JPH09118846A - Resin film - Google Patents

Resin film

Info

Publication number
JPH09118846A
JPH09118846A JP8220742A JP22074296A JPH09118846A JP H09118846 A JPH09118846 A JP H09118846A JP 8220742 A JP8220742 A JP 8220742A JP 22074296 A JP22074296 A JP 22074296A JP H09118846 A JPH09118846 A JP H09118846A
Authority
JP
Japan
Prior art keywords
silk
powder
film
silk powder
solvent
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
JP8220742A
Other languages
Japanese (ja)
Inventor
Sadao Nishibori
貞夫 西堀
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.)
AIN CORP Ltd
AIN KK
Original Assignee
AIN CORP Ltd
AIN 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 AIN CORP Ltd, AIN KK filed Critical AIN CORP Ltd
Priority to JP8220742A priority Critical patent/JPH09118846A/en
Publication of JPH09118846A publication Critical patent/JPH09118846A/en
Pending legal-status Critical Current

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  • Paints Or Removers (AREA)

Abstract

PROBLEM TO BE SOLVED: To prepare a resin film with silk powder dispersed homogeneously therein, good in skin touch feeling, having moisture absorbability/releasability and luster each unique to silk, by pulverizing a silk material by wet grinding and by using the ground silk powder suspending in the solvent used for the pulverization as a part of film-forming components. SOLUTION: A silk material in powdery, granular or short fiber form is pulverized into silk powder finer than 6μm in particle diameter by wet grinding using a solvent such as dimethylformamide or toluene as medium, and the resultant ground silk powder suspending in the solvent is used as a part of resin film-forming components. For the wet grinding, a wet ball mill, for example, can be used. In order to conduct the wet grinding more efficiently, it is preferable that the silk material be preliminarily ground and then subjected to air classification based on true specific travity or sieve classification based on bulkiness so that the silk powder finer than 50μm in particle diameter account for >=90wt.% of the whole silk powder. For the preliminary grinding, a dry grinder such as a turbo mill is normally used. The moisture content of the silk material is pref. 5wt.% or so, when it is to be subjected to the wet grinding.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【発明の属する技術分野】この発明は粉砕された絹粉を
含む絹生地様の樹脂皮膜に関する。
TECHNICAL FIELD The present invention relates to a silk-like resin film containing crushed silk powder.

【0002】[0002]

【従来の技術】通例天然の絹繊維は、しなやかで肌触り
が良く、しかも適度の吸湿性を備えており、光沢、風合
いに優れていると共に強伸度並びに耐衝撃性に優れてお
り、各種の繊維製品あるいは糸等として多方面に亘って
使用されてきている。
2. Description of the Related Art Naturally, natural silk fibers are supple, soft to the touch, and have an appropriate degree of hygroscopicity, and are excellent in gloss, texture, strength and elongation, and impact resistance. It has been used in various fields as a textile product or yarn.

【0003】かゝる絹繊維の有する特性は、この絹繊維
に含まれているセリシンが溶解除去されて、グリシン、
アラニン、セリン、チロシン等のアミノ酸残基が直鎖状
に連結したフィブロイン分子で構成されていることに由
来するものであり古来から重要な衣服等の素材とされて
きている。
The characteristic of such a silk fiber is that sericin contained in the silk fiber is dissolved and removed to give glycine,
It is derived from the fact that it is composed of a fibroin molecule in which amino acid residues such as alanine, serine, and tyrosine are linearly linked, and has been an important material for clothes since ancient times.

【0004】又、この種の天然の絹繊維は染色性に優れ
ていることからミリング染色による染色に際しても沸騰
させる必要がなく、80〜90℃で染料が絹に吸尽され、染
色中の損傷が少ないことから、各種の色調の染色が可能
であり、特に鮮かな色彩で、しかも極薄状の織編布に用
いられていた。
Since this type of natural silk fiber is excellent in dyeability, it is not necessary to boil when dyeing by milling dyeing, and the dye is exhausted to silk at 80 to 90 ° C., causing damage during dyeing. Since it has a small number of dyes, it can be dyed in various color tones, and it has been used for an extremely thin woven or knitted fabric with a particularly bright color.

【0005】[0005]

【発明が解決しようとする課題】しかしながら従前にお
ける絹素材は、絹繊維として糸又は織編生地として用い
られる以外に他の用途に向けられて用いられることが少
なかった。
However, the conventional silk material has rarely been used for other purposes besides being used as a thread or a woven or knitted material as a silk fiber.

【0006】そして、この糸あるいは織編布とされた絹
繊維は摩耗に弱く、又太陽光線で容易に褪色する不都合
を有しており、水濡れ時の保形力にも難があった。
The silk fiber made of this yarn or woven or knitted fabric is vulnerable to abrasion and has the disadvantage that it is easily discolored by the sun's rays, and its shape-retaining power when wet with water is also difficult.

【0007】又、絹素材を糸あるいは繊維として使用す
る場合には良質の連続した絹フィブロインを取り出す必
要があり、用意された繭繊維の全部を効果的に用いるこ
とができなかった。
Further, when using a silk material as a thread or a fiber, it is necessary to take out high-quality continuous silk fibroin, and it is impossible to effectively use all of the prepared cocoon fibers.

