、光沢性の改良、紡糸性の改良、着色の防止、防腐などを目的として安定剤、水溶性高分子化合物などの添加剤が適量配合されてもよい。   The resulting solubilized collagen aqueous solution contains, for example, a stabilizer, a high water-solubility for the purpose of improving mechanical strength, improving water resistance / heat resistance, improving gloss, improving spinnability, preventing coloring, and preserving. An appropriate amount of additives such as molecular compounds may be blended.

次に前記可溶化コラーゲン水溶液を、例えば紡糸ノズルやスリットを通して吐出し、pH2〜13の硫酸ナトリウム、塩化ナトリウム、硫酸アンモニウムなどの無機塩水溶液に浸漬することにより再生コラーゲン繊維が形成される。   Next, the solubilized collagen aqueous solution is discharged through, for example, a spinning nozzle or a slit and immersed in an inorganic salt aqueous solution such as sodium sulfate, sodium chloride, ammonium sulfate having a pH of 2 to 13, thereby forming regenerated collagen fibers.

かかるpHは2未満である場合および13を越える場合、コラーゲンのペプチド結合が加水分解を受けやすくなり、目的とする繊維が得られにくくなる傾向がある。また無機塩水溶液の温度は特に限定しないが、通常35℃以下であることが望ましい。かかる温度が35℃より高い場合、可溶性コラーゲンが変性したり、紡糸した繊維の強度が低下し、安定した糸の製造が困難となる。尚、前記温度の下限は特に限定はなく、通常無機塩の溶解度に応じて適宜調整されればよい。   When the pH is less than 2 or exceeds 13, the peptide bond of collagen tends to be subject to hydrolysis, and the intended fiber tends to be difficult to obtain. The temperature of the inorganic salt aqueous solution is not particularly limited, but it is usually preferably 35 ° C. or lower. When this temperature is higher than 35 ° C., the soluble collagen is denatured, the strength of the spun fiber is lowered, and it becomes difficult to produce a stable yarn. The lower limit of the temperature is not particularly limited, and may be appropriately adjusted according to the solubility of the inorganic salt.

前記コラーゲンの遊離アミノ基を、β−位又はγ−位に水酸基又はアルコキシ基を有する炭素教主鎖が2〜20のアルキル基で修飾する。前記炭素教主鎖とは、アミノ基に結合したアルキル基の連続した炭素鎖を示すものであり、他の原子を介在して存在する炭素数は考慮しないものとする。遊離アミノ基を修飾する反応としては、通常知られているアミノ基のアルキル化反応を用いることができる。反応性、反応後の処理の容易さ等から前記β−位に水酸基又はアルコキシ基を有する炭素数2〜20のアルキル基は、下記一般式(2)で表わされる化合物であることが好ましい。
−CH2−CH(OX)−R (2)
(式甲、Rは、R1−、R2−O−CH2−又はR2−COO−CH2−で表される置換基を示し、前記置換基中のR1は炭素数2以上20以下の炭化水素基又はCH2Clであり、R2は炭素数4以上20以下の炭化水素基を示し、Xは水素又は炭化水素暴を示す。)
一般式(2)の好ましい例としては、グリシジル基、1−クロル−2−ヒドロキシプロピル基、1,2−ジヒドロキシプロピル基が挙げられる。加えて、グリシジル基がコラーゲン中の遊離アミノ基に付加した構造が挙げられる。さらには、前述の好ましい基に記載されたアルキル基に含まれる水酸基を開始点として、用いたエポキシ化合物が開環付加、及び又は開環重合した構造が挙げられ、このときの付加及び又は重合の末端構造として、前述のアルキル基の構造を有しているものが挙げられる。
The free amino group of the collagen is modified with an alkyl group having 2 to 20 carbon backbones having a hydroxyl group or an alkoxy group at the β-position or γ-position. The carbon teaching main chain indicates a continuous carbon chain of an alkyl group bonded to an amino group, and the number of carbons existing through other atoms is not considered. As a reaction for modifying a free amino group, a conventionally known alkylation reaction of an amino group can be used. The C2-C20 alkyl group having a hydroxyl group or an alkoxy group at the β-position is preferably a compound represented by the following general formula (2) because of reactivity, ease of treatment after the reaction, and the like.
—CH 2 —CH (OX) —R (2)
(Formula A, R represents a substituent represented by R 1 —, R 2 —O—CH 2 — or R 2 —COO—CH 2 —, and R 1 in the substituent has 2 to 20 carbon atoms. The following hydrocarbon groups or CH 2 Cl, R 2 represents a hydrocarbon group having 4 to 20 carbon atoms, and X represents hydrogen or a hydrocarbon group.)
Preferable examples of the general formula (2) include a glycidyl group, a 1-chloro-2-hydroxypropyl group, and a 1,2-dihydroxypropyl group. In addition, a structure in which a glycidyl group is added to a free amino group in collagen can be mentioned. Furthermore, a structure in which the epoxy compound used is subjected to ring-opening addition and / or ring-opening polymerization starting from the hydroxyl group contained in the alkyl group described in the above-mentioned preferred group can be mentioned. Examples of the terminal structure include those having the aforementioned alkyl group structure.

前記再生コラーゲンの遊離アミノ基を構成するアミノ酸としては、リジン及びヒドロキシリジンが挙げられる。さらに、本来コラーゲンを構成ずるアミノ酸としてはアルギニンで存在するものの、前記再生コラーゲンを得るために、アルカリ条件下で加水分解を行う際に、一部加水分解が進行して生じたオルニチンのアミノ基もアルキル化反応される。加えて、ヒスチジンに含まれる2級アミンによっても反応が進行する。   Examples of amino acids constituting the free amino group of the regenerated collagen include lysine and hydroxylysine. Furthermore, although the amino acid that originally constitutes collagen is arginine, the amino group of ornithine, which is produced by partial hydrolysis during the hydrolysis under alkaline conditions to obtain the regenerated collagen, is also present. Alkylation reaction is performed. In addition, the reaction proceeds with a secondary amine contained in histidine.

