JPH05179300A - Production of reptile leather - Google Patents
Production of reptile leatherInfo
- Publication number
- JPH05179300A JPH05179300A JP4018304A JP1830492A JPH05179300A JP H05179300 A JPH05179300 A JP H05179300A JP 4018304 A JP4018304 A JP 4018304A JP 1830492 A JP1830492 A JP 1830492A JP H05179300 A JPH05179300 A JP H05179300A
- Authority
- JP
- Japan
- Prior art keywords
- leather
- treatment
- tanning
- dyeing
- producing
- 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.)
- Granted
Links
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】この発明は、爬虫類皮革のうちモ
ニター種のリザ−ドおよびカロンスネークの皮を用いて
柔軟性、耐ウォツシャブル性、防滑性に優れた革の製造
方法に関し、詳しくは陸や海での広範囲にわたる各種ス
ポ−ツ用、ワーキング用、服飾用、手袋用の皮革として
特徴を有する製造方法を提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing leather which is excellent in flexibility, washable resistance, and slip resistance, using lizard leather of monitor species of reptile leather and leather of Karon Snake. The present invention provides a manufacturing method characterized by being used as leather for a wide variety of sports, working, clothing, and gloves at sea.
【0002】[0002]
【従来の技術】従来一般に小牛革、鹿革、羊革、山羊革
その他の小動物革が衣料、手袋、鞄、靴等に多く利用さ
れ爬虫類革は主として鞄物、ベルト、紙幣入れ等装飾的
な物品に多用されていることはよく知られているところ
である。その理由は、爬虫類革は本質的に牛、馬、鹿革
等にくらべてコラ−ゲン繊維の絡みが粗であるにも拘わ
らず製品が硬くなる傾向があり、手袋用革などには着目
されなかったのが実情である。2. Description of the Related Art Generally, small cow leather, deer leather, sheep leather, goat leather and other small animal leather have been widely used for clothing, gloves, bags, shoes and the like, and reptile leather is mainly used for decorative items such as bags, belts and bill holders. It is well known that it is widely used in articles. The reason for this is that reptile leather tends to be harder in comparison with cows, horses, deer leather, etc., although the entanglement of collagen fibers is essentially coarse, and attention is paid to leather for gloves. The reality is that there was no such thing.
【0003】しかしながら、カロン皮(ヤスリヘビ亜
科”アクロチョウダイナ”に属し一般名カロンとして業
界では知られており東南アジヤのジャワに多く棲息する
川へびの一種)についてはDASLEDER 197
4.1 25巻 No1 第12、13頁、およびCh
emistry and technology of
novelty leather 1974.7 第2
6頁に、カロン皮は特種なもので衣料用革または手袋用
革として重要である、とあり、かなり古くから着目され
ていた事実はある。また、モニター種のリザ−ドについ
ても東南アジヤ方面で入手できる原料皮として皮革業界
では周知のものである。 しかし、それら従来の方法で
製造されたカロン革は、手袋に用いた場合柔軟性と水濡
れにたいする抵抗性いわば耐ウォツシャブル性、防滑性
に欠け、この発明で実施するところの上記欠点を改良す
るための技術に関しては何ら詳細な教示はない。However, regarding the karon skin (a kind of river snake which belongs to the subfamily "Acrochodina" belonging to the filed filed, known in the industry as the general name Karon and often inhabiting Java in Southeast Asia), it is DASLEDER 197.
4.1 Volume 25 No1 pages 12, 13 and Ch
emissary and technology of
novelty leader 1974. 7 part 2
On page 6, it is said that caron leather is a special kind and is important as leather for clothing or leather for gloves. Also, the monitor-type lizard is well known in the leather industry as a raw material leather that can be obtained from Southeast Asia. However, the Karon leather produced by those conventional methods lacks flexibility and resistance to water wetting when used in gloves, so-called washable resistance, and slip resistance, and is intended to improve the above-mentioned drawbacks of the present invention. There is no detailed teaching regarding the technology of.
【0004】[0004]
【発明が解決しようとする課題】従来、普通に行われて
いた製革技術即ち、漂白工程における過マンガン酸カリ
と重亜硫酸ソ−ダによる方法では爾後の処理工程との関
連に於いて強度が低下し柔軟性に欠け、また、これらス
キンの持っている縞やまだら模様の除去が十分でなく、
手袋として好ましくない結果をもたらした。ゴルフ、マ
リン、テニス、バッティング、マウンテンバイク等の各
種スポーツ用、ドライバ−、ワーキング、服飾用等全分
野の手袋を対象とし、それらに要求される具備すべき条
件としては強度(抗張力、引裂強度、銀面の摩擦強
度)、耐すべり性、柔軟性、耐洗濯性の高い事が必要で
あり、この点カロン皮およびリザ−ド(モニター種)皮
は銀面に特有のWart(いぼ)様の突起を有しており
上記の条件を満たし高級品として趣向される。In the conventional leathermaking technique, that is, the method of using potassium permanganate and sodium bisulfite in the bleaching process, the strength is lowered in relation to the subsequent processing step. Lacks flexibility, and the removal of streaks and mottled patterns that these skins have is not enough,
It gave unfavorable results for gloves. Targeting gloves for all fields such as golf, marine, tennis, batting, mountain biking and other sports, drivers, working, clothing, etc., the required conditions must be strength (tensile strength, tear strength, It is necessary to have high frictional strength (silver surface), slip resistance, flexibility, and washing resistance. In this respect, the caron skin and the reserve (monitor type) skin have a Wart-like appearance peculiar to the silver surface. It has protrusions and satisfies the above conditions, and is intended as a luxury product.
