JPH04226538A - Production of collagen powder - Google Patents

Production of collagen powder

Info

Publication number
JPH04226538A
JPH04226538A JP10362491A JP10362491A JPH04226538A JP H04226538 A JPH04226538 A JP H04226538A JP 10362491 A JP10362491 A JP 10362491A JP 10362491 A JP10362491 A JP 10362491A JP H04226538 A JPH04226538 A JP H04226538A
Authority
JP
Japan
Prior art keywords
collagen
powder
tanning
wet
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP10362491A
Other languages
Japanese (ja)
Inventor
Tetsuo Wada
哲夫 和田
Tetsuhiko Yamaguchi
山口 哲彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP10362491A priority Critical patent/JPH04226538A/en
Publication of JPH04226538A publication Critical patent/JPH04226538A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To provide collagen powder suitable as an additive for improving coatings, artificial leathers, molding materials, etc., which contain thermoplastic resins as base raw materials. CONSTITUTION:A purified animal tissue containing collagen as a main component is subjected to a wet grinding treatment in a collagen concentration of 1-30wt.% at a water temperature of <=37 deg.C and in a pH range of 2-8 in water, and subsequently subjected to a tanning treatment using a multivalent metal tanning agent in a pH range of 4-8 to produce a wet stabilized collagen material, which is dehydrated at a pH of 4-8 and further dried and pulverized into the powder of collagen. The powder of the collagen can be employed in an additive for improving coatings, artificial leathers, molding materials, etc., which contain synthetic resins as a base material. The addition of the powder of the collagen thereto gives the materials having excellent performances such as excellent appearances, touches, moisture-absorbing and releasing properties.

Description

【発明の詳細な説明】[Detailed description of the invention]

【0001】0001

【産業上の利用分野】本発明は新規なコラーゲン粉末の
製造方法に関する。さらに詳しくは熱可塑性樹脂等の合
成樹脂をベースとする塗料、人工皮革、成形材料等の改
質に有用な添加剤として使用するのに適したコラーゲン
粉末の製造方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing collagen powder. More specifically, the present invention relates to a method for producing collagen powder suitable for use as an additive useful in modifying paints, artificial leathers, molding materials, etc. based on synthetic resins such as thermoplastic resins.

【0002】0002

【従来の技術】近年、塗料、人工皮革等は高級化志向に
伴い、天然皮革のような外観、感触、吸放湿性、透湿性
等を持つことが要求され、これらの要求に応えるべく塗
料、人工皮革、成形材料等のベースとなるポリウレタン
樹脂、ポリアクリル樹脂、ポリ塩化ビニル樹脂等の合成
樹脂にコラーゲン粉末、皮革粉、ゼラチン粉末、ポリウ
レタンビーズ等を混合してこれらを天然皮革様に改質す
ることが試みられている。
[Prior Art] In recent years, with the trend toward higher quality paints, artificial leathers, etc., there has been a demand for paints, artificial leathers, etc. to have the appearance, feel, moisture absorbing/releasing properties, moisture permeability, etc. of natural leather. Synthetic resins such as polyurethane resin, polyacrylic resin, and polyvinyl chloride resin, which are the base of artificial leather and molding materials, are mixed with collagen powder, leather powder, gelatin powder, polyurethane beads, etc., and modified to resemble natural leather. An attempt is being made to do so.

【0003】これらに用いられるコラーゲン粉末や皮革
粉の製造方法は、従来よりいくつか提案されているが、
それらの多くはクロムなめし、又は、タンニンなめしさ
れた天然皮革を単に粉砕して粉末化するものであり、こ
れらは裸皮の状態、即ち、コラーゲン繊維束(ファイバ
ーバンドル)の状態でなめし処理がなされることから、
粉末化しても粒子状ではなく長い繊維状となり易く、特
公昭40−11075号公報に見られるように、例えば
、熱可塑性樹脂にこれらを混合して製造した人工皮革は
、表面の平滑性が失われて天然皮革様の感触が得られな
い等の問題がある。最近になって、特開昭63−992
98号公報に見られるように、これらを改良するため皮
革屑をスチームで加熱処理を加えた後に粉砕して粒子状
の粉末にする方法が提案されている。しかし、この方法
では皮革粉は粒子状となるが、スチ−ムにより100℃
以上に加熱されているので、吸湿性が小さく又見掛けか
さ比重(JIS K 6721)が大きい粉末となって
、例えば、これを塗料の添加剤として使用した場合、表
面の艶消しや吸放湿性の効果が不足する等の欠点があり
、未だ満足できるものであるとは言い難い。
[0003] Several methods have been proposed for producing collagen powder and leather powder used in these products.
Most of them are chrome-tanned or tanned natural leather that is simply crushed and powdered, and these are tanned in the state of bare skin, that is, in the state of collagen fiber bundles. Because of that,
Even when powdered, it tends to become long fibers rather than particles, and as seen in Japanese Patent Publication No. 40-11075, for example, artificial leather manufactured by mixing these with thermoplastic resin loses its surface smoothness. There are problems such as the inability to obtain a natural leather-like feel. Recently, JP-A-63-992
As seen in Japanese Patent No. 98, in order to improve these problems, a method has been proposed in which leather scraps are heat treated with steam and then ground into granular powder. However, with this method, the leather powder becomes particulate, but it is heated to 100℃ using steam.
Because it is heated to a higher temperature, it becomes a powder with low hygroscopicity and high apparent bulk specific gravity (JIS K 6721). For example, when this is used as an additive for paint, it may cause the surface to become matte or the moisture absorption/release properties to be reduced. It has drawbacks such as lack of effectiveness, and it is still difficult to say that it is satisfactory.

【0004】また、特公昭61−4419号公報におい
ては、皮革屑ではなくコラーゲンを粉末とする方法が提
案されている。これは、精製された動物の裸皮を用いて
、粗分散、なめし処理、分散、脱水、乾燥の処理を順に
行いコラーゲン粉末を得る方法であるが、粗分散により
得られるコラーゲン繊維束をなめし処理するためコラー
ゲンが繊維状となり、特公昭40−11075号公報と
同様の欠点が生じる問題がある。
[0004] Furthermore, Japanese Patent Publication No. 61-4419 proposes a method of powdering collagen instead of leather waste. In this method, collagen powder is obtained by sequentially performing coarse dispersion, tanning, dispersion, dehydration, and drying using purified animal skin, and the collagen fiber bundles obtained by coarse dispersion are tanned. Therefore, the collagen becomes fibrous, resulting in the same problem as in Japanese Patent Publication No. 40-11075.

【0005】更に、特願平1−217499号には、特
殊な方法により精製されたコラーゲンを主成分とする動
物の組織を水中で粉砕した後、なめし剤によりなめし処
理をしてコラーゲン湿体を製造する方法が提案されてい
るが、動物組織の水中での粉砕がコラーゲン濃度0.3
〜0.8重量%のような低濃度においてなされるので、
粉砕に長時間を要し、或は、コラーゲン繊維束の解繊が
不充分となりこれが粉末中に長い繊維状物となって混入
する問題点がある。
Furthermore, Japanese Patent Application No. 1-217499 discloses that after pulverizing animal tissue whose main component is collagen purified by a special method in water, it is tanned with a tanning agent to obtain wet collagen. A method for producing collagen has been proposed, but pulverizing animal tissue in water produces a collagen concentration of 0.3.
Since it is done at low concentrations such as ~0.8% by weight,
There are problems in that pulverization takes a long time or the collagen fiber bundles are insufficiently defibrated, resulting in long fibers being mixed into the powder.