遊離アミノ基の修飾率は、アミノ酸分析により測定することが可能であり、アルキル化反応前の再生コラーゲン繊維のアミノ酸分析値、又は原料として用いたコラーゲンを構成する遊離アミノ酸の既知組成を基準に算出される。尚、本発明におけるアミノ基の修飾では、β−位又はγ−位に水酸基又はアルコキシ基を有する炭素数2以上のアルキル基で修飾された構造が、遊離アミノ基の50%以上であれば良く、その他の部分は遊離アミノ基のままでもよいし他の置換基で修飾された構造であっても良い。再生コラーゲンの遊離アミノ酸の修飾率は50%以上である必要があり、より好ましくは、65%以上、更に好ましくは80%以上である。反応率が低い場合、耐熱性で良好な特性が得られない。   The modification rate of the free amino group can be measured by amino acid analysis, and calculated based on the amino acid analysis value of the regenerated collagen fiber before the alkylation reaction or the known composition of the free amino acid constituting the collagen used as the raw material Is done. In the modification of the amino group in the present invention, the structure modified with an alkyl group having 2 or more carbon atoms having a hydroxyl group or an alkoxy group at the β-position or γ-position may be 50% or more of the free amino group. The other part may be a free amino group or a structure modified with another substituent. The modification rate of the free amino acid in the regenerated collagen needs to be 50% or more, more preferably 65% or more, and still more preferably 80% or more. When the reaction rate is low, good characteristics cannot be obtained due to heat resistance.

ここで、遊離アミノ基の修飾においては、通常、遊離アミノ基1つあたり1分子のアルキル化剤が反応する。もちろん2分子以上反応していてもよい。さらに、遊離アミノ基に結合したアルキル基のβ−位又はγ−位に存在する水酸基又はアルコキシ基又はその他の官能基を介して、分子内又は分子間での架橋反応が存在していても良い。アルキル化反応の具体例としては、エポキシ化合物の付加反応、α−位又はβ−位に水酸基又はこの誘導体を有するアルデヒド化合物の付加反応とこれに続く還元反応、β−位又はγ−位に水酸基又はアルコキシ基を有する炭素数2以上のハロゲン化物、アルコール及びアミン等の置換反応が挙げられるが、これに限定されるものではない。   Here, in the modification of the free amino group, one molecule of an alkylating agent usually reacts with respect to one free amino group. Of course, two or more molecules may react. Furthermore, an intramolecular or intermolecular cross-linking reaction may exist via a hydroxyl group, an alkoxy group or other functional group present at the β-position or γ-position of the alkyl group bonded to the free amino group. . Specific examples of the alkylation reaction include an addition reaction of an epoxy compound, an addition reaction of a hydroxyl group or an aldehyde compound having this derivative at the α-position or β-position and a subsequent reduction reaction, a hydroxyl group at the β-position or γ-position. Alternatively, a substitution reaction such as a halogenated compound having 2 or more carbon atoms having an alkoxy group, an alcohol, and an amine is exemplified, but the invention is not limited thereto.

本発明において、アルキル化反応剤として使用しうる有機化合物としては、アルデヒド類、エポキシ類、フェノール誘導体等が挙げられる。この中では反応性・処理条件の容易さからエボキシ化合物による修飾反応が、優れた特性を示すことから好ましい。特に単官能エボキシ化合物が好ましい。   In the present invention, examples of the organic compound that can be used as the alkylating reagent include aldehydes, epoxies, and phenol derivatives. Of these, a modification reaction with an ethoxy compound is preferred because of its excellent reactivity and processing conditions, since it exhibits excellent characteristics. A monofunctional ethoxy compound is particularly preferred.

ここで用いられる単官能エポキシ化合物の具体例としては、たとえば、酸化エチレン、酸化プロピレン.酸化ブチレン、酸化イソブチレン、酸化オクテン、酸化スチレン、酸化メチルスチレン、エピクロロヒドリン、エピブロモヒドリン、グリシドール等のオレフィン酸化物類、グリシジルメチルエーテル、ブチルグリシジルエーテル、オクチルグリシジルエーテル、ノニルグリシジルエーテル、ウンデシルグリシジルエーテル、トリデシルグリシジルエーテル、ペンタデシルグリシジルエーテル、2−エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシシルエーテル、クレジルグリシジルエーテル、t−ブチルフェニルグリシジルエーテル、ジブロモフェニルグリシジルエーテル、ベンジルグリシジルエーテル、ポリエチレンオキシドグリシジルエーテル等のグリシジルエーテル類、蟻酸グリシジル、酢酸グリシジル、アクリル酸グリシジル、メタクリル酸グリシジル、安息香酸グリシジル等のグリシジルエステル類、グリシジルアミド類等が
挙げられるが、かかる例示のみに限定されるものではない。
Specific examples of the monofunctional epoxy compound used here include ethylene oxide and propylene oxide. Olefin oxides such as butylene oxide, isobutylene oxide, octene oxide, styrene oxide, methyl styrene oxide, epichlorohydrin, epibromohydrin, glycidol, glycidyl methyl ether, butyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, Undecyl glycidyl ether, tridecyl glycidyl ether, pentadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, t-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, benzyl glycidyl ether Glycidyl ethers such as polyethylene oxide glycidyl ether, glycidyl formate, glycidyl acetate Le, glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl benzoate, although glycidyl amides and the like, are not limited only to those exemplified.