【0005】また、なめし剤についても一般の牛皮や鹿
皮にたいして植物タンニンなめし剤、クロムなめし剤、
アルデヒドなめし剤、ジルコニウム、アルミニウム、油
等のなめし剤を用いているが、モニター種のリザードや
カロンスネークの皮を従来の方法で加工した場合製品が
硬くなり、物を握ったときフイット感に欠け汗に対して
弱く、全体的に引張強度、引裂強度、柔軟性、耐水性に
乏しく洗濯による劣化が著しく、特にスポーツ関連用品
として好適でない。染色剤についても、従来普通に用い
られている直接染料、酸性染料、塩基性染料、媒染染料
等は諸種の堅牢度が十分でなく、耐ウォツシャブル性に
問題がある。As for the tanning agent, plant tannin tanning agents, chromium tanning agents, and tanning agents for common cowhide and deer hide,
Aldehyde tanning agents, zirconium, aluminum, oils and other tanning agents are used, but when the monitor type lizard and Karon snake skin are processed by the conventional method, the product becomes hard and lacks a fit feeling when gripping something. It is weak against sweat, has poor tensile strength, tear strength, flexibility, and water resistance as a whole and is significantly deteriorated by washing, and is not particularly suitable for sports-related products. As for the dyeing agent, direct dyes, acid dyes, basic dyes, mordant dyes and the like which have been conventionally used are not sufficiently fast in various types and have a problem in washability.
【0006】つぎに、最も重要な課題である手袋革とし
ての永久柔軟性、耐汗性に与える抵抗性即ち水濡れによ
りぬるぬるしないこと、乾いてからも硬くならないこ
と、滑り抵抗性が永続すること等の性質は製品として最
も要求されるところである。従来加脂仕上げには、牛
脂、牛脚油、羊脂、抹香鯨油、サメ油や植物性のヒマシ
油、ヤシ油、オリ−ブ油等をアニオン、カチオン、ノニ
オン活性剤で乳化してこれを革内部に浸透充填せしめて
柔軟性を付与させている。これらは、親水性の活性成分
が革に残存し経時的に平行移行現象を起こしたり、ウエ
ットやドライクリ−ニングの反復により脱落や変質によ
り革の柔軟性と機械的強度を著しく阻害して好ましくな
く、最近ではこの加脂剤として長鎖アルキル基を有する
アミノ酸や、炭素数12〜14のアルキル基置換したベタイ
ン誘導体を用いる方法などが提唱されている。しかしな
がら、ウエットまたはドライクリ−ニングの反覆にたい
して、不変のしなやかさと、ぬるぬる感やすべり感のな
い手袋としての可酷条件下での耐性は不十分で、加えて
それらは牛、鹿、羊の革など一般の皮革に対してのもの
であって、モニター種のリザードやカロンスネーク革の
如き特殊なものの用途に関して教示を与えるものではな
い。Next, the most important issues are permanent flexibility as gloves leather, resistance to perspiration resistance, that is, not to be slimy due to water wetting, not to be hard even after drying, and to have permanent slip resistance. Properties such as are most required as products. Conventionally, for fattening finish, emulsify beef tallow, beef leg oil, sheep's fat, matcha whale oil, shark oil, castor oil of vegetable origin, coconut oil, olive oil, etc. with anion, cation, nonionic activator. The inside of the leather is permeated and filled to give it flexibility. These are not preferable because the hydrophilic active ingredient remains in the leather and causes a parallel shift phenomenon with time, or the softness and mechanical strength of the leather is significantly impaired due to loss or deterioration due to repeated wet and dry cleaning. Recently, a method has been proposed in which an amino acid having a long-chain alkyl group or a betaine derivative substituted with an alkyl group having 12 to 14 carbon atoms is used as the greasing agent. However, they do not have the same suppleness as wet or dry-cleaning, and they do not have sufficient resistance under the severe conditions as slimy and non-slip gloves, and in addition, they are used for cow, deer, sheep leather, etc. It is intended for general leather and does not give any teaching as to the use of special things such as monitor-type lizards or Karon snake leather.
【0007】[0007]
【課題を解決するための手段】この発明の、最も重要と
するところは加脂仕上げ工程において加脂剤としては従
来使用されている動物性または植物性の油脂にかえて、
特定の疎水性高分子柔軟剤と高沸点極性溶剤を併用する
ところにある。勿論、適用方法としては、四種類に一部
水を添加して水中油滴型エマルジョン形態で革に適用し
革組織内部に均一に浸透させ、乾燥中に油中水滴型とな
り、更に疎水性柔軟剤として革に充填される。また、一
部は革のクロムに配位して親水基を失い永久疎水性を発
揮し、革の表面の突起を形成する内部コラ−ゲン組織間
にも十分沈着固定されて永く手袋表面の突起がへたるこ
とはなく、物を握ったときキチッとして滑ることがな
い。The most important point of the present invention is to replace the animal or vegetable fats and oils conventionally used as a fatliquoring agent in the fatliquoring process.
It is a combination of a specific hydrophobic polymer softener and a high boiling point polar solvent. Of course, as an application method, some water is added to four types and it is applied to leather in the form of oil-in-water emulsion so that it penetrates evenly inside the leather tissue and becomes a water-in-oil type during drying, and it is more hydrophobic and flexible. Filled in leather as an agent. In addition, some of them are coordinated with the chrome of leather to lose their hydrophilic groups and exhibit permanent hydrophobicity, and they are also sufficiently deposited and fixed between the internal collagen tissues that form protrusions on the surface of the leather, and the protrusions on the surface of the glove for a long time. There is no sagging, and when you grasp something, you do not slip tightly.