【0006】[0006]

【発明が解決しようとする課題】本発明の目的は、上記
従来技術の問題点が改良された見かけかさ密度は低いが
、繊維状物を含まず、粒子状であって、塗料、人工皮革
、成形材料等のベースである合成樹脂に添加して、これ
らに天然皮革に近い性質を付与することのできるコラー
ゲン粉末を製造する方法を提供することにある。
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a material that has a low apparent bulk density, does not contain fibrous materials, is particulate, and can be used in paints, artificial leather, etc. The object of the present invention is to provide a method for producing collagen powder that can be added to synthetic resins that are the base of molding materials and the like to impart properties similar to those of natural leather.

【0007】[0007]

【課題を解決するための手段】上記目的を達成するため
に鋭意検討した結果、豚、牛等の裸皮等の動物の組織を
石灰漬け、酵素処理、水洗等の処理をして得られる精製
されたコラーゲン塊状物を細断し、更に水中において、
コラーゲン濃度を1〜30重量%、水温37℃以下及び
pH2〜8の範囲で湿式粉砕することによりコラーゲン
細繊維(フィブリル)分散物または溶解物が効率よく得
られ、これになめし剤として従来裸皮のなめし剤として
使用されている硫酸クロム、硫酸アルミニウム、硫酸ジ
ルコニル等の多価金属塩類をpH2〜7の範囲で加えて
安定化コラーゲン湿体とした後、これをpH4〜8の範
囲にpHを調整して脱水し、さらに乾燥、粉砕すること
により見掛けかさ密度は低いが、コラーゲンが繊維状で
はなく粒子状となるコラーゲン粉末が得られることを見
出し本発明を完成するに至った。
[Means for solving the problem] As a result of intensive studies to achieve the above object, we have developed a purified animal tissue obtained by treating animal tissues such as naked skins of pigs, cows, etc. with lime pickling, enzyme treatment, washing with water, etc. The resulting collagen mass was shredded and further submerged in water.
By wet milling at a collagen concentration of 1 to 30% by weight, a water temperature of 37°C or less, and a pH of 2 to 8, a collagen fibril dispersion or dissolution can be efficiently obtained, and this can be used as a tanning agent for conventional skin peels. Polyvalent metal salts such as chromium sulfate, aluminum sulfate, and zirconyl sulfate, which are used as tanning agents, are added at a pH range of 2 to 7 to form a stabilized collagen wet mass, and then the pH is adjusted to a pH range of 4 to 8. By adjusting, dehydrating, further drying and pulverizing, it was found that a collagen powder having a low apparent bulk density but in which the collagen is not fibrous but granular was obtained, leading to the completion of the present invention.

【0008】本発明のコラーゲン粉末の製造方法は、上
記のようなコラーゲン粉末を得るためには、精製された
コラーゲン塊状物を細断して水中で湿式粉砕後、なめし
処理をしてコラーゲン湿体とする過程において、コラー
ゲンを均一になめし処理すること、及び、コラーゲンの
加水分解(ゼラチン化)を極力抑えることが必要である
との観点にたち、その手段として、精製処理された、コ
ラーゲンを主成分とする動物組織を濃度が1〜30重量
%、さらに好ましくは3〜15重量%として水中で充分
に湿式粉砕して、細繊維分散物または溶解物とした後、
なめし剤を加えてなめし処理をすること、及び、湿式粉
砕のpHを2〜8、温度を37℃以下、なめし処理に多
価金属なめし剤を用い、pH2〜7で処理を行い、脱水
のpHを4〜8に調整する等の細かい限定条件下で製造
を行うことが特徴である。
[0008] In the method for producing collagen powder of the present invention, in order to obtain the collagen powder as described above, a purified collagen mass is shredded, wet-pulverized in water, and tanned to form a collagen wet powder. Based on the viewpoint that it is necessary to uniformly tan collagen and to suppress collagen hydrolysis (gelatinization) as much as possible in the process of After fully wet-pulverizing the animal tissue as a component in water to a concentration of 1 to 30% by weight, more preferably 3 to 15% by weight, to obtain a fine fiber dispersion or a dissolved substance,
Adding a tanning agent to the tanning process, and wet grinding at a pH of 2 to 8 and a temperature of 37 degrees Celsius or less, using a polyvalent metal tanning agent in the tanning process at a pH of 2 to 7, and dehydrating to a pH of 2 to 7. It is characterized by manufacturing under narrowly limited conditions such as adjusting the value to 4 to 8.

【0009】更に本発明を詳しく説明する。即ち、本発
明は、例えば、精製された動物の皮のような動物組織を
水中で分散または溶解、なめし、脱水、乾燥、粉砕の各
処理を順次なすことによりコラーゲン粉末を製造する方
法である。この動物組織としては、牛、馬、豚、羊等の
哺乳動物を始めとするあらゆる脊椎動物の皮、骨、腱等
のコラーゲンを多量に含む組織が使用でき、精製方法は
、特に制限はなく、プロテアーゼ、リパーゼ系の酵素を
1種または2種以上使用する方法、石灰等のアルカリを
使用する方法、イオン性又は非イオン性の界面活性剤を
使用する方法などがあるが、上記酵素処理及び界面活性
剤処理を併用して夾雑物をよく除いた動物の裸皮を使用
するのが好ましい。又、ここで用いる界面活性剤は、洗
浄しても裸皮中に残存し易いイオン性のものではなく、
非イオン性のものを使用するのが好ましい。
The present invention will be further explained in detail. That is, the present invention is a method for producing collagen powder by sequentially dispersing or dissolving animal tissue such as purified animal skin in water, tanning, dehydration, drying, and pulverization. As this animal tissue, tissues containing a large amount of collagen such as the skin, bones, tendons, etc. of all vertebrate animals including mammals such as cows, horses, pigs, and sheep can be used, and there are no particular restrictions on the purification method. , a method using one or more types of enzymes such as protease and lipase, a method using an alkali such as lime, and a method using an ionic or nonionic surfactant. It is preferable to use naked animal hides that have been thoroughly cleaned of impurities by treatment with a surfactant. In addition, the surfactant used here is not an ionic one that tends to remain in naked skin even after washing.
Preferably, non-ionic materials are used.

【0010】湿式粉砕による分散または溶解は、コラー
ゲン粉末の性質を一定にし、長繊維状化を防止すると同
時に見掛けかさ密度の低い粒子とする目的で、湿式粉砕
処理に次いでなされるなめし処理を、容易、且つ、均一
にするため、精製処理されたコラーゲン塊状物を水によ
り膨潤し、コラーゲン細繊維の分散物或は溶解物にする
処理である。
[0010] Dispersion or dissolution by wet pulverization is intended to make the properties of the collagen powder constant, prevent it from forming into long fibers, and at the same time make the tanning treatment that follows the wet pulverization process easier. In addition, in order to make the collagen uniform, the purified collagen mass is swollen with water to form a dispersion or melt of collagen fibrils.