単官能エポキシ化合物の中でも、再生コラーゲンの吸水率が低下するため、下記一般式(1)で表される単官能エポキシ化合物を用いて処理することが好ましい,   Among monofunctional epoxy compounds, since the water absorption rate of regenerated collagen decreases, it is preferable to treat with a monofunctional epoxy compound represented by the following general formula (1).

但し、RはR1−、R2−O−CH2−またはR2−COO−CH2−で表される置換基を示し、R1は炭素数2以上20以下の炭化水素基またはCH2Clであり、R2は炭素数4以上20以下の炭化水素基を示す。 R represents a substituent represented by R 1 —, R 2 —O—CH 2 — or R 2 —COO—CH 2 —, and R 1 represents a hydrocarbon group having 2 to 20 carbon atoms or CH 2. Cl and R 2 represents a hydrocarbon group having 4 to 20 carbon atoms.

このようにして得られた再生コラーゲンは、水又は無機塩の水溶液で膨潤した状態になっている。この膨潤体は再生コラーゲンの重量に対して4〜15倍の水又は無機塩の水溶液を含有した状態が良い。水又は無機塩の水溶液の含有量が4倍以上では再生コラーゲン中のアルミニウム塩含有量が多いため、耐水性が充分となる。また15倍以下であれば、強度が低下せず、取扱い性は良好である。   The regenerated collagen thus obtained is swollen with water or an aqueous solution of an inorganic salt. The swollen body preferably contains 4 to 15 times the weight of regenerated collagen and contains an aqueous solution of water or an inorganic salt. If the content of the aqueous solution of water or inorganic salt is 4 times or more, the aluminum salt content in the regenerated collagen is large, so the water resistance is sufficient. Moreover, if it is 15 times or less, intensity | strength does not fall and handleability is favorable.

膨潤した再生コラーゲン繊維は、次いでアルミニウム塩の水溶液に浸漬する。このアルミニウム塩水溶液のアルミニウム塩としては、次の式、Al(OH)nCl3-n、又はAl2(OH)2n(SO43n、(式中、nは0.5〜2.5である)で表される塩基性塩化アルミニウム又は塩基性硫酸アルミニウムが好ましい。具体的には、例えば硫酸アルミニウム、塩化アルミニウム、ミョウバン等が用いられる。これらのアルミニウムは単独で又は2種以上混合して用いることができる。このアルミニウム塩水溶液のアルミニウム塩濃度としては、酸化アルミニウムに換算して0.3〜5質量%であることが好ましい。アルミニウム塩の濃度が0.3質量%以上であれば、再生コラーゲン繊維中のアルミニウム塩含有量が高く、耐水性が充分となる。また5質量%以下であれば、処理後もそれほど硬くなく、取り扱い性が良好である。 The swollen regenerated collagen fibers are then immersed in an aqueous solution of an aluminum salt. The aluminum salts of the aluminum salt aqueous solution, the following formula, Al (OH) n Cl 3 -n, or Al 2 (OH) 2n (SO 4) 3 - n, ( wherein, n 0.5-2 .5) is preferred. Basic aluminum chloride or basic aluminum sulfate represented by Specifically, for example, aluminum sulfate, aluminum chloride, alum or the like is used. These aluminum can be used individually or in mixture of 2 or more types. The aluminum salt concentration of the aluminum salt aqueous solution is preferably 0.3 to 5% by mass in terms of aluminum oxide. When the concentration of the aluminum salt is 0.3% by mass or more, the content of the aluminum salt in the regenerated collagen fiber is high and the water resistance is sufficient. Moreover, if it is 5 mass% or less, it will not be so hard after a process, and handleability will be favorable.

このアルミニウム塩水溶液のpHは、例えば塩酸、硫酸、酢酸、水酸化ナトリウム、炭酸ナトリウム等を用いて通常2.5〜5に調整する。このpHは、2.5以上であればコラーゲンの構造を良好に維持できる。pHが5以下であれば、アルミニウム塩の沈殿も生じず、均一に浸透し易くなる。このpHは、最初は2.2〜3.5に調整して充分にアルミニウム塩水溶液を再生コラーゲン内に浸透させ、その後に、例えば水酸化ナトリウム、炭酸ナトリウム等を添カロして3.5〜5に調整して処理を完結させることが好ましい。塩基性の高いアルミニウム塩を用いる場合には、2.5〜5の最初のpH調整だけでもかまわない。また、このアルミニウム塩水溶液の液温は特に限定されないが、50℃以下が好ましい。この液温が50℃以下であれば、再生コラーゲンの変性や変質は起きにくい。   The pH of the aluminum salt aqueous solution is usually adjusted to 2.5 to 5 using, for example, hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate or the like. If this pH is 2.5 or more, the structure of collagen can be maintained well. If pH is 5 or less, precipitation of aluminum salt does not occur, and it becomes easy to penetrate uniformly. This pH is initially adjusted to 2.2 to 3.5, and the aluminum salt aqueous solution is sufficiently permeated into the regenerated collagen, and then added with, for example, sodium hydroxide, sodium carbonate, etc. It is preferable to adjust to 5 to complete the treatment. When a highly basic aluminum salt is used, only the first pH adjustment of 2.5 to 5 may be used. Moreover, the liquid temperature of this aluminum salt aqueous solution is although it does not specifically limit, 50 degrees C or less is preferable. If the liquid temperature is 50 ° C. or lower, the regenerated collagen is hardly denatured or altered.