【0008】本発明は、このように天然に存在している
絹素材を微粉状に粉砕して、これを樹脂皮膜の形成用の
樹脂に配合することによって天然の絹素材に近い特性を
この皮膜にもたらそうとするものであり、天然の絹繊維
の欠点とされていたところの劣悪な耐摩耗性を補うと共
に、耐水、耐湿特性を向上させ、更に褪色の不都合を無
くしたものである。更に繊維以外の皮膜を絹状のものと
することによって、絹素材の新たな使用展開を試みたも
のである。
According to the present invention, such a naturally existing silk material is pulverized into a fine powder, and this is blended with a resin for forming a resin film, so that the film has characteristics close to those of a natural silk material. In addition to supplementing the poor abrasion resistance, which has been considered to be a drawback of natural silk fibers, improving the water resistance and moisture resistance, and eliminating the disadvantage of fading. Furthermore, by using a silk-like film other than the fibers, a new use development of the silk material was attempted.

【0009】しかしながら、かゝる絹素材を粉砕して樹
脂皮膜中に含ませ絹様の表面特性を有する皮膜を形成す
るためには絹素材を微粉状に粉砕する必要があり、かゝ
る粉砕絹粉の粒径の大きい場合、この粉砕絹粉を混配合
してなる皮膜の面が荒れ出し、ザラつき感を生ずる不都
合があった。
However, in order to crush such a silk material to be contained in the resin film to form a film having a silk-like surface characteristic, it is necessary to crush the silk material into a fine powder. When the particle size of the silk powder is large, the surface of the film formed by mixing and blending the crushed silk powder becomes rough and there is a problem that a rough feeling is generated.

【0010】そこで、絹素材を種々の方法で粉砕して微
粉状の絹粉を形成することが試みられ、主として機械的
な剪断による粉砕と乾式ボールミルによる磨砕粉砕によ
り絹素材の粉砕を試みた。
Therefore, it has been attempted to pulverize the silk material by various methods to form finely powdered silk powder, and mainly to pulverize the silk material by pulverization by mechanical shearing and grinding by a dry ball mill. .

【0011】この乾燥条件下での剪断粉砕と磨砕粉砕で
は絹繊維が粒状に粉砕されず、微細な繊毛部分を有する
多毛の繊維塊状とされるため、剪断粉砕あるいは磨砕粉
砕によって形成される絹粉相互が綿状に絡み合って凝集
してしまう不都合があった。
Since the silk fibers are not crushed into particles by the shear crushing and the crushing and crushing under the dry condition and are made into a fluffy fiber mass having fine cilia, they are formed by the shear crushing or the crushing and crushing. There is a disadvantage that the silk powders are entangled in a cotton shape and aggregate.

【0012】そして、このような綿状凝集は絹粉の粉砕
の過程においても生ずることから絹素材の粉砕が均一に
なされず、大き目の繊維塊状の粉砕品と、極微細な多毛
状繊維粉とが混在された状態となり、均一の粒径の絹粉
が得られない欠点を有していた。又、この絹素材の微細
化に多くの粉砕時間を要する欠点を有していた。
Since such cotton-like agglomeration also occurs in the process of crushing silk powder, the crushing of the silk material is not uniform, and a crushed product in the form of a large fiber lump and an extremely fine hairy fiber powder are crushed. However, there is a drawback that silk powder having a uniform particle size cannot be obtained. Further, there is a drawback that it takes a long crushing time to make the silk material fine.

【0013】かゝる粉砕に伴って絹粉に生ずる繊毛は、
絹素材の粉砕が長時間に及ぶにつれて、より多く生ずる
傾向を示し、又粉砕された絹素材が微細になればなる
程、この粉砕された絹粉に多毛様の繊毛が生ずる傾向を
示している。
The cilia generated in the silk powder due to such crushing are
The more crushed the silk material is, the more it tends to occur, and the finer the crushed silk material, the more lithe-like cilia tend to occur in the crushed silk powder. .

【0014】この結果、絹素材を剪断粉砕あるい磨砕粉
砕によって極微細な絹粉を得ようとした場合、粉砕形成
された絹粉相互が綿状に絡み合って、皮膜形成用の樹脂
中に、これらの粉砕絹粉を混配合した場合、この樹脂中
に混配合した粉砕絹粉が均一に分散されない欠点を有し
ていた。
As a result, when an attempt is made to obtain ultrafine silk powder by shear crushing or crushing the silk material, the crushed and formed silk powders are entangled in a cotton-like shape, and the silk powders are formed in the resin for film formation. However, when these crushed silk powders were mixed and mixed, there was a drawback that the crushed silk powder mixed and mixed in this resin was not uniformly dispersed.

【0015】又、粉砕された絹粉が綿状に絡み合って、
より大きな固まりとなる現象は、これらの絹粉を皮膜成
形用の樹脂と混配合して用いる場合に限らず、絹粉の成
形工程においても、又、絹粉の保管過程においても生ず
る。このことから、皮膜成形用の樹脂との混配合に際し
て、これらの混配合絹粉の綿状凝集を防止するだけで
は、この樹脂中に均一に粉砕絹粉が分散されない欠点を
有していた。
Further, the crushed silk powder is entwined in a cotton shape,
The phenomenon of becoming larger lumps occurs not only when these silk powders are mixed and mixed with a resin for forming a film, but also in the molding process of the silk powders and the storage process of the silk powders. From this, when mixed with the resin for forming the film, there is a drawback that the crushed silk powder is not uniformly dispersed in the resin only by preventing flocculation of the mixed blended silk powder.