【0011】精製された動物組織を、肉挽機等を用いて
粗く切断した後、水により希釈し、コラーゲン濃度を1
〜30重量%、pH2〜8に調整し、水温が37℃を越
えない様に注意して、製紙用叩解機、回転刃解砕機等の
機器を用いてなされる。コラーゲンの濃度が1重量%未
満では、湿式粉砕が充分に均一になされず、繊維束状の
部分の残存が著しく増加し、その上、湿式粉砕の効率が
大きく低下するので好ましくない。また、コラーゲンの
濃度が30重量%を越えるときは、分散液の粘度が高く
なり、湿式粉砕時に水温が上昇して37℃以上になりコ
ラーゲンの加水分解が起こってしまうので、粉砕速度を
遅くする等の措置が必要となり、粉砕の効率が著しく低
下するので好ましくない。
[0011] The purified animal tissue is roughly cut using a meat grinder, etc., and then diluted with water to bring the collagen concentration to 1.
-30% by weight, pH is adjusted to 2-8, and the water temperature is adjusted to not exceed 37°C using equipment such as a paper-making beater or a rotary blade crusher. If the concentration of collagen is less than 1% by weight, the wet grinding will not be sufficiently uniform, the residual portion of fiber bundles will increase significantly, and the efficiency of the wet grinding will decrease significantly, which is not preferable. Additionally, if the concentration of collagen exceeds 30% by weight, the viscosity of the dispersion will increase and the water temperature will rise to 37°C or higher during wet milling, causing collagen hydrolysis, so the milling speed should be slowed down. This is not preferable because it requires measures such as the following, which significantly reduces the efficiency of pulverization.

【0012】このときのpHは、pH2〜8の範囲内で
これをを選ぶことにより、コラーゲンの性状を決定し、
更には、コラーゲン粉末の見かけかさ密度等の物性を決
めることが出来る。即ち、pH2〜8の範囲内でpHを
高くするとコラーゲンは繊維状分散物となって、粉末の
見掛けかさ比重は低くなり、pHを低くするとコラーゲ
ンは強膨潤物又は溶解物となって、粉末の見掛けかさ密
度を高くすることが出来る。
[0012] The pH at this time is selected within the range of pH 2 to 8 to determine the properties of collagen.
Furthermore, physical properties such as the apparent bulk density of the collagen powder can be determined. That is, when the pH is increased within the range of pH 2 to 8, collagen becomes a fibrous dispersion, and the apparent bulk specific gravity of the powder becomes low; when the pH is decreased, collagen becomes a strongly swollen or dissolved material, and the powder becomes less dense. The apparent bulk density can be increased.

【0013】但し、pH2未満、又は、pH8を越える
と、湿式粉砕処理によりコラーゲンの加水分解が起こり
易くなるので好ましくない。ここでpHを調整する為に
用いられる酸、アルカリは、一般に用いられているもの
で良く、酸では、塩酸・硫酸等の鉱酸、酢酸・乳酸・ク
エン酸・酒石酸・コハク酸・リンゴ酸等の有機酸のいず
れでも良く、アルカリでは、水酸化ナトリウム・重炭酸
ナトリウム・アンモニア水・有機アミン類等が使用でき
る。
[0013] However, if the pH is less than 2 or more than 8, hydrolysis of collagen tends to occur during the wet grinding process, which is not preferable. The acids and alkalis used to adjust the pH here may be those commonly used. Examples of acids include mineral acids such as hydrochloric acid and sulfuric acid, acetic acid, lactic acid, citric acid, tartaric acid, succinic acid, malic acid, etc. Any of the organic acids may be used, and as alkalis, sodium hydroxide, sodium bicarbonate, aqueous ammonia, organic amines, etc. can be used.

【0014】なめし処理は、コラーゲン粉末の吸水度{
規格化された測定方法が現在の時点では定められていな
いので、次に記す方法により測定した。粉末試料約1.
0g(WA )を水に1時間以上浸漬して吸水させた後
、よく水をきり、更に濾紙(東洋濾紙(株)製No.5
Cφ9cm)上に直径約4cmになる様にのせ、この上
下に数枚の濾紙を積層した後、これらの上に20Kgの
重りをのせて3分間加圧脱水し、過剰付着水を除去し、
秤量(WB )して、下式吸水度=(WB −WA )
/WA ×100(重量%)により算出した。}を所定
の値に保ち、耐熱安定性を高める目的から、コラーゲン
繊維の分散物或は溶解物になめし剤を加えて、繊維間或
は分子間になめし剤を沈着させるか、繊維間・分子間を
結び付ける処理である。
[0014] The tanning process depends on the water absorption of collagen powder {
Since no standardized measurement method has been established at present, the following method was used for measurement. Powder sample approx.
After soaking 0g (WA) in water for over 1 hour to absorb water, drain the water thoroughly and add filter paper (No. 5 manufactured by Toyo Roshi Co., Ltd.).
Cφ9cm) to a diameter of approximately 4cm, and after layering several pieces of filter paper above and below this, a 20kg weight was placed on top of these and dehydrated under pressure for 3 minutes to remove excess adhering water.
Weigh (WB) and use the following formula: Water absorption = (WB - WA)
/WA×100 (weight%). } for the purpose of maintaining a predetermined value and increasing heat resistance stability, a tanning agent is added to a dispersion or melt of collagen fibers, and the tanning agent is deposited between fibers or molecules, or between fibers or molecules. This is a process that connects the two.

【0015】なめし剤としては、硫酸クロム、硫酸ジル
コニル、硫酸アルミニウム等の多価金属化合物が挙げら
れるが、これらの他に、ホルムアルデヒド、グルタルア
ルデヒド、タンニン等の有機化合物なめし剤を併用する
ことも可能である。なめし剤の主剤に多価金属なめし剤
を用いることにより、コラーゲンの熱変性温度をかなり
上昇させることが可能となるので、後工程の脱水・乾燥
において高い温度を用いることが出来、これらの工程の
効率化をはかることが出来る様になる。又、なめし剤の
添加量を変えることにより、コラーゲン粉末の吸水度を
変化させることが可能となる。
[0015] Tanning agents include polyvalent metal compounds such as chromium sulfate, zirconyl sulfate, and aluminum sulfate, but in addition to these, it is also possible to use organic compound tanning agents such as formaldehyde, glutaraldehyde, and tannin. It is. By using a polyvalent metal tanning agent as the main ingredient of the tanning agent, it is possible to considerably raise the thermal denaturation temperature of collagen, so high temperatures can be used in the dehydration and drying steps in the post-processes, and the It will be possible to improve efficiency. Furthermore, by changing the amount of tanning agent added, it is possible to change the water absorption of the collagen powder.

【0016】例えば塗料、人工皮革、成形材料等の添加
剤として好ましい吸水度150〜300重量%とするの
に必要ななめし剤の添加量は、コラーゲン100重量部
当り、硫酸クロムでは1〜2重量部、硫酸ジルコニルで
は1〜10重量部、硫酸アルミニウムでは2〜20重量
部が好適である。尚、コラーゲン粉末の外観を白色にし
たい場合は、なめし剤として硫酸ジルコニル、硫酸アル
ミニウムを用いるのが好ましい。
[0016] For example, the amount of tanning agent necessary to achieve a water absorption of 150 to 300% by weight, which is preferable as an additive for paints, artificial leather, molding materials, etc., is 1 to 2 parts by weight for chromium sulfate per 100 parts by weight of collagen. 1 to 10 parts by weight for zirconyl sulfate and 2 to 20 parts by weight for aluminum sulfate. In addition, when it is desired to make the appearance of collagen powder white, it is preferable to use zirconyl sulfate or aluminum sulfate as a tanning agent.