このアルミニウム塩水溶液に再生コラーゲンを浸漬ずる時間は、3時間以上、好ましくは6〜25時間とする。この浸漬時間は、3時間以上であればアルミニウム塩の反応が進み、再生コラーゲンの剤水性が充分となる。また、浸漬時間の上限には特に制限はないが、25時間以内でアルミニウム塩の反応は充分に進行し、耐水性も良好となる。なお、アルミニウム塩が再生コラーゲン中に急激に吸収されて温度むらを生じないようにするため、塩化ナトリウム、硫酸ナトリウム、塩化カリウム等の無機塩を適宜前記アルミニウム塩の水溶液に添加しても良い。   The time for immersing the regenerated collagen in this aluminum salt aqueous solution is 3 hours or more, preferably 6 to 25 hours. If the immersion time is 3 hours or longer, the reaction of the aluminum salt proceeds, and the aqueous solution of regenerated collagen becomes sufficient. Moreover, although there is no restriction | limiting in particular in the upper limit of immersion time, reaction of aluminum salt will fully advance within 25 hours, and water resistance will also become favorable. In order to prevent the aluminum salt from being rapidly absorbed into the regenerated collagen and causing temperature unevenness, an inorganic salt such as sodium chloride, sodium sulfate, or potassium chloride may be appropriately added to the aqueous solution of the aluminum salt.

本発明においては、処理終了後の繊維に含有されるアルミニウム含量が1〜10質量%となるように処理することが好ましい。さらに好ましい範囲は3〜9質量%である。アルミニウム含有量が、1質量%より少ないと、湿触感が不良となる傾向にある。また10質量%をこえると、処理後の繊維が硬くなって風合いを損ねてしまう傾向にある。   In this invention, it is preferable to process so that the aluminum content contained in the fiber after completion | finish of processing may be 1-10 mass%. A more preferable range is 3 to 9% by mass. When the aluminum content is less than 1% by mass, the wet feeling tends to be poor. Moreover, when it exceeds 10 mass%, the fiber after a process will become hard and there exists a tendency for a texture to be impaired.

このようにアルミニウム塩で処理された再生コラーゲン繊維は、ついで水洗、オイリング、乾燥を行なう。水洗は、たとえば、10分間〜4時間流水水洗することにより行なうことができる。オイリングに用いる油剤としては、たとえば、アミノ変性シリコーン、エポキシ変性シリコーン、ポリエーテル変性シリコーンなどのエマルジョンおよびプルロニック型ポリエーテル系静電防止剤からなる油剤などを用いることができる。乾燥温度は、好ましくは100℃以下、さらに好ましくは75℃以下、乾燥時の荷重は、1dtexに対して0.01〜0.25g、好ましくは0.02〜0.15gの重力下で行なうことが好ましい。   The regenerated collagen fiber thus treated with the aluminum salt is then washed, oiled and dried. The washing with water can be performed, for example, by washing with running water for 10 minutes to 4 hours. As an oil agent used for oiling, for example, an oil agent composed of an emulsion such as amino-modified silicone, epoxy-modified silicone, or polyether-modified silicone, and a pluronic polyether-based antistatic agent can be used. The drying temperature is preferably 100 ° C. or less, more preferably 75 ° C. or less, and the load during drying is 0.01 to 0.25 g, preferably 0.02 to 0.15 g based on 1 dtex. Is preferred.

ここで、水洗を施すのは、塩による油剤の析出を防止したり、乾燥機内で乾燥時に再生コラーゲン繊維から塩が析出し、かかる塩によって再生コラーゲン繊維に切れが発生したり、生成した塩が乾燥機内で飛散し、乾燥機内の熱交換器に付着して伝熱係数が低下ずるのを防ぐためである。また、オイリングを施した場合には、乾燥時における繊維の膠着防止や表面性の改善に効果がある。   Here, washing with water prevents oil from precipitating due to salt, or salt is precipitated from the regenerated collagen fiber during drying in the dryer, and the regenerated collagen fiber is broken by such salt, This is to prevent the heat transfer coefficient from decreasing due to scattering in the dryer and adhering to the heat exchanger in the dryer. In addition, when oiling is applied, it is effective in preventing fiber sticking and improving surface properties during drying.

また、コラーゲン溶液の紡糸の際には、溶液中又は紡出直前に顔料や染料を混合して着色することもできる(原着法)。使用する顔料や染料は用途に応じて、紡糸工程での溶出分離が無いこと、また使用製品の要求品質に対応して種類や色相を選択することができる。また必要に応じて、充填剤、老化防止剤、難燃剤、酸化防止剤等を添加することもできる。   Further, when spinning a collagen solution, it can be colored by mixing pigments or dyes in the solution or immediately before spinning (original deposition method). The pigments and dyes to be used can be selected in accordance with the application without any elution separation in the spinning process and according to the required quality of the product used. Moreover, a filler, an anti-aging agent, a flame retardant, an antioxidant, etc. can also be added as needed.

このようにして製造される再生コラーゲン繊維の繊度は、頭髪用として使用されるため、30dtex〜90dtexが好ましい。30dtexより小さいと、櫛通り性が悪くなり、頭髪用としては好ましくない。また、90dtexより大きくなると、頭髪用としては太すぎ、自然な外観を呈しないため好ましくない。   The fineness of the regenerated collagen fiber thus produced is preferably 30 dtex to 90 dtex because it is used for hair. When it is less than 30 dtex, the combing property is deteriorated, which is not preferable for hair. On the other hand, if it is larger than 90 dtex, it is not preferable because it is too thick for hair and does not exhibit a natural appearance.

こうして得られた再生コラーゲン繊維は、天然蛋白繊維の持つ風合いを保ちながら、人毛に近い光沢及びボリュームを有しており、人毛の代替としてより好適に使用することができる。   The regenerated collagen fiber thus obtained has gloss and volume similar to human hair while maintaining the texture of natural protein fiber, and can be more suitably used as a substitute for human hair.