【0016】更に、叙上手法による剪断ないしは磨砕で
は、粉砕時に多量の摩擦ないしは衝撃に伴う熱を生じ、
この粉砕に伴う熱によって粉砕絹粉のフィブロインが変
質したり、変色したりすることがあり、特に粉砕絹粉が
磨砕装置の内壁面あるいは磨砕用のボールの面に融着あ
るいは結着する不都合があった。
Further, in the shearing or grinding by the above-mentioned method, a large amount of heat due to friction or impact is generated during grinding,
The heat associated with this crushing may cause the fibroin of the crushed silk powder to deteriorate or discolor, and in particular, the crushed silk powder is fused or bonded to the inner wall surface of the grinding device or the surface of the grinding ball. There was an inconvenience.

【0017】そこで、粉又は粒又は短繊維状をなす絹素
材を液状ポリマーあるいは各種の溶剤で希釈した樹脂溶
液に混配合し、この粉又は粒又は短繊維状の絹素材の混
配合された液状ポリマーあるいは樹脂溶液を湿式粉砕機
に投入して粉砕することを試みた。
Therefore, a powder or granular or short fiber silk material is mixed and mixed with a liquid polymer or a resin solution diluted with various solvents, and this powder, particle or short fiber silk material is mixed and mixed with the liquid. An attempt was made to throw the polymer or resin solution into a wet pulverizer and pulverize it.

【0018】かゝる湿式粉砕の方法では、液状ポリマー
あるいは樹脂溶液の流動抵抗が大きく、撹拌粉砕が円滑
になされないと共に、混配合した絹素材がポリマー中に
均一に分散されない欠点を有していた。特に、この種の
液状ポリマーあるいは樹脂溶液の撹拌を続行した場合、
これらのポリマーあるいは樹脂溶液の粘性が経時的に高
められる傾向にあり、湿式粉砕機による円滑な粉砕処理
が困難とされる場合が多い。そして、粉砕機の撹拌に伴
って粉砕機中の粉砕温度が上昇された場合には、かゝる
粉砕上の不都合が更に顕著に生じた。
In such a wet pulverization method, the flow resistance of the liquid polymer or resin solution is large, stirring and pulverization cannot be carried out smoothly, and the mixed and blended silk materials are not uniformly dispersed in the polymer. It was Especially when continuing stirring of this type of liquid polymer or resin solution,
The viscosity of these polymers or resin solutions tends to increase with time, and smooth pulverization by a wet pulverizer is often difficult. Then, when the pulverizing temperature in the pulverizer was increased with the stirring of the pulverizer, such inconvenience in pulverization occurred more remarkably.

【0019】本発明は、かゝる絹粉の粉砕を容易、確実
になし、粉砕された絹粉が相互に綿状に絡み合って凝集
することのないようになすと共に、絹粉々砕時における
粉砕熱の発生を無くし品質に変化が無く、しかも均一の
粒径からなる6ミクロン(粒が細長状である場合は、そ
の短径側で測定した粒径を意味し、以下μm と表示す
る。)よりも微細な絹粉の提供をなし、このように6μ
m よりも微細な範囲の絹粉とされ、しかも均一の粒径と
された絹粉を含む0.02〜0.002mm の厚さからなる皮膜の
形成を目的としている。
According to the present invention, such silk powder can be easily and surely crushed, the crushed silk powder is prevented from being entangled with each other in a cotton-like shape and aggregated, and the crushed silk powder is crushed. The heat generation is eliminated, the quality does not change, and the particle size is uniform. 6 micron (If the particle is elongated, it means the particle size measured on the shorter diameter side, and will be referred to as μm hereinafter). We provide finer silk powder than
The purpose is to form a film with a thickness of 0.02 to 0.002 mm that contains silk powder in a finer range than m and that has a uniform particle size.

【0020】[0020]

【課題を解決するための手段】本発明に係る樹脂皮膜は
叙上の目的を達成するものとして、粉又は粒又は短繊維
状をなす絹素材を用意し、この絹素材をジメチルフォル
ムアミド、トルエン等の主として有機系の溶剤を媒体と
して粉砕した6μm よりも細かい絹粉を、この粉砕絹粉
を含む溶剤と共に樹脂皮膜の成形樹脂溶液の一成分とす
るものであり、形成された樹脂皮膜が6μm よりも微細
な範囲に属する絹素材を含む構成としてある。
Means for Solving the Problems In order to achieve the above object, the resin film according to the present invention is prepared by preparing a silk material in the form of powder, granules or short fibers, and using this silk material as dimethylformamide and toluene. A finely divided silk powder smaller than 6 μm crushed mainly with an organic solvent as a medium is used as a component of the resin solution for forming a resin film together with the solvent containing the crushed silk powder, and the formed resin film is 6 μm. The composition includes a silk material belonging to a finer range.

【0021】[0021]

【発明の実施の形態】以下、本発明の典型的な一実施例
にかかる樹脂皮膜について説明する。
BEST MODE FOR CARRYING OUT THE INVENTION A resin film according to a typical embodiment of the present invention will be described below.