【0008】然も革のコラ−ゲン繊維束間に沈着したミ
クロンオ−ダ−の微粒子は、潤滑緩衝的役割を果たし、
手袋として永く柔軟性を保ち続け再度の水や汗の濡れに
も液切れがよく、例えばゴルフ手袋として用いた場合フ
アッション性もよくぬるぬる感もなく、よくクラブグリ
ップに密着して滑らない。この発明で用いる疎水性高分
子柔軟剤は長鎖ジアルキルスルフォコハク酸塩を主剤と
し、長鎖モノアルキル燐酸エステルおよび無水マレイン
酸ー不飽和オレフィンモノマーとの共重合体を、高沸点
で極性基を有するジエチレングリコールモノブチルエー
テルを溶剤として用い乾燥後は親水基が革中に残存する
ことなく好適な作用をもたらす。The micron-order fine particles deposited between the leather collagen fiber bundles play a role as a lubricating buffer.
As a glove, it retains its flexibility for a long time and has good drainage against re-wetting with water or sweat. For example, when it is used as a golf glove, it has good fashionability and no slimy feel, and it does not come in close contact with the club grip and slip. The hydrophobic polymer softener used in the present invention is mainly composed of a long-chain dialkylsulfosuccinate, and is a copolymer of a long-chain monoalkyl phosphate ester and a maleic anhydride-unsaturated olefin monomer at a high boiling point with a polar group. After using as a solvent diethylene glycol monobutyl ether having, the hydrophilic group does not remain in the leather and exhibits a suitable action.
【0009】つぎに漂白剤について、この発明で使用す
る亜塩素酸ソ−ダは、一般の繊維類や紙類の漂白剤とし
て用いられているものではあるが、生皮には多用されて
いないのが現状であリ、この発明では、まづ亜塩素酸ソ
−ダで初段処理して後、過マンガン酸カリと重亜硫酸ソ
−ダで後段処理することにより他の工程との相関関係で
製品に対して前記問題点の改善に予想外の効果をもたら
した。小牛皮その他小動物皮の漂白は、一般的には5%
程度の過マンガン酸カリ液で30分ドラミングしたの
ち、12%の重亜硫酸ソーダ液で45分ほどドラミング
するか、または合成なめし剤(一般には芳香族系のナフ
タレン、アンスラセンなどの混合物をフォルムアルデヒ
ドなどで縮合してつくる)で白色化させる方法が多々と
られているが、生皮自体に斑や縞模様を有するリザード
やカロンスネークの皮は従来例によってはきれいには除
ききれず、この発明の如く二段の処理を行うことによっ
てそれらの欠点を改良すると共に、従来法の過マンガン
酸カリ−重亜硫酸法単独で行うより革の強度(抗張力、
引裂強度等)の低下を防ぎ、漂白操作を全うすることが
出来た。Regarding the bleaching agent, the sodium chlorite used in the present invention is used as a bleaching agent for general fibers and papers, but it is not widely used for rawhide. However, in the present invention, after the first stage treatment with soda chlorite, the latter stage treatment with potassium permanganate and sodium bisulfite is performed to obtain a product in correlation with other steps. On the other hand, the unexpected effect was brought about in the improvement of the said problem. The bleaching of small cowhide and other small animal skin is generally 5%.
Drumming with potassium permanganate solution for about 30 minutes and then with 12% sodium bisulfite solution for about 45 minutes, or using a synthetic tanning agent (generally a mixture of aromatic naphthalene, anthracene, etc. However, the lizard and Karon snake skin that have mottled or striped patterns on the raw hide itself cannot be completely removed by the conventional method, and it is not possible to remove it as in the present invention. These defects are improved by carrying out a step treatment, and the strength of leather (tensile strength, tensile strength,
It was possible to complete the bleaching operation while preventing a decrease in tear strength).
【0010】この発明において複合なめし(コンビネ−
ションなめし)する理由は、いつに革の品質改良を計る
ためであるが、通常クロムなめし後に表面を植物タンニ
ン(又は合成なめし剤)で再なめしするか、クロムなめ
しと塩基性アルミニウムなめしとの複合なめし、フォル
マリンと油でのなめし等が知られているが、リザードカ
ロンスネーク革を柔らかく均整のとれた表面に仕上げる
ものとして従来特筆されるものはなく、しかもそれらを
手袋を意図して行うこと自体非常に稀な事であった。そ
して、数多くの実験の結果次の複合なめしが予想外の物
理的強度、柔軟性、耐ウォツシャブル性、防滑性に寄与
する効果が見出されたのである。即ち、クロムなめしし
た後グルタルアルデヒドでなめす事により上記の性質が
悉く改善されたのである。ただしアルデヒドのなかでも
フォルムアルデヒドやアセトアルデヒドは耐汗性に劣る
ので好ましくない。その他に特に白革を得たい場合には
フォルマリンとジルコニウムによる複合なめしを行う方
法も推奨されるところである。In the present invention, complex tanning (combination
The reason for doing so is to improve the quality of the leather at any time. Usually, the surface is re-tanned with vegetable tannin (or a synthetic tanning agent) after chrome tanning, or a composite of chrome tanning and basic aluminum tanning is used. Tanning, formalin and oil tanning, etc. are known, but no one has hitherto been particularly noted for finishing lizard Karon snake leather on a soft and well-balanced surface, and those should be done with the intention of wearing gloves. It was a very rare thing in itself. As a result of numerous experiments, the following complex tanning was found to have an effect of contributing to unexpected physical strength, flexibility, washable resistance, and slip resistance. That is, the above properties were dramatically improved by chrome tanning and then glutaraldehyde tanning. However, among aldehydes, formaldehyde and acetaldehyde are not preferable because they have poor sweat resistance. In addition, if it is desired to obtain white leather, a method of performing complex tanning with formalin and zirconium is also recommended.