本発明の再生コラーゲン系人工毛髪用繊維は、複数の断面形状の繊維を組み合わせても構わない。複数の断面形状の繊維とは、Y字形、S字形、C字形、繭形、4〜8葉形、キ形の繊維であっても構わないし、Y字形、S字形、C字形、繭形、4〜8葉形、キ形よりなる群から選ばれる少なくとも1種の断面形状を含んでいればその他の断面繊維を含んでいても構わない。再生コラーゲン系人工毛髪用繊維におけるその他の断面繊維とは、例えば、楕円形、円形、三角形などの人工毛髪用繊維として用いられる繊維断面をいう。   The regenerated collagen-based artificial hair fiber of the present invention may be a combination of fibers having a plurality of cross-sectional shapes. The fibers having a plurality of cross-sectional shapes may be Y-shaped, S-shaped, C-shaped, cocoon-shaped, 4- to 8-leaf-shaped, or K-shaped fibers, and may be Y-shaped, S-shaped, C-shaped, cocoon-shaped, Other cross-sectional fibers may be included as long as at least one cross-sectional shape selected from the group consisting of 4 to 8 leaf shapes and key shapes is included. The other cross-sectional fibers in the regenerated collagen-based artificial hair fibers refer to fiber cross-sections used as artificial hair fibers such as ellipse, circle, and triangle.

また、本発明の再生コラーゲン系人工毛髪用繊維は、他の合成繊維や人毛繊維と混繊しても構わない。他の合成繊維としては、例えば、アクリル系繊維、塩化ビニル系繊維、モダアクリル系繊維、ポリエステル系繊維、ポリアミド系繊維、ポリオレフィン系繊維などが挙げられる。   The regenerated collagen-based artificial hair fiber of the present invention may be mixed with other synthetic fibers or human hair fibers. Examples of other synthetic fibers include acrylic fibers, vinyl chloride fibers, modacrylic fibers, polyester fibers, polyamide fibers, and polyolefin fibers.

本発明の人工毛髪とは、本発明の再生コラーゲン繊維を含み、ウイッグ、ツーぺ、ブレード、エクステンションやウィービング等のヘアアクセサリー、ドールヘアー等に使用されるものである。   The artificial hair of the present invention includes the regenerated collagen fiber of the present invention and is used for hair accessories such as wigs, two-pieces, blades, extensions and weaving, doll hairs, and the like.

次に本発明を実施例により具体的に説明するが、本発明はかかる実施例のみに限定されるものではない。   EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to such examples.

なお、特性の評価方法は以下の通りである。
(光沢)
長さ30cm、総繊度10万dtexのトウを、太陽光の下、目視により評価する。
The characteristic evaluation method is as follows.
(Glossy)
A tow having a length of 30 cm and a total fineness of 100,000 dtex is evaluated visually under sunlight.

A:人毛に等しい光沢である。   A: Gloss equivalent to human hair.

B:人毛よりやや光沢が強い。   B: Gloss is slightly stronger than human hair.

C:人毛より光沢が強い。   C: Gloss is stronger than human hair.

D:人毛よりかなり光沢が強すぎる。
(ボリューム)
長さ10cm、7gの繊維を計量し、インシュロックにより最密充填させた後、その断面の面積を求めた。
D: Gloss is much stronger than human hair.
(volume)
A 10 cm long, 7 g fiber was weighed and closely packed with an insulation lock, and then the area of the cross section was determined.

A:断面積0.62cm2以上(人毛以上にボリュームがある)
B:0.60cm2以上〜0.62cm2未満(人毛並のボリュームがある)
C:0.58cm2以上〜0.60cm2未満(人毛よりボリュームが劣る)
D:0.58cm2未満(人毛よりかなりボリュームが劣る)
(触感)
A:人毛に等しいレベルの触感である。
A: Cross-sectional area 0.62 cm 2 or more (there is more volume than human hair)
B: 0.60 cm 2 or more and less than 0.62 cm 2 (there is a volume comparable to human hair)
C: 0.58 cm 2 or more to less than 0.60 cm 2 (volume is inferior to human hair)
D: Less than 0.58 cm 2 (volume is considerably inferior to human hair)
(Feel)
A: Tactile sensation equivalent to human hair.

B:人毛にやや劣るがソフトな触感である。   B: Soft touch but slightly inferior to human hair.

C:人毛に劣る触感である。   C: Tactile inferior to human hair.

D:ガサツキ感が強く、人毛とかけ離れた触感である。
(実施例1)
牛の床皮を原料とし、アルカリで可溶化した皮片1200g(コラーゲン分180g)に30重量%に希釈した過酸化水素水溶液30gを投入後、乳酸水溶液で溶解し、pH3.5、固形分7.5重量%に調整した原液を作製した。原液を減圧下で撹拌脱泡機((株)ダルトン製、8DMV型)により撹拌脱泡処理し、ピストン式紡糸原液タンクに移送し、さらに減圧下で静置し、脱泡を行った。かかる原液をピストンで押し出した後、ギアポンプ定量送液し、孔径10μmの焼結フィルターで濾過後、図6に示す断面形状及び孔径で、孔長0.5mm、孔数300の紡糸ノズルを通し、硫酸ナトリウム20重量%を含有してなる25℃の凝固浴(ホウ酸及び水酸化ナトリウムでpH11に調整)へ紡出速度5m/分で吐出した。
次に、得られた再生コラーゲン繊維(300本、20m)を、エピクロロヒドリン1.7
重量%、水酸化ナトリウム0.0246重量%、及び硫酸ナトリウム17重量%を含有し
た水溶液1.32kgに25℃で4時間浸漬した後、さらに反応液温度を43℃に昇温し
て2時間含浸した。
D: A feeling of harshness is strong, and the touch is far from human hair.
Example 1
30 g of hydrogen peroxide solution diluted to 30% by weight was added to 1200 g of skin sliced with alkali (180 g of collagen) using cow's floor skin as a raw material, and then dissolved in lactic acid aqueous solution, pH 3.5, solid content 7 A stock solution adjusted to 5% by weight was prepared. The stock solution was subjected to stirring and defoaming treatment with a stirring deaerator (manufactured by Dalton Co., Ltd., 8DMV type) under reduced pressure, transferred to a piston-type spinning stock solution tank, and further allowed to stand under reduced pressure for defoaming. After extruding the stock solution with a piston, the gear pump was fed in a fixed amount, filtered through a sintered filter having a pore diameter of 10 μm, passed through a spinning nozzle having a cross-sectional shape and a pore diameter of 0.5 mm, a hole length of 0.5 mm, and a hole number of 300, It was discharged at a spinning speed of 5 m / min into a 25 ° C. coagulation bath (adjusted to pH 11 with boric acid and sodium hydroxide) containing 20% by weight of sodium sulfate.
Next, the obtained regenerated collagen fiber (300 fibers, 20 m) was converted into epichlorohydrin 1.7.
After dipping in 1.32 kg of an aqueous solution containing 10% by weight of sodium hydroxide, 0.0246% by weight of sodium hydroxide and 17% by weight of sodium sulfate at 25 ° C. for 4 hours, the reaction solution temperature was further raised to 43 ° C. and impregnation for 2 hours did.