【0017】さらに、コラーゲン分散液のpHは2〜7
でなめし処理がなされるが、これは、pH2未満では、
金属なめし剤がコラーゲン繊維間に沈着しにくくなるか
、或は、コラーゲン中のカルボキシル基が解離せずなめ
し剤との結合が非常に遅くなり、又、pH7を越えると
、酢酸、クエン酸、乳酸等の有機酸イオンの存在下でも
なめし剤の多価金属イオンが水酸化物として、添加と同
時に沈澱してしまい、なめしが均一に行われない為であ
る。また、なめし工程において、二酸化チタン、酸化鉄
等の顔料やカオリン、シリカ等の体質顔料を添加して着
色したり、硬さを変化させたコラーゲン粉末を得ること
も可能である。
Furthermore, the pH of the collagen dispersion is 2 to 7.
The tanning process is carried out at a pH of less than 2.
If the metal tanning agent becomes difficult to deposit between collagen fibers, or the carboxyl groups in collagen do not dissociate and bonding with the tanning agent becomes very slow, or if the pH exceeds 7, acetic acid, citric acid, lactic acid This is because even in the presence of organic acid ions such as tanning agents, polyvalent metal ions in the tanning agent precipitate as hydroxides upon addition, resulting in uneven tanning. Furthermore, in the tanning process, it is also possible to add pigments such as titanium dioxide and iron oxide, and extender pigments such as kaolin and silica to obtain collagen powder that is colored or has a different hardness.

【0018】脱水処理は、なめし処理で得られたコラー
ゲン凝集物の水分率を下げて、乾燥を容易にする目的で
通常の遠心分離機、フィルタープレス機、スクリュウプ
レス機等を使用してなされる。このとき、pH4〜8の
範囲にpHを調整して脱水を行うが、これは、pH4未
満、又は、pH8を越えると、乾燥時にコラーゲンの加
水分解が起こり易くなる為で、さらに、得られたコラー
ゲン粉末が酸性又はアルカリ性となる為、これを合成樹
脂等と混合した場合に樹脂の加水分解が起こり易くなり
、製品物性を著しく損なう為である。
[0018] The dehydration treatment is carried out using a conventional centrifuge, filter press, screw press, etc., in order to lower the moisture content of the collagen aggregates obtained during the tanning treatment and to facilitate drying. . At this time, dehydration is performed by adjusting the pH to a range of pH 4 to 8. This is because if the pH is less than 4 or exceeds pH 8, hydrolysis of collagen tends to occur during drying. This is because collagen powder becomes acidic or alkaline, so when it is mixed with a synthetic resin, etc., the resin tends to be hydrolyzed, which significantly impairs the physical properties of the product.

【0019】尚、脱水時の安定化コラーゲン湿体の温度
に特に制限はないが、約70℃以上に加温すると、コラ
ーゲン湿体の凝集が起こり、保持している水分の一部を
吐き出し、脱水効率が上昇するので好ましい。但し、使
用したなめし剤の種類・量により決まるコラーゲン湿体
の熱変性温度以上への加温は、コラーゲンの加水分解を
引き起こすので避けなければならない。
[0019] There is no particular limit to the temperature of the stabilized collagen wet body during dehydration, but if it is heated to about 70°C or higher, the collagen wet body will coagulate, expel some of the retained water, and This is preferred because the dehydration efficiency increases. However, heating the collagen wet body above the heat denaturation temperature, which is determined by the type and amount of tanning agent used, must be avoided as this will cause collagen hydrolysis.

【0020】乾燥処理は、脱水処理で水分率を下げて塊
状となったコラーゲン湿体の水分率を更に下げて粉砕処
理を容易にする目的で、流動式、棚段式、ベルト式、パ
ドル式、スプレー式等の乾燥機を用いて通常の方法によ
りなされる。粉砕処理をするためには、水分率は10重
量%以下とすることが好ましい。
[0020] The drying process is performed using a fluid type, tray type, belt type, or paddle type in order to further reduce the moisture content of the wet collagen that has become lumpy due to the dehydration process and to facilitate the pulverization process. This is done by a conventional method using a dryer such as a spray type dryer. In order to carry out the pulverization treatment, the moisture content is preferably 10% by weight or less.

【0021】粉砕処理は、乾燥処理で得られたコラーゲ
ン塊を、塗料、人工皮革、成形材料等の実用に適した粒
子径とする目的で通常のジェットミル、ハンマーミル、
ボールミル等を使用してなされる。生成する粉末の性質
はこれを使用する目的により異なるが、一般には、粒度
は正規分布に近く、中間径が4〜25μm、粒子径40
μm以下が85%以上とするのが好ましい。(粉末の粒
子径及び粒径分布はコールターカウンター法により測定
した。)このようにして製造されるコラーゲン粉末は、
精製裸皮をなめし処理して製造した皮革を単に粉砕して
得られる皮革粉とは異なり、水中における粉砕処理によ
りコラーゲン繊維束が一旦完全に解繊或は溶解された後
に、なめし処理により凝集されて構成されるので、粗密
で複雑な空隙の多い構造となり、その為吸水度が高く、
見掛けかさ比重が低くなるのが特徴である。
[0021] The pulverization process is carried out using a conventional jet mill, hammer mill, or
This is done using a ball mill, etc. The properties of the powder produced vary depending on the purpose for which it is used, but in general, the particle size is close to a normal distribution, with a median diameter of 4 to 25 μm, and a particle size of 40 μm.
It is preferable that 85% or more be less than μm. (The particle size and particle size distribution of the powder were measured by the Coulter counter method.) The collagen powder produced in this way is
Unlike leather powder obtained by simply pulverizing leather produced by tanning purified bare skin, collagen fiber bundles are completely defibrated or dissolved by pulverization in water and then aggregated by tanning. Because it is made up of
It is characterized by a low apparent bulk specific gravity.

【0022】尚、上記条件中、湿式粉砕及びなめし処理
をコラーゲンが析出している状態で行った場合、吸水度
が高く、さらに、吸油度(JIS K 5101)が特
に高いコラーゲン粉末が得られる。コラーゲン粉末の吸
油度が低いと、合成樹脂等と混合して塗料・人工皮革・
成形材料に使用する場合、樹脂またはその溶液中におい
てコラーゲン粉末の真比重と樹脂溶液の比重との差によ
りコラーゲン粉末が沈降してケーキ状に固まり再分散が
不可能になるなど分散安定性に乏しくなる問題点があり
好ましくなく、吸油度の高いコラーゲン粉末は上記の点
でも特に有用である。
[0022] If wet milling and tanning are performed under the above conditions while collagen is precipitated, a collagen powder with high water absorption and particularly high oil absorption (JIS K 5101) can be obtained. If the oil absorption of collagen powder is low, it may be mixed with synthetic resins etc. and used in paints, artificial leather, etc.
When used as a molding material, due to the difference between the true specific gravity of the collagen powder and the specific gravity of the resin solution in the resin or its solution, the collagen powder will settle and solidify into a cake, making redispersion impossible, resulting in poor dispersion stability. Collagen powder with high oil absorption is particularly useful in the above points as well.