【0022】先ず、通例、繭を湯で煮込んでセリシンを
柔かくした状態でフィブロイン繊維を適宜の大きさに切
断する。又は、繭を加熱、乾燥して内部のさなぎを取除
いた状態で繭そのものを粉砕して適宜の粉、粒又は短繊
維とする。更に、石鹸液で精練してセリシンを溶解除去
した後にフィブロイン繊維を粉砕して適宜の大きさから
なる絹素材を用意する。
First, the fibroin fiber is usually cut into an appropriate size while the cocoon is boiled in hot water to soften the sericin. Alternatively, the cocoon itself is pulverized in a state where the cocoon is heated and dried to remove the pupa therein, thereby obtaining appropriate powder, granules or short fibers. Furthermore, after sericin is dissolved and removed by scouring with a soap solution, fibroin fibers are pulverized to prepare a silk material having an appropriate size.

【0023】この絹素材を5重量%前後の含水率となる
まで乾燥して粉砕媒体としての溶剤に投入する。
This silk material is dried to a water content of about 5% by weight and added to a solvent as a grinding medium.

【0024】この絹素材の乾燥は、乾燥の度合いが高い
程以下の粉砕が容易となり、しかも樹脂等に配合した場
合に、これらの樹脂溶液中に円滑且つ均一に分散される
特長を有しており、更に成形される皮膜に発生水蒸気に
よるピンホール等を生ずることがない特長を有してい
る。
With respect to the drying of this silk material, the higher the degree of drying, the easier the following pulverization becomes, and when it is blended with a resin or the like, it has the characteristic that it is smoothly and uniformly dispersed in these resin solutions. Moreover, it has a feature that pinholes and the like due to generated steam are not generated in the formed film.

【0025】かゝる絹素材をジメチルフォルムアミド、
トルエン等の溶剤と共に湿式ボールミル等の湿式粉砕機
に投入し、この溶剤によって絹素材相互が接触されない
状態で粉砕する。この湿式ボールミル等の粉砕機による
粉砕は粉砕絹粉の粒径が6μm よりも微細な範囲となる
まで続けられる。又、この湿式粉砕機により粉砕される
絹粉の粒径を均一とし、しかも短時間に粉砕絹粉を目的
とする粒径にまで粉砕するためには、湿式粉砕機に投入
する絹素材を分級し、粉又は粒又は短繊維状の絹粉が50
μm よりも細かい範囲に属している微細絹粉を絹粉全量
の90重量%以上となるように篩又は風量分級機で分級し
ておくのが良い。
[0025] The silk material is dimethylformamide,
It is put into a wet crusher such as a wet ball mill together with a solvent such as toluene, and crushed in a state where the silk materials are not in contact with each other by this solvent. The pulverization by a pulverizer such as a wet ball mill is continued until the particle size of the pulverized silk powder becomes finer than 6 μm. In order to make the particle size of the silk powder crushed by this wet crusher uniform and to crush the crushed silk powder to the target particle size in a short time, classify the silk material to be put into the wet crusher. 50 pieces of powder or granules or short fiber silk powder
It is advisable to classify fine silk powder belonging to a finer range than μm with a sieve or an air flow classifier so as to be 90% by weight or more of the total amount of silk powder.

【0026】尚、叙上において用いられる溶剤は有機溶
剤を典型例とするものであり、この粉砕絹粉を混入使用
する皮膜形成用の樹脂溶液等の樹脂素材に適応する溶剤
が用いられる。そして、この溶剤は蛋白質を主成分とす
る絹粉が不溶であることを要し、典型的にはジメチルフ
ォルムアミド、トルエン、メチルエチルケトン等が用い
られる他メタノール、イソプロピルアルコール、n-ブタ
ノール、ベンジルアルコール、酢酸エチル、酢酸ブチ
ル、アセトン、メチルイソブチルケトン、シクロヘキサ
ン、テトラヒドロフラン、ジオキサン、キシロール、2
・ニトロプロパン、二塩化エタン、トリクロ−ルエチレ
ン、パ−クロ−ルエチレン、メチルセロソルブ、エチル
セロソルブ等が用いられている。かゝる溶剤は絹素材が
不溶のものであることから、これに絹粉を混入しても絹
粉が膨潤したり、溶けだしたりすることがなく、又絹粉
中の水分等が溶剤に吸収されて絹粉が硬化したりするこ
とがなく、絹素材の粉砕過程のいずれにおいても、溶剤
に混入したときと同様の状態が絹素材に約束される特長
を有している。
The solvent used in the above is typically an organic solvent, and a solvent suitable for a resin material such as a resin solution for forming a film containing crushed silk powder is used. And, this solvent requires that silk powder containing protein as a main component is insoluble, and typically dimethylformamide, toluene, other methanol such as methyl ethyl ketone, isopropyl alcohol, n-butanol, benzyl alcohol, Ethyl acetate, butyl acetate, acetone, methyl isobutyl ketone, cyclohexane, tetrahydrofuran, dioxane, xylol, 2
-Nitropropane, ethane dichloride, trichloroethylene, perchloroethylene, methyl cellosolve, ethyl cellosolve, etc. are used. Since such a solvent is insoluble in the silk material, the silk powder does not swell or melt even when mixed with the silk powder, and the water in the silk powder is absorbed by the solvent. The silk material does not harden as a result, and has the characteristic that the same state as when mixed with a solvent is promised to the silk material in any of the pulverization processes of the silk material.