【0011】また、この発明の染色工程で最初に使用す
るビニルスルフォン系反応性染料としては市販名:Re
mazol Brill Yellow 7GL、Ye
llow GNL、Yellow RTN、Brill
Orang 3R、Brill Red 2B、Br
ill Violet 5R、Brill Blue
B、Black B(Heochst)等が使用される
が、これらは皮質の官能基と共有結合により染着し革組
織を保護して風合いを損なう事がなく、後段で用いる燐
酸化染料は染料の水酸基を燐酸エステルに変性したもの
で、クロムなめし革のクロムに配位結合することにより
染着するが、その際他の結合が起きないよう使用量の規
制を行う事は色落ちを誘起する要因を抑える意味で重要
である。The vinyl sulfone-based reactive dye used first in the dyeing process of the present invention has a commercial name: Re
mazol Brill Yellow 7GL, Ye
low GNL, Yellow RTN, Brill
Orange 3R, Brill Red 2B, Br
ill Violet 5R, Brill Blue
B, Black B (Heochst), etc. are used, but these do not damage the texture by dyeing by covalent bonding with the functional groups of the cortex and protecting the leather tissue, and the phosphorylated dye used in the latter stage is the hydroxyl group of the dye. Is modified with phosphoric acid ester, and dyes by coordinatively bonding to chromium of chrome-tanned leather, but controlling the amount used to prevent other bonds at that time suppresses factors that induce discoloration. Important in meaning.
【0012】ビニルスルフォン系反応性染料のみでは革
の銀面を濃色に染色することが難しく、濃度を高める染
色手段は革を硬くするばかりでなく物理的強度を落とす
要因となる。そこに結合態様を代えて燐酸化染料を適量
使用することが反応性染料をいたづらに多く使用しなく
とも特に革の銀面が極めて濃色に染まるばかりでなく、
柔軟性や強度のすぐれた製品とし得ることを見出したの
である。後段で使用する染料としては市販名:RCR
Yellow#1、Red#19、Blue#1、Or
enge#1、Brown#21、Black P−2
が代表的なものである。[0012] It is difficult to dye the silver surface of leather in a dark color only with the vinyl sulfone-based reactive dye, and the dyeing means for increasing the density not only hardens the leather but also reduces the physical strength. It is not only that the silver surface of the leather is dyed in an extremely dark color even if a large amount of the reactive dye is not used by changing the binding mode and using an appropriate amount of the phosphorescent dye.
They found that it could be a product with excellent flexibility and strength. Commercially available dye: RCR
Yellow # 1, Red # 19, Blue # 1, Or
engine # 1, Brown # 21, Black P-2
Is a typical one.
【0013】[0013]
【作用】前述のとおり、漂白を二段工程で行うこと、お
よびなめし処理を複合して行うこと、染色にビニルスル
フォン系反応性染料と燐酸化染料との二段で行ったこ
と、注目すべきこととして、加脂剤として三種の組成物
からなる特殊の疎水性柔軟剤を添加使用したことによ
り、予測の域をはるかに凌ぐ手袋革としての柔軟性と耐
ウォツシャブル性、防滑性が十二分に改善された製品が
得られた。それらの作用に関し、各工程の結合による実
験を多々繰り返した事により優れた結果をもたらすに至
ったのである。As mentioned above, it should be noted that the bleaching was carried out in two steps and the tanning treatment was performed in combination, and the dyeing was carried out in two steps of the vinyl sulfone-based reactive dye and the phosphorylated dye. By using a special hydrophobic softener consisting of three compositions as a fatliquoring agent, the flexibility, washable resistance and anti-slip properties of glove leather far surpasses the prediction range. An improved product was obtained. With regard to these actions, excellent results were obtained by repeating experiments by combining each step.
【0014】考えられることとして、漂白工程で亜塩素
酸ソ−ダ予備処理したことで石灰漬けによっても除きき
れなかった汚物や水溶性タンパク質を除去しコラ−ゲン
繊維をほぐし縞やまだら模様を消し滑らかな皮とするこ
とが出来たのと、染色工程を二段で行い、前段でビニル
スルフォン系反応性染料を革の官能基に共有結合させた
事はもとより、後段に燐酸化染料で革のクロムに配位さ
せたことによりなめし革中に結合しているクロムイオン
との複雑な反応を完結し得たと言え柔軟性と強度を保っ
た上、洗濯の際の褪色防止を完成させた。加えて、前記
三成分からなる柔軟剤が革構成繊維のバンドルに埋設固
定されているため汗や水に対する耐性が得られたこと
と、不変の柔らかさを保つことが可能となったものであ
る。It is conceivable that contaminants and water-soluble proteins that could not be removed by lime picking by pretreatment with sodium chlorite in the bleaching step are removed, and collagen fibers are loosened to eliminate streaks and mottled patterns. In addition to being able to make a smooth leather, the dyeing process was performed in two steps, and the vinyl sulfone-based reactive dye was covalently bonded to the functional group of the leather in the first step, and the leather dye was made with a phosphorylated dye in the second step. It can be said that the complex reaction with the chromium ions bound in the tanned leather can be completed by coordinating to chrome, and the flexibility and strength are maintained, and the prevention of fading during washing is completed. In addition, since the softener composed of the above three components is embedded and fixed in the bundle of leather constituent fibers, resistance to sweat and water is obtained, and it is possible to maintain invariable softness. ..