反応終了後に反応液を除去後、流動型装置にて1.32kgの25℃の水を用いて3回バッチ水洗を行った。この後、硫酸アルミニウム5重量%、クエン酸三ナトリウム塩0.9重量%、水酸化ナトリウム1.2重量%を含有した水溶液1.32kgに30℃で含浸し、反応開始から2時間後、3時間後及び4時間にそれぞれ5重量%水酸化ナトリウム水溶液13.2gを反応液に添加し、合計6時間反応させた。反応終了後に反応液を除去後、流動型装置にて1.32kgの25℃の水を用いて3回バッチ水洗を行った。   After the reaction was completed, the reaction solution was removed, and then washed with water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus. Thereafter, it was impregnated with 1.32 kg of an aqueous solution containing 5% by weight of aluminum sulfate, 0.9% by weight of trisodium citrate, and 1.2% by weight of sodium hydroxide at 30 ° C. After 5 hours and 4 hours, 13.2 g of a 5% by weight aqueous sodium hydroxide solution was added to the reaction solution and reacted for a total of 6 hours. After the reaction was completed, the reaction solution was removed, and then washed with water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus.

ついで、作製した繊維の一部をアミノ変性シリコーンのエマルジョン及びプルロニック型ポリエーテル系静電防止剤からなる油剤を満たした浴槽に浸漬して油剤を付着させた。50℃に設定した熱風対流式乾燥機内部で繊維束の一方の端を固定し、他方の端に繊維1本に対して2.8gの重りを吊り下げ2時間緊張下で乾燥させ、その後測定を実施した。評価結果を表1に示す。また、得られた繊維の断面写真を図19に示す
(実施例2〜6及び比較例1〜3)
実施例1同様に、図7〜図16に示す紡糸ノズルを用いて再生コラーゲン繊維を作製し、評価した。評価結果を表1に示す。また、得られた繊維の断面写真を図20〜図30に示す。
(比較例4)
アクリロニトリル49重量%、塩化ビニル50重量%、スチレンスルホン酸ソーダ1重量%からなる共重合体をアセトンに溶解して28.5重量%の紡糸原液を調整した。この原液を図17に示すY字形の紡糸ノズル(孔数=50)を用いて、25重量%のアセトン水溶液中に紡出し、65℃の温水浴中で1.5倍延伸し、ついで120℃で乾燥後、1.8倍の熱延伸を行い、更に160℃で緩和熱処理(0.92倍)を施して単糸繊度50dtexのモダクリル繊維を作製した。評価結果を表1に示す。また、得られた繊維の断面写真を図31に示す。
(比較例5、6)
比較例4と同様に、図18,図19に示す紡糸ノズルを用いてモダクリル繊維を作製した。評価結果を表1に示す。また得られた繊維の断面写真を図32、図33に示す。
Next, a part of the prepared fiber was immersed in a bath filled with an oil agent comprising an amino-modified silicone emulsion and a pluronic polyether-based antistatic agent to adhere the oil agent. One end of a fiber bundle is fixed inside a hot air convection dryer set to 50 ° C., and a weight of 2.8 g is hung from one fiber on the other end, dried under tension for 2 hours, and then measured. Carried out. The evaluation results are shown in Table 1. Moreover, the cross-sectional photograph of the obtained fiber is shown in FIG. 19 (Examples 2-6 and Comparative Examples 1-3).
As in Example 1, regenerated collagen fibers were prepared and evaluated using the spinning nozzles shown in FIGS. The evaluation results are shown in Table 1. Moreover, the cross-sectional photograph of the obtained fiber is shown in FIGS.
(Comparative Example 4)
A copolymer consisting of 49% by weight of acrylonitrile, 50% by weight of vinyl chloride and 1% by weight of sodium styrenesulfonate was dissolved in acetone to prepare a 28.5% by weight spinning dope. This stock solution was spun into a 25% by weight acetone aqueous solution using a Y-shaped spinning nozzle (number of holes = 50) shown in FIG. 17, stretched 1.5 times in a 65 ° C. hot water bath, and then 120 ° C. After drying, the film was stretched 1.8 times and further subjected to relaxation heat treatment (0.92 times) at 160 ° C. to produce a modacrylic fiber having a single yarn fineness of 50 dtex. The evaluation results are shown in Table 1. Moreover, the cross-sectional photograph of the obtained fiber is shown in FIG.
(Comparative Examples 5 and 6)
Similarly to Comparative Example 4, modacrylic fibers were produced using the spinning nozzles shown in FIGS. The evaluation results are shown in Table 1. Moreover, the cross-sectional photograph of the obtained fiber is shown to FIG. 32, FIG.