【0027】このような溶剤を湿式媒体として粒又は粉
又は短繊維状の絹素材を粉砕機に投入して粉砕処理を施
す。
Granules, powders or short fiber silk materials are put into a crusher using such a solvent as a wet medium to perform crushing treatment.

【0028】この粉砕装置は粉又は粒又は短繊維状物の
湿式粉砕に適するものであれば、いかなる装置であって
も良く、主として各種のボ−ルミルの中で湿式粉砕に適
するものが用いられる。
The crushing device may be any device as long as it is suitable for wet crushing of powder, granules or short fibrous substances, and a device suitable for wet crushing is mainly used among various ball mills. .

【0029】又、この粉砕機による粉砕は、投入された
粒又は粉又は短繊維状の絹粉の粒径が6μm よりも微細
なものとなるまで続行される。従って、この粉砕機によ
る粉砕時間等の粉砕条件は、粉砕機の容量と、この粉砕
機で用いられるボールの径及び投入量と、この粉砕機に
投入される絹素材の種別及び投入量と、使用溶剤の種別
及び投入量と、粉砕機の撹拌速度並びに粉砕温度等の諸
条件によって随時変更されるが、極力粉砕中の溶剤温度
が上昇されない範囲で絹粉の粉砕をなすことが、粉砕絹
粉の品質の劣化をもたらさないために必要である。
The pulverization by the pulverizer is continued until the grain size of the introduced particles or powder or the short fiber silk powder becomes finer than 6 μm. Therefore, crushing conditions such as crushing time by the crusher, the capacity of the crusher, the diameter and input amount of the ball used in the crusher, the type and input amount of the silk material to be input to the crusher, The type and amount of the solvent used, the stirring speed of the crusher, and various conditions such as the crushing temperature are changed as needed.However, crushing of the silk powder as long as the solvent temperature during crushing is not increased as much as possible Necessary in order not to cause deterioration of the powder quality.

【0030】又、叙上の粉砕機による粉砕をより効果的
になすために、粉砕される絹素材に対し予備粉砕を施
し、これを真比重による風量分級又は嵩による篩分級に
よって、その粒径を略50μm よりも細かい範囲に揃える
ものであり、通例ターボミル等の乾式粉砕機による粉砕
により用意する。
In order to make the crushing by the above-mentioned crusher more effective, the crushed silk material is subjected to preliminary crushing and the particle size thereof is determined by air classification by true specific gravity or sieve classification by bulk. Is prepared in a range finer than about 50 μm, and is usually prepared by pulverization with a dry pulverizer such as a turbo mill.

【0031】このように、絹素材が不溶であるところの
溶剤を粉砕媒体とした湿式粉砕では、粉砕中の絹素材が
溶剤によって溶け出したり、膨潤したり、あるいは硬く
なったりすることが無く、しかも外気と遮断された状態
で粉砕されることから、粉砕中における絹素材の吸放湿
現象が無い特長を有している。この結果、絹素材の粉砕
の過程において絹素材の含水率が高められて相互に融着
し合ったり、柔らかくなって磨砕あるいは衝撃粉砕に適
しなくなったりすることがなく、粉砕形成された絹粉が
繊毛状の枝毛を有せず粒状に粉砕される特長を有してい
る。又、絹素材の粉砕の過程において絹素材の含水率が
低められて親水性を阻害されるまで品質が劣化されるこ
ともない。このようにして粉砕された絹粉を、粉砕時の
溶剤と共に樹脂の成形用に用いる。
Thus, in wet pulverization using a solvent in which the silk material is insoluble as a pulverizing medium, the silk material being pulverized does not dissolve, swell, or harden due to the solvent, Moreover, since the silk material is crushed in a state of being shielded from the outside air, it has the feature that there is no moisture absorption / release phenomenon of the silk material during crushing. As a result, in the process of crushing the silk material, the water content of the silk material is increased and the silk materials are not fused to each other, or become soft and not suitable for grinding or impact crushing. Has the characteristic that it has no cilia-like split ends and is crushed into particles. In addition, the quality of the silk material is not deteriorated until the water content of the silk material is lowered and the hydrophilicity is hindered in the process of crushing the silk material. The silk powder crushed in this way is used for molding a resin together with a solvent at the time of crushing.

【0032】例1 繭から繰り出した絹フィブロインを5重量%の含水率ま
で乾燥し、この状態でターボミルにより粉砕し、これを
分級して以下の絹素材を用意した。この絹素材の含有水
分は5重量%であったが、実際の絹素材の粉砕では3〜
10重量%の範囲にある含水率の絹素材の使用が可能であ
った。
Example 1 Silk fibroin fed from a cocoon was dried to a water content of 5% by weight, ground in this state with a turbo mill, and then classified to prepare the following silk material. The water content of this silk material was 5% by weight.
It was possible to use a silk material having a water content in the range of 10% by weight.