【0015】[0015]
【実施例1、2】(1はカロンスネーク皮、2はモニタ
ー種のリザード皮で以下の〜の各工程は全く同様と
する。) 水漬け−皮革製造の最初の工程は原料皮の水洗に始
まり水槽、パドルまたは太鼓で処理するが、原料皮に付
着している泥や血液などの汚物を除去し、塩蔵皮の食塩
を十分除去すると共に吸水軟化させ、皮の中の可溶成分
とくにアルブミン、グロブリンの様なタンパク質分を溶
出させるが、細菌類による影響を受けやすいから地方や
季節によってはpHや温度の調整に注意を要する。ま
づ、ドラムに塩蔵皮を投入し略5倍の水を流水しながら
20分程回転し、そのまま新しい水を乾燥皮に対して4
00%入替え24時間漬けておく。 裏打ち−続く石灰漬けの際均一な石灰浸透を促すた
めと裏面の結締組織を除去しつつ揉みほぐしながら皮を
均整化させる。Examples 1 and 2 (1 is Karon snake skin, 2 is lizard skin of monitor species, and the following steps are exactly the same.) Soaked-The first step of leather production is to wash the raw leather with water. It is first treated with a water tank, paddle or drum, but it removes dirt such as mud and blood adhering to the raw material skin, sufficiently removes salt from the salted skin and softens water absorption, and soluble components in the skin, especially albumin. , Proteins such as globulin are eluted, but since they are easily affected by bacteria, careful adjustment of pH and temperature is required depending on the region and season. First, add salted skin to the drum and rotate it for about 20 minutes while running approximately 5 times the amount of water, and then add new water to dry skin 4 times.
Replace with 00% and let it soak for 24 hours. Lining-to promote uniform lime penetration during subsequent lime picking and to smooth the skin while rubbing and loosening while removing the tightening tissue on the back side.
【0016】 石灰漬け−水漬けドラム中に消石灰5
%と濃度35%の水硫化ソーダ2%を投入し約30分回
転し停止30分を二回繰り返し、以降4時間毎に5分宛
4回回転し十分に皮を膨潤させ一昼夜放置しておく。
(使用量%は絶乾皮重量に対する重量%) 脱灰、ベ−ティング−石灰漬けで高いアルカリ状態
にある皮から中間的にアルカリをのぞくためドラム中で
水洗したのち300%の水に0.3%の硫酸アンモニウ
ム、0 .5%の酸性亜硫酸ソーダを溶解した30℃の液中に
て約一時間回転させ、新たに37〜38℃の水に硫酸アンモ
ニウム0.7%酵素剤1.0%を溶解させた液を入れたパド
ルで約3時間回転させる。使用する酵素剤としては一般
的なパンクレアチン、ペプシン、トリプシン、プロテア
−ゼ、アミラ−ゼ等いづれも使用できる。Lime pickling-5 slaked lime in a water pickling drum
% And 2% sodium hydrosulfide with a concentration of 35%, rotate for about 30 minutes, stop for 30 minutes, repeat twice, then rotate 4 times every 5 hours for 5 minutes 4 times to swell the skin and leave it overnight ..
(The amount used is% by weight based on the weight of the absolutely dried skin.) After decalcification, beating, and lime pickling, the skin in a highly alkaline state is washed with water in a drum to remove alkali in the middle, and then washed with 300% water. Rotate for about 1 hour in a solution of 3% ammonium sulphate and 0.5% acidic sodium bisulfite dissolved at 30 ° C, and add 0.7% ammonium sulphate 0.7% enzyme preparation to 37-38 ° C water. Rotate with a paddle containing the dissolved liquid for about 3 hours. As the enzyme agent to be used, any of general pancreatin, pepsin, trypsin, protease, amylase and the like can be used.
【0017】 浸酸−予備なめしとも言える処理であ
り、いちめいピックリングとも言い弱アルカリ性を呈す
る皮をクロムなめし液のpHに更に近づけるために弱酸
性にするが、この場合中性塩を添加して酸膨潤による皮
の破壊が起こらないようにする。使用する酸は、無機酸
も有機酸も使用されるがいづれも一長一短があり、この
発明では蟻酸と硫酸とを併用した。 Acid treatment-a treatment that can be said to be preliminary tanning, also referred to as ichimei pickling, is made weakly acidic in order to bring the skin exhibiting weak alkalinity closer to the pH of the chrome tanning solution, in which case neutral salt is added. To prevent the destruction of the skin due to acid swelling. As the acid to be used, both an inorganic acid and an organic acid are used, but both have advantages and disadvantages. In the present invention, formic acid and sulfuric acid were used in combination.