表1に示すように、実施例1〜8は比較例1〜3に比べて光沢及びボリュームに優れる事が判る。また、実施例1,2、7,8は比較例4〜6に比べて、触感に優れることが判る。従って、今回の繊維断面に明確な凹部を有する再生コラーゲン系人工毛髪繊維は、再生コラーゲン系人工毛髪繊維の特徴である自然な触感を損なうことなく、光沢、ボリュームが改善された人工毛髪用繊維として用いる事が可能である。 As shown in Table 1, it can be seen that Examples 1 to 8 are superior in gloss and volume as compared with Comparative Examples 1 to 3. Moreover, it turns out that Example 1, 2, 7, 8 is excellent in tactile sense compared with Comparative Examples 4-6. Therefore, the regenerated collagen-based artificial hair fiber having a clear recess on the fiber cross section is a fiber for artificial hair with improved gloss and volume without impairing the natural touch that is characteristic of the regenerated collagen-based artificial hair fiber. It can be used.

図1は本発明における再生コラーゲン繊維のY字形断面説明図FIG. 1 is a cross-sectional explanatory view of a Y-shaped regenerated collagen fiber according to the present invention. (2−1)は本発明における再生コラーゲン繊維のS字形断面説明図 (2−2)は本発明における再生コラーゲン繊維のS字形断面説明図 (2−3)は本発明における再生コラーゲン繊維のS字形断面説明図(2-1) is an S-shaped cross-sectional view of the regenerated collagen fiber in the present invention. (2-2) is an S-shaped cross-sectional view of the regenerated collagen fiber in the present invention. (2-3) is the S of the regenerated collagen fiber in the present invention. Characteristic cross-sectional illustration 図3は本発明における再生コラーゲン繊維のS字形断面説明図FIG. 3 is an S-shaped cross-sectional view of the regenerated collagen fiber in the present invention. 図4は本発明における再生コラーゲン繊維の繭形断面説明図FIG. 4 is a cross-sectional explanatory view of a regenerated collagen fiber according to the present invention. (5−1)は本発明における再生コラーゲン繊維の4葉形断面説明図 (5−2)は本発明における再生コラーゲン繊維の5葉形断面説明図 (5−3)は本発明における再生コラーゲン繊維の6葉形断面説明図 (5−4)は本発明における再生コラーゲン繊維の7葉形断面説明図 (5−5)は本発明における再生コラーゲン繊維の8葉形断面説明図(5-1) is a cross-sectional explanatory view of the regenerated collagen fiber according to the present invention. (5-2) is a cross-sectional explanatory view of the regenerated collagen fiber according to the present invention. (5-3) is a regenerated collagen fiber according to the present invention. (5-4) is a 7-leaf cross-sectional explanatory view of the regenerated collagen fiber in the present invention. (5-5) is an 8-leaf cross-sectional explanatory view of the regenerated collagen fiber in the present invention. 図6は本発明における再生コラーゲン繊維のキ形断面説明図FIG. 6 is an explanatory diagram of a cross section of a regenerated collagen fiber according to the present invention. 図7は本発明の実施例1に用いたノズル形状説明図FIG. 7 is an explanatory diagram of the nozzle shape used in Example 1 of the present invention. 図8は本発明の実施例2に用いたノズル形状説明図FIG. 8 is an explanatory diagram of the nozzle shape used in Example 2 of the present invention. 図9は本発明の実施例3に用いたノズル形形状説明図FIG. 9 is an explanatory diagram of the nozzle shape used in Example 3 of the present invention. 図10は本発明の実施例4に用いたノズル形状説明図FIG. 10 is an explanatory diagram of the nozzle shape used in Example 4 of the present invention. 図11は本発明の実施例5に用いたノズル形状説明図FIG. 11 is an explanatory diagram of the nozzle shape used in Example 5 of the present invention. 図12は本発明の実施例6に用いたノズル形状説明図FIG. 12 is an explanatory diagram of the nozzle shape used in Example 6 of the present invention. 図13は本発明の実施例7に用いたノズル形状説明図FIG. 13 is an explanatory diagram of the nozzle shape used in Example 7 of the present invention. 図14は本発明の実施例8に用いたノズル形状説明図FIG. 14 is an explanatory diagram of the nozzle shape used in Example 8 of the present invention. 図15は本発明の比較例2に用いたノズル形状説明図FIG. 15 is an explanatory diagram of the nozzle shape used in Comparative Example 2 of the present invention. 図16は本発明の比較例3に用いたノズル形状説明図FIG. 16 is an explanatory diagram of the nozzle shape used in Comparative Example 3 of the present invention. 図17は本発明の比較例4に用いたノズル形状説明図FIG. 17 is an explanatory diagram of the nozzle shape used in Comparative Example 4 of the present invention. 図18は本発明の比較例5に用いたノズル形状説明図FIG. 18 is an explanatory diagram of the nozzle shape used in Comparative Example 5 of the present invention. 図19は本発明の比較例6に用いたノズル形状説明図FIG. 19 is an explanatory diagram of the nozzle shape used in Comparative Example 6 of the present invention. 図20は本発明の実施例1で得られた再生コラーゲン繊維の断面説明図FIG. 20 is a cross-sectional explanatory view of the regenerated collagen fiber obtained in Example 1 of the present invention. 図21は本発明の実施例2で得られた再生コラーゲン繊維の断面説明図FIG. 21 is a cross-sectional explanatory view of the regenerated collagen fiber obtained in Example 2 of the present invention. 図22は本発明の実施例3で得られた再生コラーゲン繊維の断面説明図FIG. 22 is a cross-sectional explanatory view of the regenerated collagen fiber obtained in Example 3 of the present invention. 図23は本発明の実施例4で得られた再生コラーゲン繊維の断面説明図FIG. 23 is a cross-sectional explanatory view of a regenerated collagen fiber obtained in Example 4 of the present invention. 図24は本発明の実施例5で得られた再生コラーゲン繊維の断面説明図FIG. 24 is a sectional explanatory view of the regenerated collagen fiber obtained in Example 5 of the present invention. 図25は本発明の実施例6で得られた再生コラーゲン繊維の断面説明図FIG. 25 is a cross-sectional explanatory view of the regenerated collagen fiber obtained in Example 6 of the present invention. 図26は本発明の実施例7で得られた再生コラーゲン繊維の断面説明図FIG. 26 is a cross-sectional explanatory view of the regenerated collagen fiber obtained in Example 7 of the present invention. 図27は本発明の実施例8で得られた再生コラーゲン繊維の断面説明図FIG. 27 is a cross-sectional explanatory view of the regenerated collagen fiber obtained in Example 8 of the present invention. 図28は本発明の比較例1で得られた再生コラーゲン繊維の断面説明図FIG. 28 is a cross-sectional explanatory view of a regenerated collagen fiber obtained in Comparative Example 1 of the present invention. 図29は本発明の比較例2で得られた再生コラーゲン繊維の断面説明図FIG. 29 is a cross-sectional explanatory view of a regenerated collagen fiber obtained in Comparative Example 2 of the present invention. 図30は本発明の比較例3で得られた再生コラーゲン繊維の断面説明図FIG. 30 is a cross-sectional explanatory view of the regenerated collagen fiber obtained in Comparative Example 3 of the present invention. 図31は本発明の比較例4で得られた再生コラーゲン繊維の断面説明図FIG. 31 is a cross-sectional explanatory view of a regenerated collagen fiber obtained in Comparative Example 4 of the present invention. 図32は本発明の比較例5で得られた再生コラーゲン繊維の断面説明図FIG. 32 is a cross-sectional explanatory view of a regenerated collagen fiber obtained in Comparative Example 5 of the present invention. 図33は本発明の比較例6で得られた再生コラーゲン繊維の断面説明図FIG. 33 is a cross-sectional explanatory view of a regenerated collagen fiber obtained in Comparative Example 6 of the present invention.