【0033】前記の絹粉をジメチルフォルムアミド100
重量部に対し25重量部の割合で粉砕機に投入した。この
粉砕機に対し3mm径のアルミナ系ボールを体積比で70
%、絹粉を含む溶剤を体積比25%投入して90分間撹拌し
たところ以下の粒径からなる絹粉とすることができた。
The above-mentioned silk powder was added to dimethylformamide 100
It was charged into the crusher at a ratio of 25 parts by weight with respect to parts by weight. Alumina-based balls with a diameter of 3 mm were used for this crusher at a volume ratio of 70
%, A solvent containing silk powder was added at a volume ratio of 25%, and the mixture was stirred for 90 minutes, whereby a silk powder having the following particle size could be obtained.

【0034】例2 前記のタ−ボミルで粉砕した粒又は粉又は短繊維状の絹
素材をジリコニア系の3mm径のボ−ルを充填した粉砕機
で以下の条件で粉砕したところ、120分〜180分で
粉砕絹粉の粒径が6μm 以下となった。 トルエン100 重量部に絹粉40重量部を配合した配合液50
%(体積比) 3mm径のジリコニア系ボ−ル50%(体積比)
Example 2 The grain or powder or short fiber silk material pulverized by the above-mentioned terbomill was pulverized by a pulverizer filled with a zirconia-based ball having a diameter of 3 mm under the following conditions: 120 minutes- The particle size of the crushed silk powder became 6 μm or less in 180 minutes. Formulation liquid 50 in which 40 parts by weight of silk powder is mixed with 100 parts by weight of toluene
% (Volume ratio) 3mm diameter zirconia-based ball 50% (volume ratio)

【0035】尚、溶剤に配合される絹粉の量は、溶剤の
性状、特に溶剤の有する粘性の度合いにより夫々適量が
あり、ジメチルフォルムアミドはトルエンに比して粘性
が高いことから、絹粉の配合量をトルエンよりも少なく
する必要がある。
The amount of silk powder blended in the solvent depends on the nature of the solvent, especially the viscosity of the solvent, and dimethylformamide has a higher viscosity than toluene. It is necessary to make the compounding amount of the compound less than that of toluene.

【0036】又、粉砕機に投入される絹素材及び溶剤の
量を増した場合、その増量相当分前記の6μm の絹粉と
するのに多くの粉砕時間を必要としている。尚、粉砕機
に投入されるボールの径を大きくしたところ粉砕時間の
短縮化がはかられたものゝ、径の大きい絹粉及び繊毛部
分を有する絹粉が残溜される傾向があり、必要以上に大
きい径のボールの使用では均一の粒径の絹粉を得ること
ができなかった。
Further, when the amount of the silk material and the solvent to be put into the crusher is increased, it takes a long crushing time to obtain the above-mentioned 6 μm silk powder by the increased amount. In addition, when the diameter of the ball put into the crusher was increased, the crushing time was shortened when the diameter was increased. However, silk powder having a large diameter and silk powder having cilia tended to remain. With the use of balls having a larger diameter, silk powder having a uniform particle size could not be obtained.

【0037】又、前記例1のように事前に粉又は粒又は
短繊維状の絹素材の粒径を揃えることなしにジメチルフ
ォルムアミドを用いて湿式ボールミルで絹素材の粉砕を
なしたところ、粒径を揃えた絹素材の利用に比し略30分
程粉砕時間を長目にする必要があった。尚、この方法で
も6μm よりも微細で均一の絹粉を作り出すことができ
た。
When the silk material was pulverized by a wet ball mill using dimethylformamide without adjusting the particle diameters of the powder or particles or the short fiber silk material in advance as in Example 1, the particles were It was necessary to prolong the crushing time by about 30 minutes compared with the use of silk materials of uniform diameter. Even with this method, silk powder finer than 6 μm could be produced.

【0038】叙上の方法で粉砕された絹粉は、その粉砕
の過程並びに作り出された絹粉に以下の特長が認められ
た。先ず、粉砕機に投入された粒又は粉又は短繊維状の
絹素材は、この絹素材が不溶とされるところの、主とし
て有機系の溶剤中に取りこまれ、絹素材相互が、この溶
剤により包みこまれた状態で粉砕されるため、絹素材相
互が融着し合うことがなく多毛状の破断繊毛を生ずるこ
となく粉砕され、又ボールないしは粉砕機の面に融着す
ることがない。特に、ボールの磨砕ないしは衝撃に伴っ
て生ずる熱が、この溶剤により分散されて直接絹素材に
伝達されないことから、熱による絹素材の変質ないしは
絹粉相互の溶融着を生ずる虞れがない。又、絹粉が溶剤
によって覆われた状態で粉砕されていることから、この
絹粉の粉砕過程において、絹素材が湿気を帯びて膨潤な
いしは、この粉砕過程での水分の蒸散加熱に伴う硬化現
象を生ずることがなく、溶剤に混合された絹素材が溶剤
に混入時の含水率を含み、絹素材特有の膨潤機能あるい
は親水性と特有の強伸性等の特性を損なうことがない。
又、絹素材の粉砕過程において絹素材が湿気を帯び、し
かも加熱に伴って強伸性を帯びることによって粉砕が困
難とされることもなく、均一の粒径からなる微細な絹粉
を確実且つ容易に作り出すことができる。
The silk powder crushed by the above method has the following features in the crushing process and the silk powder produced. First, the granular or powdery or short-fibrous silk material put into the pulverizer is incorporated into mainly an organic solvent where the silk material is insoluble, and the silk materials are mutually exchanged by this solvent. Since the material is crushed in the wrapped state, the silk materials are not fused to each other, are crushed without generating hairy broken cilia, and are not fused to the ball or the surface of the crusher. In particular, since the heat generated by grinding or impact of the ball is dispersed by the solvent and is not directly transmitted to the silk material, there is no danger that the heat will alter the silk material or cause the fusion of the silk powder to each other. In addition, since the silk powder is crushed in a state of being covered with a solvent, the silk material is swelled with moisture in the crushing process of the silk powder, or the hardening phenomenon caused by evaporation and heating of water in the crushing process. Does not occur, and the silk material mixed with the solvent contains the water content when mixed in the solvent, and does not impair the swelling function peculiar to the silk material or the properties such as hydrophilicity and peculiar strength and elongation.
Also, in the process of crushing the silk material, the silk material becomes humid, and the crushing becomes difficult due to the strong elongation accompanying heating. Can be easily produced.