【0018】 漂白−ピックリングを終えた皮は水洗
して酸や夾雑物を除去し、下記の処理を行う。 初段漂白 200% 水 (25℃) 20% 食塩 30% 亜塩素酸ソーダ (24時間ドラミング) 15% チオ硫酸ソーダ (1時間ドラミング) 後段漂白 200% 水 (25℃) 20% 食塩 3% 過マンガン酸カリ(30分ドラミング) 10% 重亜硫酸ソーダ (45分ドラミング) この操作によりケラチン質を分解し塩素吸着により疑似
なめし作用が生じ後段漂白によるも皮質を傷めない。The skin that has been bleached and pickled is washed with water to remove acid and contaminants, and the following treatment is performed. First stage bleaching 200% Water (25 ° C) 20% Salt 30% Sodium chlorite (24 hours drumming) 15% Sodium thiosulfate (1 hour drumming) Second stage bleaching 200% Water (25 ° C) 20% Salt 3% Permanganate Potassium (Drumming for 30 minutes) 10% Sodium bisulfite (Drumming for 45 minutes) By this operation, the keratin substance is decomposed and a pseudo-tanning action occurs due to chlorine adsorption, and the cortex is not damaged even by bleaching in the subsequent stage.
【0019】 なめし クロム予備なめし 25%クロムなめし液(塩基度33% Cr2O3 5%)
を加えて約2時間ドラミングし、次いで25%クロムな
めし液(塩基度41% Cr2O3 5%)を加えて約3時
間ドラミングして一夜浸漬して、後2%程度のNa HC
O3 液でpH3.5に調節する。 グルタルアルデヒド後なめし グルタルアルデヒドの30%液を皮に対して3%となる
よう蟻酸ナトリウム1%と共に60分間ドラミングす
る。 処理後の皮は白色に近い表面の滑らかな状態であった。The tanning chrome pre-tanned 25% chrome tanning solution (basicity 33% C r2 O 3 5% )
Was about 2 hours drumming added, followed by 25% chrome tanning solution (basicity 41% C r2 O 3 5% ) to be about 3 hours drumming added to soaked overnight, about 2% after Na HC
The pH is adjusted to 3.5 with O 3 solution. Glutaraldehyde post-tanning Drumming a 30% glutaraldehyde solution with 1% sodium formate to 3% on the skin. The skin after the treatment had a smooth surface with a color close to white.
【0020】 染色 一工程ではアルカリ剤としてNa2CO3 とNa2Al2O3
を2:1.5 の割合で用いる。 Brill Blue B(反応性染料)5% Na2SO4 20% Na2CO3 Na2Al2 O3 } 5% ドラム中で90分染色 次いで蟻酸 2%を添加して中和し、後水洗する。二工
程で使用する燐酸化染料はクロムなめし革に配位結合せ
しめて染着するもので、配位結合以外の染着が起きない
よう適切な使用量に調整して染色を行った。 Blue #1(燐酸化染料) 0.5〜1.5% ドラム中で30分染色 次いで蟻酸 1%を添加して中和し、後水洗する。Dyeing In one step, Na 2 CO 3 and Na 2 Al 2 O 3 are used as alkaline agents.
Is used at a ratio of 2: 1.5. Brilli Blue B (reactive dye) 5% Na 2 SO 4 20% Na 2 CO 3 Na 2 Al 2 O 3 } 5% Dye for 90 minutes in a drum, then add 2% formic acid to neutralize and wash with water. .. The phosphorylated dye used in the two steps is dyed with chrome-tanned leather by coordination bonding, and the dyeing was carried out by adjusting the amount used so that dyeing other than coordination bonding does not occur. Blue # 1 (phosphorylated dye) 0.5 to 1.5% Dyeing for 30 minutes in a drum. Then, formic acid 1% is added for neutralization, followed by washing with water.
【0021】 加脂仕上げ 水洗された染色革に下記の配合比の加脂柔軟剤を30%
注加して約1時間ドラミングして十分に革内に剤を浸透
安定化せしめ、後これを若干風乾して板張りし味取り乾
燥する。 長鎖ジアルキルスルフォコハク酸ソーダ 6部 (R:C12〜C18) 長鎖モノアルキル燐酸エステル 6部 ジエチレングリコールモノブチルエーテル 10部 無水マレイン酸−オレフィン共重合体 6部 (オレフィン:C2 〜C5 ) 水 2部Greasing finish 30% of a fattening softener having the following mixing ratio is added to dyed leather washed with water.
Add the agent and drum it for about 1 hour to sufficiently permeate and stabilize the agent in the leather, and then air-dry it slightly, plate it, and taste-dry it. Long-chain sodium dialkylsulfosuccinate 6 parts (R: C 12 to C 18 ) Long-chain monoalkyl phosphate ester 6 parts Diethylene glycol monobutyl ether 10 parts Maleic anhydride-olefin copolymer 6 parts (Olefin: C 2 to C 5 ) 2 parts of water
【0022】[0022]
【比較例】 注−比較例1〜3は全てへび革カロンを使
用した。比較例1は、染色工程でクロムなめし革の染色
に多用されているスルフォン酸のソーダ塩基をもつ酸性
染料である、アシドーブルーブラックを反応性染料に代
えて5%用いた以外は実施例1・2と同様とする。結果
は後記する表1に示されている通り洗濯の反復に対して
色落ちすると共に次第に革が硬化した。比較例2は、実
施例1・2で使用した疎水性高分子柔軟剤に替えてC12
〜14のアルキル基で置換したベタイン誘導体と硫酸化魚
油を乳化して革に対し10%適用した。これは時間が経
過すると共に革内部で平行移動して硬さをまし、耐水性
が低く水濡れによりぬるぬる感が強く不快な感じを与え
た。比較例3は、染色も加脂も比較例1・2と同じ従来
方法に準じて行ったもので、結果的にこの発明の物とは
比較にならないものであった。[Comparative Example] Note-Comparative Examples 1 to 3 used snake leather caron. Comparative Example 1 is an acid dye having a soda base of sulfonic acid, which is often used for dyeing chrome-tanned leather in the dyeing process, except that 5% of acid blue was used instead of the reactive dye. Same as 2. The results are shown in Table 1 below, in which the leather faded and the leather gradually hardened with repeated washing. In Comparative Example 2, the hydrophobic polymer softener used in Examples 1 and 2 was replaced by C 12
~ 14 alkyl-substituted betaine derivatives and sulfated fish oil were emulsified and applied at 10% to leather. This moved parallel with the inside of the leather over time to increase hardness, and was low in water resistance, giving a strong slimy sensation due to water wetting and giving an unpleasant feeling. Comparative Example 3 was carried out according to the same conventional method as Comparative Examples 1 and 2 for dyeing and fatliquoring, and as a result, it was not comparable to the product of the present invention.