【0023】又、コラーゲンが析出している状態とは、
コラーゲンが水に溶解・膨潤しておらず、繊維状に沈降
している、又は、スラリーとなっている状態であり、析
出形態は規則的集合体及びアモルファス集合体のいずれ
でも良い。さらに、コラーゲンが析出している状態とす
るには、pHをコラーゲンの等電点以上に調整するか、
或は、塩化ナトリウム、硫酸ナトリウム等の塩類によっ
てコラーゲンを塩析することによって行われるが、この
2つの方法を併用しても差し支えない。
[0023] Also, the state in which collagen is precipitated is
Collagen is not dissolved or swollen in water, but is precipitated in the form of fibers, or is in the form of a slurry, and the precipitation form may be either regular aggregates or amorphous aggregates. Furthermore, in order to obtain a state in which collagen is precipitated, the pH should be adjusted to a value higher than the isoelectric point of collagen, or
Alternatively, collagen may be salted out using salts such as sodium chloride or sodium sulfate, but these two methods may be used in combination.

【0024】尚、ここで言うコラーゲンの等電点とは、
コラーゲン中に存在する+(プラス)の電荷と−(マイ
ナス)の電荷がちょうど相殺され、コラーゲンが見かけ
上、無電荷となるpH値のことであり、コラーゲンの場
合、精製処理の方法によって異なるが、動物皮をアルカ
リ処理して精製した場合には、一般にpH4〜5が等電
点pHとなる。pHを等電点以上に調整するとは、pH
を4〜5より高くすることである。
[0024] The isoelectric point of collagen mentioned here is
This is the pH value at which the + (plus) charges and - (minus) charges that exist in collagen are exactly canceled out, and the collagen appears to be uncharged. When animal skin is purified by alkali treatment, the isoelectric point pH is generally between pH 4 and 5. Adjusting the pH above the isoelectric point means adjusting the pH
is higher than 4 to 5.

【0025】[0025]

【作用】本発明の方法により製造されるコラーゲン粉末
は、特にポリウレタン樹脂、ポリエステル樹脂、ポリア
クリル樹脂、ポリ塩化ビニル樹脂等の合成樹脂をベース
とする塗料、人工皮革、成形材料に混合して使用するの
に有用であり、それぞれ天然皮革様の外観、感触、並び
に吸放湿性等の性能をもった塗料、人工皮革、成形材料
を得ることが出来る。
[Action] Collagen powder produced by the method of the present invention can be mixed with paints, artificial leathers, and molding materials based on synthetic resins such as polyurethane resins, polyester resins, polyacrylic resins, and polyvinyl chloride resins. It is possible to obtain paints, artificial leathers, and molding materials that have natural leather-like appearance, feel, and performance such as moisture absorption and desorption properties.

【0026】例えば、塗料においては、代表例として、
ポリウレタン樹脂塗料をベースにコラーゲン粉末を塗料
固形分100部に対し30〜200重量部を加えてよく
分散し、必要に応じて溶剤を加えて適当な濃度にするこ
とにより調製され、これをスプレーガン、コーター等に
より塗工して使用される。人工皮革においては、代表例
として、ポリウレタン樹脂100重量部に対しコラーゲ
ン粉末を30〜200重量部加えて混練し、これをポリ
塩化ビニルシートや不織布シートに貼合わせて使用され
る。また成形材料は、代表例として、人工皮革と同様に
ポリウレタン樹脂100重量部に対し30〜200重量
部を加えて混練し、押し出し機等により成形されて使用
される。これらはいずれも天然皮革と同様のすぐれた外
観、感触、並びに吸放湿性等の性能を持つ。本発明を以
下の実施例により更に詳しく説明する。
For example, in paints, as a typical example,
It is prepared by adding 30 to 200 parts by weight of collagen powder to 100 parts of the solid content of the paint based on a polyurethane resin paint, dispersing it well, and adding a solvent as necessary to make an appropriate concentration. It is used by coating with a coater, etc. In the case of artificial leather, as a typical example, 30 to 200 parts by weight of collagen powder is added to 100 parts by weight of polyurethane resin and kneaded, and this is used by laminating it on a polyvinyl chloride sheet or a nonwoven fabric sheet. The molding material is typically used by adding 30 to 200 parts by weight to 100 parts by weight of a polyurethane resin, kneading the mixture, and molding it using an extruder or the like, similar to artificial leather. All of these have excellent appearance, feel, moisture absorption and desorption properties similar to natural leather. The present invention will be explained in more detail by the following examples.

【0027】[0027]

【実施例】実施例11)精製及び湿式粉砕処理石灰によ
るアルカリ処理後水洗された牛の床皮500重量部(乾
量は100重量部、以下、重量部は部と省略する)を、
重炭酸ナトリウムによりpHを8.1に調整した下記の
処理液に漬け、 パパイン                     
   0.60部パンクレアチン          
        0.15部L−グルタミン酸    
            0.35部コンドロイチン硫
酸ナトリウム    0.003 部L−酒石酸水素カ
リウム          0.35部トリトン  X
−100  *        0.50部水    
                         
 5000部*;非イオン性界面活性剤(ポリオキシエ
チレン−アルキルフェニルエ−テルの商品名)家庭用洗
濯機内にて室温下で12時間かき混ぜて夾雑物を除去し
、更に水洗した後、乳酸を添加してpHを3.5に調整
して得られた精製コラーゲン組織を肉挽機を用いてミン
チ状とし、これを、原床皮の乾量の重量濃度が3.5%
となるように水で希釈し(pH4.0)、製紙用叩解機
を用いて水温25℃で湿式粉砕した。
[Example] Example 11) Purification and wet pulverization treatment 500 parts by weight of cow hide (dry amount is 100 parts by weight, hereinafter abbreviated as parts), which was washed with water after being treated with alkali with lime,
Papain was soaked in the following treatment solution whose pH was adjusted to 8.1 with sodium bicarbonate.
0.60 parts pancreatin
0.15 parts L-glutamic acid
0.35 part Sodium chondroitin sulfate 0.003 part L-potassium hydrogen tartrate 0.35 part Triton X
-100 * 0.50 part water

5,000 parts*; Nonionic surfactant (trade name of polyoxyethylene-alkylphenyl ether) Stir in a household washing machine at room temperature for 12 hours to remove impurities, then wash with water, and remove lactic acid. The purified collagen tissue obtained by adjusting the pH to 3.5 was minced using a meat grinder, and the dry weight concentration of the original bed skin was 3.5%.
The mixture was diluted with water (pH 4.0) and wet-pulverized using a paper mill at a water temperature of 25°C.

【0028】2)なめし処理湿式粉砕処理後、製紙用叩
解機内(pH3.8)で下記のなめし剤を順次加えて、
塩基性硫酸アルミニウム      4.5 部硫酸ジ
ルコニル              2.5 部なめ
し処理をし、安定化コラーゲン湿体を得た。
2) Tanning treatment After the wet grinding treatment, the following tanning agents were sequentially added in a paper beating machine (pH 3.8).
Basic aluminum sulfate 4.5 parts zirconyl sulfate 2.5 parts Tanning treatment was carried out to obtain a stabilized collagen wet body.