【0039】更に、粉砕されて得られた絹粉は、叙上の
粉砕方法による場合では、その粒径がいずれも6μm よ
りも微細なものとされ、相互に融着し合ったり、絡み合
ったりしていない特長を有しており、しかも粉砕に用い
た溶剤中に均一に分散され、概ね絹粉が懸濁様に溶剤中
に分散されている特長を有している。そして、これらの
溶剤中の絹粉は一個一個が夫々に独立の状態で溶剤中に
浮遊していおり、外気から遮断されている。このことか
ら粉砕された絹粉の管理が容易とされ、粉砕後に絹粉が
湿気を帯びたり、硬化したり、あるいは相互に融着し合
ったりすることがない。
Further, the silk powder obtained by crushing has a particle size smaller than 6 μm in the case of the above-mentioned crushing method, and is fused or entangled with each other. In addition, it has the feature that it is uniformly dispersed in the solvent used for crushing, and that the silk powder is generally dispersed in the solvent like suspension. Each of the silk powders in these solvents floats in the solvent in an independent state and is shielded from the outside air. This facilitates the management of the crushed silk powder, and the crushed silk powder does not become wet, harden, or fuse with each other after the crushing.

【0040】尚、前記の絹素材の粉砕に先立って、絹素
材を蒸気で加熱して、セリシンを充分に除去し、しかも
フィブロインに充分な膨潤加熱を施すことによってフィ
ブロイン組織の収縮をはかり、更に、この膨潤加熱の施
されたフィブロインを、その含有水分が3重量%未満と
なるように乾燥することによりフィブロイン組織の脆弱
化をはかることがなされた。この方法で、フィブロイン
を粗粉砕して、フィブロインの粉、粒又は短繊維の径寸
法を50μm よりも細かい範囲のものに揃え、これを前記
の溶剤を媒体とした湿式粉砕の方法で粉砕した。
Prior to the crushing of the silk material, the silk material is heated with steam to sufficiently remove sericin, and the swelling heat is applied to the fibroin to measure the contraction of the fibroin tissue. The fibroin tissue was fragile by drying the swelling-heated fibroin so that the water content was less than 3% by weight. By this method, fibroin was coarsely pulverized to obtain fibroin powder, particles or short fibers having a diameter size smaller than 50 μm and pulverized by a wet pulverization method using the solvent as a medium.

【0041】かゝる方法で粉砕されたフィブロインの
粉、粒又は短繊維には繊毛部分がなく、これらを溶剤を
媒体として粉砕したところ粉砕絹粉が略“粒”状となっ
た。又、かゝる方法で溶剤を媒体としてフィブロインを
粉砕した場合、この粉砕が極めて容易且つ円滑になさ
れ、粉砕効率が飛躍的に向上することが明らかとなっ
た。更に、かゝる方法でフィブロインを粉砕したとこ
ろ、その粉砕絹粉の粒径が6μm よりも更に細かい範囲
のものとされた。このようにして6μm よりも細かく粉
砕された絹粉を、この絹粉の粉砕に用いた溶液と共に皮
膜成形用の樹脂に配合する。この配合の方法と配合の量
は、成形される樹脂製品の特性に合せて適宜決定され
る。
The fibroin powder, particles or short fibers crushed by such a method have no cilia, and when these were crushed using a solvent as a medium, the crushed silk powder became substantially "grainy". In addition, when fibroin was pulverized using a solvent as a medium by such a method, it was revealed that the pulverization was extremely easy and smooth, and the pulverization efficiency was dramatically improved. Further, when fibroin was pulverized by such a method, the grain size of the pulverized silk powder was found to be in a range finer than 6 μm. Thus, the silk powder finely pulverized to a size of 6 μm or less is blended with the resin used for film formation together with the solution used for pulverizing the silk powder. The compounding method and the compounding amount are appropriately determined according to the characteristics of the resin product to be molded.

【0042】尚、絹粉を有する溶剤の配合される樹脂
は、この溶剤の配合によって作り出される成形用の樹脂
溶液の樹脂であって、通例は成形される樹脂皮膜の樹脂
素材に適する溶剤を用いて前記の絹粉の粉砕をなす。
The resin with which the solvent containing the silk powder is blended is the resin of the resin solution for molding produced by blending this solvent, and usually a solvent suitable for the resin material of the resin film to be molded is used. And crush the above-mentioned silk powder.