【0023】[0023]
【表1】 [Table 1]
【0024】なお、表中の漂白工程は比較例も本発明方
法によったが、これを従来法で漂白した場合は、全体に
更に劣ることは言うまでもない。 評価────5:優れている 4:良い 3:普通
2:劣る 1:極めて劣る 引張強度──JIS K 6550 引裂強度──JIS K 6550 染色堅牢度─JIS 6086(洗濯法により革に添付
した、タテ糸毛糸、ヨコ糸ポリエステルの白布の汚染度
を級で表し、5級 が最強、1級が最弱)耐水度───JIS K 655
0(革の表面に80cmの水圧をかけ反対面に水滴の表
れるまでの時間) 柔軟度───これはJIS L 1005の剛軟度測定
法によった。数値は5回洗濯を繰り返した後の値であ
る。(試験片25mm×150mm を先端が45°の
斜面をもつ台から長さ方向にゆるやかに押出し、先端が
斜面に接したときの試験片の押出し長さ、但し、試験片
はタテ方向にとった。比較例のものは硬化により100
mm以上となる)The bleaching process shown in the table was based on the method of the present invention in the comparative example, but it goes without saying that bleaching by the conventional method is inferior to the whole. Rating ──── 5: Excellent 4: Good 3: Normal
2: Inferior 1: Extremely inferior Tensile strength ─ JIS K 6550 Tear strength ─ JIS K 6550 Dyeing fastness ─ JIS 6086 (The degree of contamination of white cloth of vertical yarn wool and weft polyester attached to leather by washing method is graded. Shown with, grade 5 is the strongest, grade 1 is the weakest) Water resistance ─── JIS K 655
0 (time until 80 cm of water pressure is applied to the leather surface and water droplets appear on the opposite surface) Flexibility: This was measured by the JIS L 1005 bending resistance measurement method. The value is the value after repeating washing five times. (25 mm x 150 mm test piece was gently extruded in the longitudinal direction from a table having a slope of 45 ° at the tip, and the extruded length of the test piece when the tip was in contact with the slope, provided that the test piece was taken in the vertical direction. The comparative example is 100 when cured.
mm or more)
【0025】[0025]
【発明の効果】まづ、蜥蜴および、へびの皮を手袋用に
着目したことと、これに改良を加えて無類の柔軟性と強
度(引張、引裂、表面摩擦抵抗)の高さや色落ちがない
ようにしたこと、繰り返しの洗濯に対してぬるぬる感が
無いばかりでなく、柔らかさが失われない手袋製品を提
供したことに多大の意義を持ち高級品としての価値が極
めて高い物である。特に注目する点は、加脂剤を皮に適
用する手法として三種類の高分子物質から構成される、
加脂剤であると共に柔軟剤である組成物を発見したこ
と、並びに溶剤系の分散液で皮に沈着させたため固定が
強固であり、長期の使用に対しても変質しない特徴を持
つ。[Effects of the Invention] First of all, attention has been paid to lizard and snake skin for gloves, and improvements have been made to achieve excellent flexibility and strength (tensile, tearing, surface friction resistance) and discoloration. It is very valuable as a luxury item because it has great significance in that it does not lose its luster upon repeated washing and that it does not lose its softness. Of particular interest is the application of a greasing agent to the skin, which consists of three types of polymeric substances,
It was discovered that a composition that is both a fatliquor and a softener, and that it is firmly fixed because it is deposited on the skin with a solvent-based dispersion, and has the characteristics that it does not deteriorate even after long-term use.
【0026】従来の加脂剤は界面活性剤を乳化剤として
使用するため乾燥後に革内部に残るので移行したり変質
して問題を起こし、いづれにしても水に弱く、この発明
の物は溶剤と水が飛べば後には有効物質だけが残るから
優れた効果を奏するのである。つぎに、みるべき効果と
して染色工程で反応性染料を多くしてゆけば濃色には染
まるものの革のポリペプチド結合を切ってしまい強度を
著しく損なうこととなり問題があったが、燐酸化染料を
僅かに用いたことにより燐が一種のなめし作用をもたら
し、じゅう皮度を阻害することがないため革の収縮温度
も高く染色堅牢度と物理的強度を高める事が出来たので
ある。漂白においても上記事項との相乗効果をもたらす
とともに、蜥蜴やへび皮の縞やまだら模様を残すこと無
く美しい革表面を持っているので商品価値としての大切
な要因の一つである。Since the conventional fatliquoring agent uses a surfactant as an emulsifier, it remains inside the leather after drying, which causes problems such as migration and deterioration, and it is weak against water in any case. If the water flies away, only the active substance remains, so it has an excellent effect. Next, as an effect to be seen, if the amount of reactive dye is increased in the dyeing process, it will be dyed in a dark color, but the polypeptide bond of the leather will be cut and the strength will be significantly impaired. Phosphorus brings about a kind of tanning effect even when used in a small amount, and since it does not hinder the leatheriness, the shrinkage temperature of the leather is high and the dyeing fastness and physical strength can be increased. In bleaching, it has a synergistic effect with the above items, and because it has a beautiful leather surface without leaving stripes or mottled patterns on lizards and snakeskin, it is one of the important factors as a commercial value.