符号の説明Explanation of symbols

α Y字形断面の突起部分のなす角度
β Y字形断面の突起部分のなす角度
γ Y字形断面の突起部分のなす角度
p Y字形断面の突起部分の長さ
q Y字形断面の突起部分の幅
a S字形断面の幅
b C字形断面の開口部の長さ
c C字形断面の外径
d 繭形断面の長さ
e 繭形断面の窪み部分の長さ
f キ形断面の突起部の長さ
g キ形断面の突起部の長さ
h キ形断面の突起部の長さ
i キ形断面の突起部の長さ
W 4〜8葉形断面の突起部の幅
L 4〜8葉形断面の突起部の高さ
R 繭型断面の円形部の半径
α Angle formed by the protruding portion of the Y-shaped cross section β Angle formed by the protruding portion of the Y-shaped cross section γ Angle formed by the protruding portion of the Y-shaped cross section p Length of the protruding portion of the Y-shaped cross section q Width of the protruding portion of the Y-shaped cross section a Width of S-shaped section b Length of opening of C-shaped section c Outer diameter of C-shaped section d Length of bowl-shaped section e Length of recess in bowl-shaped section f Length of protrusion of key-shaped section g Projection length of key section h Length of protrusion section of key section i Length of protrusion section of key section W Width of protrusion section of 4-8 leaf section L Projection of leaf section of L 4-8 Part height R Radius of the circular part of the vertical cross section

Claims (5)

Y字形、S字形、C字形、繭形、4〜8葉形、キ形よりなる群から選ばれる少なくとも1種の断面形状を有することを特徴とする再生コラーゲン系人工毛髪用繊維。   A fiber for regenerated collagen-based artificial hair, characterized by having at least one cross-sectional shape selected from the group consisting of Y-shape, S-shape, C-shape, cocoon shape, 4-8 leaf shape, and key shape. 再生コラーゲン繊維が単官能エポキシ化合物及び金属アルミニウム塩を含むことを特徴とする請求項1に記載の再生コラーゲン系人工毛髪用繊維。   The regenerated collagen fiber for artificial hair according to claim 1, wherein the regenerated collagen fiber contains a monofunctional epoxy compound and a metal aluminum salt. 単官能エポキシ化合物が下記一般式(1)で表される単官能エポキシ化合物である請求項2に記載の再生コラーゲン系人工毛髪用繊維。
但し、RはR1−、R2−O−CH2−またはR2−COO−CH2−で表される置換基を示し、R1は炭素数2以上20以下の炭化水素基またはCH2Clであり、R2は炭素数4以上20以下の炭化水素基を示す。
The fiber for regenerated collagen-based artificial hair according to claim 2, wherein the monofunctional epoxy compound is a monofunctional epoxy compound represented by the following general formula (1).
R represents a substituent represented by R 1 —, R 2 —O—CH 2 — or R 2 —COO—CH 2 —, and R 1 represents a hydrocarbon group having 2 to 20 carbon atoms or CH 2. Cl and R 2 represents a hydrocarbon group having 4 to 20 carbon atoms.
再生コラーゲン繊維が金属アルミニウム塩で架橋されていることを特徴とする請求項1〜請求項3のいずれかに記載の再生コラーゲン系人工毛髪用繊維。   The regenerated collagen-based artificial hair fiber according to any one of claims 1 to 3, wherein the regenerated collagen fiber is crosslinked with a metal aluminum salt. 請求項1〜請求項4のいずれかに記載の再生コラーゲン系人工毛髪用繊維を含む、人工毛髪。   Artificial hair containing the fiber for regenerated collagen type artificial hair according to any one of claims 1 to 4.
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