【0029】3)脱水、乾燥、粉砕処理なめし処理して
得られた安定化コラーゲン湿体を、重炭酸ナトリウムに
てpHを6.0に調整した後、スクリュウプレス脱水機
を用いて水分率が67重量%になるまで脱水した後、熱
風棚段式乾燥機を用いて乾燥して、水分率を9.5重量
%とし、更に、ボ−ルミルを用いて粉砕し表1に示す物
性値を持ったコラーゲン粉末とした。
3) Dehydration, drying, and pulverization After adjusting the pH of the stabilized collagen wet body obtained by tanning to 6.0 with sodium bicarbonate, the moisture content was reduced using a screw press dehydrator. After dehydrating to 67% by weight, it was dried using a hot air tray dryer to give a moisture content of 9.5% by weight, and then ground using a ball mill to obtain the physical properties shown in Table 1. It was made into collagen powder.

【0030】実施例2 1)精製および湿式粉砕処理石灰によりアルカリ処理後
水洗された牛の床皮を500部(乾量は100部)を、
硫酸アンモニウムによりpHを9.0に調整した下記の
処理液に漬け、 パパイン                    0
.55部パンクレアチン              
0.15部L−酒石酸水素カリウム      0.3
0部トリトン  X−100        0.50
部水                       
   5000部家庭用洗濯機内にて室温下で12時間
かき混ぜて夾雑物を除去し、更に水洗した後、乳酸を添
加してpHを4.0に調整して得られた精製コラーゲン
組織を肉挽機を用いてミンチ状とし、これを、原床皮の
乾量の重量濃度が6.0%となるように水で希釈し、更
に乳酸にてpHを3.2に調整して、回転刃解砕機を用
いて水温30℃で湿式粉砕した。
Example 2 1) Purification and Wet Grinding 500 parts (dry weight: 100 parts) of cow bedding skin that had been alkali treated with lime and washed with water were
Soaked in the following treatment solution whose pH was adjusted to 9.0 with ammonium sulfate, and papain 0
.. 55 parts pancreatin
0.15 parts L-potassium hydrogen tartrate 0.3
0 parts Triton X-100 0.50
Department water
5,000 copies were stirred in a household washing machine at room temperature for 12 hours to remove impurities, and after further washing with water, the purified collagen tissue obtained by adding lactic acid to adjust the pH to 4.0 was passed through a meat grinder. This was minced using water, diluted with water so that the weight concentration of the dry amount of raw hide was 6.0%, the pH was adjusted to 3.2 with lactic acid, and the mixture was decomposed with a rotary blade. Wet pulverization was performed using a pulverizer at a water temperature of 30°C.

【0031】2)なめし処理湿式粉砕処理後、家庭用ミ
キサー内(pH3.0)で下記のなめし剤を順次加えて
、 塩基性硫酸アルミニウム      2.5 部硫酸ジ
ルコニル              3.0 部なめ
し処理をし、安定化コラーゲン湿体を得た。
2) Tanning treatment After wet grinding, the following tanning agents were sequentially added in a household mixer (pH 3.0) to carry out tanning treatment using 2.5 parts of basic aluminum sulfate and 3.0 parts of zirconyl sulfate. A stabilized collagen wet body was obtained.

【0032】3)脱水、乾燥、粉砕処理なめし処理して
得られた安定化コラーゲン湿体を水酸化ナトリウムを用
いてpH7.0に調整した後、70℃まで昇温して遠心
脱水機を用いて水分率が65重量%になるまで脱水した
後、流動乾燥機を用いて乾燥して、水分率を5.0重量
%とし、更に、ジェットミルを用いて粉砕し表1に示す
物性値を持ったコラーゲン粉末とした。
3) Dehydration, drying, and pulverization The stabilized collagen wet body obtained through the tanning process was adjusted to pH 7.0 using sodium hydroxide, heated to 70°C, and then dried using a centrifugal dehydrator. After dehydration until the moisture content becomes 65% by weight, it is dried using a fluidized fluid dryer to reduce the moisture content to 5.0% by weight, and then pulverized using a jet mill to obtain the physical properties shown in Table 1. It was made into collagen powder.

【0033】実施例3(コラーゲン析出状態での湿式粉
砕・なめし処理)1)精製及び湿式粉砕処理石灰による
アルカリ処理後水洗された牛の床皮500部(乾量は1
00部)を、重炭酸ナトリウムによりpHを8.1に調
整した下記の処理液に漬け、 パパイン                     
   0.60部パンクレアチン          
        0.15部L−グルタミン酸    
            0.35部コンドロイチン硫
酸ナトリウム    0.003 部L−酒石酸水素カ
リウム          0.35部トリトン  X
−100            0.50部水   
                         
  5000部家庭用洗濯機内にて室温下で12時間か
き混ぜて夾雑物を除去し、更に水洗した後、乳酸を添加
してpHを4.0に調整して得られた精製コラーゲン組
織を肉挽機を用いてミンチ状とし、これを、原床皮の乾
量の重量濃度が12.5%となるように水で希釈し、重
炭酸ナトリウムにてpHを7.3に調整してコラーゲン
繊維を析出させ、製紙用叩解機を用いて水温20℃で湿
式粉砕した。
Example 3 (Wet grinding and tanning treatment in a state where collagen is precipitated) 1) Purification and wet grinding treatment 500 parts of cow bedding skin (dry weight: 1
00 parts) in the following treatment solution whose pH was adjusted to 8.1 with sodium bicarbonate, and papain
0.60 parts pancreatin
0.15 parts L-glutamic acid
0.35 part Sodium chondroitin sulfate 0.003 part L-potassium hydrogen tartrate 0.35 part Triton X
-100 0.50 part water

5,000 copies were stirred in a household washing machine at room temperature for 12 hours to remove impurities, and after further washing with water, the purified collagen tissue obtained by adding lactic acid to adjust the pH to 4.0 was passed through a meat grinder. This was minced using water, diluted with water so that the dry weight concentration of the original skin was 12.5%, and the pH was adjusted to 7.3 with sodium bicarbonate to extract collagen fibers. It was precipitated and wet-pulverized using a paper mill at a water temperature of 20°C.

【0034】2)なめし処理湿式粉砕処理後、家庭用ミ
キサー内(pH6.7)でコラーゲンが析出した状態で
下記のなめし剤を順次加えて、 塩基性硫酸アルミニウム      4.5 部硫酸ジ
ルコニル              2.5 部なめ
し処理をし、安定化コラーゲン湿体を得た。
2) Tanning After wet grinding, the following tanning agents were sequentially added in a household mixer (pH 6.7) with collagen precipitated, and 4.5 parts of basic aluminum sulfate and 2.5 parts of zirconyl sulfate were added. A stabilized collagen wet material was obtained by partial tanning.