Claims (4)
スネークの皮を原皮とし、順次水漬け、石灰漬け、脱
灰、酵素処理、漂白、浸酸、なめし処理、染色、加脂仕
上げしてなめし革を製造する方法において、加脂仕上工
程で長鎖ジアルキルスルフォコハク酸塩を主剤とし、こ
れに長鎖モノアルキル燐酸エステルおよび無水マレイン
酸−オレフィン共重合体からなる疎水性高分子重合体
を、溶媒として高沸点で極性基をもつジエチレングリコ
ールモノブチルエーテルで乳化した液を加脂剤とし、特
定の方法で革に適用せしめることを特徴とする柔軟性、
耐ウオッシャブル性、防滑性に富む各種スポーツ用品お
よび各種手袋用、ガーメント用の爬虫類皮革の製造方
法。1. A tanned leather that is made from the skins of lizard and / or Karon snake of the monitor species as a raw hide, and is successively soaked in water, lime picked, decalcified, enzyme treated, bleached, soaked, tanned, dyed and greased. In the method for producing, a long-chain dialkylsulfosuccinate is used as a main component in a fatliquoring step, and a hydrophobic high-molecular polymer consisting of a long-chain monoalkyl phosphate ester and maleic anhydride-olefin copolymer is used as a solvent. As a softening agent, a liquid emulsified with diethylene glycol monobutyl ether having a high boiling point and a polar group as a fatliquoring agent, and being applied to leather by a specific method,
A method for producing reptile leather for various sports goods and various gloves and garments, which has excellent washability and slip resistance.
ォン系反応性染料で染色したのち燐酸化染料で処理する
請求項1の爬虫類皮革の製造方法。2. The method for producing reptile leather according to claim 1, wherein the dyeing step is carried out in two steps, first dyeing with a vinyl sulfone reactive dye and then treating with a phosphorylated dye.
過マンガン酸カリと重亜硫酸ソーダ処理する請求項1の
爬虫類皮革の製造方法。3. The method for producing reptile leather according to claim 1, wherein the bleaching step is first treated with sodium chlorite and then treated with potassium permanganate and sodium bisulfite.
ドとの複合なめしするか、またはフォルマリンとジルコ
ニウムとの複合なめしとする請求項1の爬虫類皮革の製
造方法。4. The method for producing reptile leather according to claim 1, wherein the tanning treatment is a composite tanning of chromium and glutaraldehyde or a composite tanning of formalin and zirconium.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4018304A JPH0655960B2 (en) | 1992-01-06 | 1992-01-06 | Reptile leather manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4018304A JPH0655960B2 (en) | 1992-01-06 | 1992-01-06 | Reptile leather manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05179300A true JPH05179300A (en) | 1993-07-20 |
JPH0655960B2 JPH0655960B2 (en) | 1994-07-27 |
Family
ID=11967877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4018304A Expired - Lifetime JPH0655960B2 (en) | 1992-01-06 | 1992-01-06 | Reptile leather manufacturing method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0655960B2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6497860B1 (en) | 1996-11-04 | 2002-12-24 | Children's Hospital Medical Center | Skin lightening compositions |
JP2003092997A (en) * | 2001-09-21 | 2003-04-02 | Kaiji Watanabe | Method for treating sharkskin and method for obtaining collagen |
CN104294679A (en) * | 2014-10-23 | 2015-01-21 | 北京泛博化学股份有限公司 | Oxidation dyeing method utilizing potassium permanganate as medium |
CN104498646A (en) * | 2014-11-25 | 2015-04-08 | 浙江中辉皮草有限公司 | Method for imitating beige mink fur by using chalybeous mink fur |
CN106834564A (en) * | 2017-02-22 | 2017-06-13 | 陈顶凯 | Collagen skin technique |
EP3249058A1 (en) * | 2016-05-04 | 2017-11-29 | Richemont International S.A. | Method for preparing leather from raw hide |
-
1992
- 1992-01-06 JP JP4018304A patent/JPH0655960B2/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6497860B1 (en) | 1996-11-04 | 2002-12-24 | Children's Hospital Medical Center | Skin lightening compositions |
JP2003092997A (en) * | 2001-09-21 | 2003-04-02 | Kaiji Watanabe | Method for treating sharkskin and method for obtaining collagen |
CN104294679A (en) * | 2014-10-23 | 2015-01-21 | 北京泛博化学股份有限公司 | Oxidation dyeing method utilizing potassium permanganate as medium |
CN104498646A (en) * | 2014-11-25 | 2015-04-08 | 浙江中辉皮草有限公司 | Method for imitating beige mink fur by using chalybeous mink fur |
CN104498646B (en) * | 2014-11-25 | 2016-08-24 | 浙江中辉皮草有限公司 | A kind of process copying ecru mink fur with chalybeate mink fur |
EP3249058A1 (en) * | 2016-05-04 | 2017-11-29 | Richemont International S.A. | Method for preparing leather from raw hide |
CN106834564A (en) * | 2017-02-22 | 2017-06-13 | 陈顶凯 | Collagen skin technique |
Also Published As
Publication number | Publication date |
---|---|
JPH0655960B2 (en) | 1994-07-27 |
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