【0035】3)脱水、乾燥、粉砕処理なめし処理して
得られた安定化コラーゲン湿体をpH5.3でスクリュ
ウプレス脱水機を用いて水分率が69重量%になるまで
脱水した後、熱風棚段式乾燥機を用いて乾燥して、水分
率を1.2重量%とし、更に、ハンマーミルを用いて粉
砕し表1に示す物性値を持ったコラーゲン粉末とした。
3) Dehydration, drying, and pulverization The stabilized collagen wet body obtained through the tanning process was dehydrated at pH 5.3 using a screw press dehydrator until the moisture content reached 69% by weight, and then heated in a hot air rack. It was dried using a stage dryer to have a moisture content of 1.2% by weight, and then ground using a hammer mill to obtain collagen powder having the physical properties shown in Table 1.

【0036】比較例1(湿式粉砕を低コラーゲン濃度で
する方法) 1)精製および湿式粉砕処理湿式粉砕時の濃度を0.7
重量%とした以外は実施例1と同様にして、精製および
湿式粉砕した。 2)なめし処理湿式粉砕処理後、実施例1と同様になめ
し処理をし、安定化コラーゲン湿体を得た。3)脱水、
乾燥、粉砕処理 なめし処理して得られた安定化コラーゲン湿体を水酸化
ナトリウムを用いてpH6.3に調整した後、スクリュ
ウプレス脱水機を用いて水分率が72重量%になるまで
脱水し、熱風棚段式乾燥機を用いて乾燥して、水分率を
9.0重量%とし、更に、ジェットミルを用いて粉砕し
表1に示す物性値を持ったコラーゲン粉末とした。
Comparative Example 1 (method of wet pulverization with low collagen concentration) 1) Purification and wet pulverization treatment The concentration during wet pulverization was 0.7
Purification and wet pulverization were carried out in the same manner as in Example 1 except that the weight % was used. 2) Tanning Treatment After the wet grinding treatment, tanning treatment was performed in the same manner as in Example 1 to obtain a stabilized collagen wet body. 3) Dehydration;
The stabilized collagen wet body obtained by drying, crushing and tanning was adjusted to pH 6.3 using sodium hydroxide, and then dehydrated using a screw press dehydrator until the moisture content reached 72% by weight. It was dried using a hot air tray dryer to have a moisture content of 9.0% by weight, and then ground using a jet mill to obtain collagen powder having the physical properties shown in Table 1.

【0037】比較例2(皮革屑を粉砕する方法)通常の
クロムなめしをした皮革屑を細断後、加熱水蒸気により
オートクレーブ内で3時間110℃に加熱、膨潤し、実
施例1と同様に乾燥、粉砕して表1に示す物性値を持っ
た皮革紛とした。
Comparative Example 2 (Method of Grinding Leather Scraps) Normal chrome-tanned leather scraps were shredded, heated to 110°C for 3 hours in an autoclave with heated steam, swollen, and dried in the same manner as in Example 1. The powder was ground into leather powder having the physical properties shown in Table 1.

【0038】比較例3(繊維束分散物を有機なめし剤で
処理する方法)1)精製および粗分散処理石灰によるア
ルカリ処理後水洗された牛の床皮500部(乾量は10
0部)を、硫酸アンモニウムによりpHを9.0に調整
し、下記の処理液に漬け、 パパイン                    0
.55部パンクレアチン              
0.15部L−酒石酸水素カリウム      0.3
0部トリトン  X−100        0.50
部水                       
   5000部家庭用洗濯機内にて室温下で12時間
かき混ぜて夾雑物を除去し、更に水洗した後、乳酸を添
加してpHを5.0に調整して得られた精製コラーゲン
組織を肉挽機を用いてミンチ状とし、更にディスパース
ミルを用いて粗分散し、これを、原床皮の乾量の重量濃
度が4.0%となるように15重量%硫酸ナトリウム水
溶液で希釈し、更に炭酸ナトリウムにてpHを8.5に
調整して粗分散物とした。
Comparative Example 3 (Method of treating a fiber bundle dispersion with an organic tanning agent) 1) Purification and coarse dispersion treatment 500 parts of cow's bedding skin (dry amount: 10
0 parts) was adjusted to pH 9.0 with ammonium sulfate, immersed in the following treatment solution, and papain 0
.. 55 parts pancreatin
0.15 parts L-potassium hydrogen tartrate 0.3
0 parts Triton X-100 0.50
Department water
5,000 copies were stirred in a household washing machine at room temperature for 12 hours to remove impurities, further washed with water, and the resulting purified collagen tissue was added to a meat grinder to adjust the pH to 5.0. This was ground into minced pieces using a dispersion mill, and this was then diluted with a 15% by weight aqueous sodium sulfate solution so that the weight concentration of the dry weight of the raw skin was 4.0%, and further mixed with carbonate. The pH was adjusted to 8.5 with sodium to obtain a crude dispersion.

【0039】2)なめし処理粗分散されたコラーゲン繊
維束分散物にグルタルアルデヒド0.5gを添加して5
時間なめし処理をし、水洗後全量を5000部(分散物
濃度として2.0%)とした。3)分散処理なめし処理
された分散物を塩酸によりpHを5.0に調整後、ディ
スパースミルを用いて再分散し、コラーゲン繊維分散物
を得た。
2) Tanning treatment 0.5 g of glutaraldehyde was added to the roughly dispersed collagen fiber bundle dispersion.
A time tanning treatment was carried out, and after washing with water, the total amount was 5000 parts (dispersion concentration: 2.0%). 3) Dispersion Treatment The pH of the tanned dispersion was adjusted to 5.0 with hydrochloric acid, and then redispersed using a dispersion mill to obtain a collagen fiber dispersion.

【0040】4)脱水、乾燥、粉砕処理再分散して得ら
れたコラーゲン繊維分散物をスクリュウプレス脱水機を
用いて水分率が69重量%になるまで脱水した後、熱風
棚段式乾燥機を用いて乾燥して、水分率を9.5重量%
とし、更に、ハンマーミルを用いて粉砕し表1に示す物
性値を持ったコラーゲン粉末とした。
4) Dehydration, drying, and pulverization The collagen fiber dispersion obtained by redispersion was dehydrated using a screw press dehydrator until the moisture content reached 69% by weight, and then dried using a hot air tray dryer. and dried to a moisture content of 9.5% by weight.
This was further ground using a hammer mill to obtain collagen powder having the physical properties shown in Table 1.

【0041】応用試験例実施例1、2及び3、比較例2
及び3において得られたコラーゲン粉末または皮革粉そ
れぞれを用いて、下記のようにA.塗料、B.人工皮革
、C.成形材料に応用し、表1に示された項目の試験を
実施して表1の結果を得た。しかし比較例1の粉末は長
繊維状物の割合が多いので応用試験に供することが出来
なかった。
Application test examples Examples 1, 2 and 3, comparative example 2
Using the collagen powder or leather powder obtained in A. and 3, respectively, A. Paint, B. Artificial leather, C. The results shown in Table 1 were obtained by applying the test to molding materials and conducting tests on the items shown in Table 1. However, since the powder of Comparative Example 1 had a high proportion of long fibers, it could not be used for application tests.

【0042】A.塗料ポリウレタン樹脂100部を酢酸
エチル200部に溶解した樹脂溶液にコラーゲン粉末5
0部を加え、よく分散してクリヤー塗料とした。この塗
料をスプレーガンを用いて、乾燥後の塗膜層の厚さが5
0μmになるように透明のポリカーボネート板の表面に
塗布して乾燥した。
A. Add 5 parts of collagen powder to a resin solution prepared by dissolving 100 parts of paint polyurethane resin in 200 parts of ethyl acetate.
0 parts was added and dispersed well to obtain a clear paint. This paint was applied using a spray gun until the thickness of the paint layer after drying was 5.
It was coated on the surface of a transparent polycarbonate plate to a thickness of 0 μm and dried.

【0043】B.人工皮革ポリウレタン樹脂100部を
酢酸エチル200部に溶解した樹脂溶液にコラーゲン粉
末50部及びカーボンブラック8部を加え、よく分散し
て表面処理剤とした。この処理剤をグラビアコーターを
用いて、乾燥後の塗膜層の厚さが30μmになるように
離型紙の表面に塗布して乾燥し、この表面に接着層を設
けて不織布シートに貼付けて人工皮革とした。
B. 50 parts of collagen powder and 8 parts of carbon black were added to a resin solution in which 100 parts of artificial leather polyurethane resin was dissolved in 200 parts of ethyl acetate, and the mixture was well dispersed to obtain a surface treatment agent. This treatment agent is applied to the surface of release paper using a gravure coater so that the thickness of the coating layer after drying is 30 μm, dried, an adhesive layer is provided on this surface, and it is attached to a nonwoven fabric sheet to create an artificial Made of leather.

【0044】C.成形材料発泡ポリウレタン樹脂100
部にコラーゲン粉末50部及びカーボンブラック8部を
加え、よく混練りした後、溶融成形機によりシート状に
溶融成形し、成形物シートとした。
C. Molding material polyurethane foam resin 100
After adding 50 parts of collagen powder and 8 parts of carbon black to the mixture and thoroughly kneading the mixture, the mixture was melt-molded into a sheet using a melt-molding machine to obtain a molded product sheet.

【0045】[0045]

【表1】[Table 1]

【0046】表1の結果から、本発明の方法により製造
されたコラーゲン粉末は、従来の方法により製造された
コラーゲン粉末と比較して、いずれの基材への使用によ
っても、外観、感触、吸放湿性等の性能の改質性が高い
ことが示されている。又、実施例3の粉末を用いて調整
したクリヤー塗料は、他のいずれよりも分散安定性に優
れていた。
From the results in Table 1, it can be seen that the collagen powder produced by the method of the present invention has improved appearance, feel, and absorbency when used on any base material, compared to collagen powder produced by the conventional method. It has been shown that it has a high ability to improve performance such as moisture release. Furthermore, the clear paint prepared using the powder of Example 3 had better dispersion stability than any of the others.

【0046】[0046]

【発明の効果】本発明により、コラーゲン粉末が製造で
き、この粉末を用いて塗料、人工皮革、成形材料いずれ
の応用によっても外観、感触、吸放湿性等の性能の優れ
た材料が得られる。
Effects of the Invention According to the present invention, collagen powder can be produced, and this powder can be used to produce materials with excellent performance in terms of appearance, feel, moisture absorption and desorption properties, etc. when applied to paints, artificial leathers, and molding materials.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】  コラーゲンを主成分とする精製された
動物組織を、水中において、コラーゲン濃度1〜30重
量%、水温37℃以下及びpH2〜8の範囲で湿式粉砕
した後、多価金属なめし剤を用いて、pH2〜7の範囲
でなめし処理を行い安定化コラーゲン湿体を得、次いで
、pH4〜8の範囲にて脱水し、さらに乾燥及び粉砕を
行って粉末とすることを特徴とするコラーゲン粉末の製
造方法。
Claim 1: Purified animal tissue containing collagen as a main component is wet-pulverized in water at a collagen concentration of 1 to 30% by weight, a water temperature of 37°C or less, and a pH of 2 to 8, and then processed into a polyvalent metal tanning agent. A stabilized collagen wet body is obtained by tanning the collagen at a pH range of 2 to 7, followed by dehydration at a pH range of 4 to 8, and further drying and pulverization to form a powder. Method of manufacturing powder.
【請求項2】  pHをコラーゲンの等電点以上に調整
するか、塩類によってコラーゲンを塩析することにより
、コラーゲンが析出している状態で、湿式粉砕及びなめ
し処理を行う請求項1のコラーゲン粉末の製造方法。
2. The collagen powder according to claim 1, wherein the collagen powder is wet-milled and tanned in a state in which collagen is precipitated by adjusting the pH to a value higher than the isoelectric point of collagen or by salting out the collagen with salts. manufacturing method.
JP10362491A 1990-08-08 1991-04-10 Production of collagen powder Pending JPH04226538A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10362491A JPH04226538A (en) 1990-08-08 1991-04-10 Production of collagen powder

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2-211416 1990-08-08
JP21141690 1990-08-08
JP10362491A JPH04226538A (en) 1990-08-08 1991-04-10 Production of collagen powder

Publications (1)

Publication Number Publication Date
JPH04226538A true JPH04226538A (en) 1992-08-17

Family

ID=26444245

Family Applications (1)

Application Number Title Priority Date Filing Date
JP10362491A Pending JPH04226538A (en) 1990-08-08 1991-04-10 Production of collagen powder

Country Status (1)

Country Link
JP (1) JPH04226538A (en)

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JP2006016381A (en) * 2004-06-04 2006-01-19 Katsumi Koide Method for processing collagen
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006016381A (en) * 2004-06-04 2006-01-19 Katsumi Koide Method for processing collagen
US8153176B2 (en) 2006-03-13 2012-04-10 Naturin Gmbh & Co. Biodegradable protein based thermoset compositions, preparation methods and applications thereof
WO2007142097A1 (en) * 2006-06-02 2007-12-13 Kaneka Corporation Resin powder containing aluminum salt, process for production of the same, and resin composition, phosphorous adsorbent, antibacterial agent or antifungal agent comprising the same
JP5426879B2 (en) * 2006-06-02 2014-02-26 株式会社カネカ Phosphorous adsorbents, antibacterial agents and antifungal agents containing resin powder containing aluminum salt
JP2009030009A (en) * 2007-06-27 2009-02-12 Kaneka Corp Coating agent, filler for coating film, and coated sheet
WO2009066635A1 (en) * 2007-11-21 2009-05-28 Kaneka Corporation Permeable film and method for producing the same
JP2009127163A (en) * 2007-11-27 2009-06-11 Kaneka Corp Composition imparting antiviral property and method for producing antiviral product by using the composition
JP2010077202A (en) * 2008-09-24 2010-04-08 Kaneka Corp Moisture-permeable film, coating agent, filler for coating film, and coated sheet
WO2012015055A1 (en) * 2010-07-30 2012-02-02 株式会社ニッピ Collagen powder and/or collagen-derived powder, and production method for same
JP5845181B2 (en) * 2010-07-30 2016-01-20 株式会社ニッピ Method for producing collagen powder and / or collagen derivative powder
JP2016028093A (en) * 2010-07-30 2016-02-25 株式会社ニッピ Collagen powder and/or collagen derivative powder
US9617298B2 (en) 2010-07-30 2017-04-11 Nippi, Incorporated Collagen powder and/or collagen-derived powder, and production method for the same

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