【0043】従って、前記に湿式粉砕に用いる溶剤と樹
脂素材の選択により、各種の樹脂皮膜の形成がされる。
又、この絹粉を含む溶剤に配合される樹脂は、ペ−スト
状であっても粉体状ないしは液状であっても良く、この
溶剤の配合量を調節することによってペ−スト状ないし
は粘性の高い溶液状又は粘性の低い希釈溶液状とされ
る。
Therefore, various resin films are formed by selecting the solvent and the resin material used for the wet pulverization.
The resin mixed with the solvent containing the silk powder may be in a paste form, a powder form or a liquid form, and the paste form or the viscosity can be adjusted by adjusting the blending amount of the solvent. It is in the form of a solution with high viscosity or a diluted solution with low viscosity.

【0044】このようにして6μm よりも細かい絹粉を
有する溶剤の配合された樹脂を用いて皮膜を作り出す。
各種の皮膜は布、紙、皮革あるいは木製品その他の製品
の表面に塗布形成する方法と、前記溶剤を配合された樹
脂溶液中に布、紙等を漬け込み形成する方法及び離型紙
の表面にコーティングした後、この離型紙面上の樹脂皮
膜を布、樹脂シート、紙、皮革等の面に転写接着する方
法等によって作り出す。
In this way, a film is formed by using a solvent-blended resin having a silk powder finer than 6 μm.
Various coatings are formed by coating on the surface of cloth, paper, leather or wood products and other products, forming by dipping cloth, paper, etc. in a resin solution containing the above solvent, and coating on the surface of release paper. After that, the resin film on the release paper surface is created by a method such as transfer adhesion to a surface of cloth, resin sheet, paper, leather or the like.

【0045】このようにして作り出される皮膜は、素材
中に含まれる絹粉の粒径が6μm よりも微細な範囲に属
していることから皮膜の厚さが0.02〜0.002mm の範囲で
あっても、この皮膜の面から混入絹粉が浮き出したり、
突き出したりすることがなく、平滑で良好な肌触り感の
ある皮膜とされた。又、この皮膜の樹脂成形品中に含ま
れる絹粉の組成分の一部を溶出することにより、この皮
膜の面に数ミクロンよりも微細な多数の孔を設けること
ができる。
The film thus produced has a particle size of silk powder contained in the material in the range of finer than 6 μm, so that even if the film thickness is in the range of 0.02 to 0.002 mm. , Mixed silk powder is raised from the surface of this film,
The film did not stick out and was smooth and had a good feel on the skin. Further, by eluting a part of the composition of the silk powder contained in the resin molded product of this coating, it is possible to form a large number of pores finer than several microns on the surface of this coating.

【0046】このように2〜3μm よりも微細な孔を皮
膜の面に設けることによって、この皮膜に通気性がもた
らされることゝなり、特にこの皮膜にもたらされる通気
性は、0.0004μm 前後の粒径からなる水蒸気を通し、水
滴を通さない特長を有していることから耐水、透湿機能
を皮膜にもたらすものである。
By providing the surface of the film with pores finer than 2 to 3 μm, the film is provided with air permeability. Particularly, the air permeability of the film is about 0.0004 μm. Since it has the characteristic of allowing water vapor of a certain diameter to pass through and impervious to water droplets, it imparts water resistance and moisture permeability to the film.

【0047】従って、各種の布地、皮革あるいは木製品
等の表面に前記の絹粉を含む0.02〜0.002 mm厚さからな
る皮膜を形成し、この皮膜中の絹粉成分の一部を溶出し
た場合、この皮膜中の絹粉と溶出された孔とによってこ
れらの布地、皮革あるいは木製品等に特有の耐水性と透
湿性とがもたらされることゝなる。因みに、通例の雨滴
の径は2000μm であり、微細な霖雨においても100 μm
であって、この皮膜に設けられた微細な孔を通過するこ
とがない。又、この皮膜面に付着した雨滴も表面張力の
関係から前記の微細な孔を通して滲潤することがない。
Therefore, when a film having a thickness of 0.02 to 0.002 mm containing the above-mentioned silk powder is formed on the surface of various kinds of cloth, leather or wood products, and a part of the silk powder component in this film is eluted, The silk powder and the eluted pores in this film provide water resistance and moisture permeability specific to these cloths, leathers, wood products and the like. By the way, the diameter of a raindrop is 2000 μm, which is 100 μm even in the case of fine rain.
However, it does not pass through the fine holes provided in this film. Also, raindrops attached to the surface of the film do not seep through the fine holes due to the surface tension.

【0048】例3 前記6μm よりも細かい範囲の絹粉を含む溶剤を用いて
ポリウレタン樹脂塗液を作り、この塗液によってフィル
ム状の皮膜を作り、この皮膜を織編布の面に転写した。
Example 3 A polyurethane resin coating liquid was prepared by using a solvent containing silk powder in a range finer than 6 μm, a film-like film was formed by this coating liquid, and this film was transferred onto the surface of a woven or knitted fabric.

【0049】 6μm よりも微細な絹粉 15重量部 トルエン 70重量部 ポリウレタン樹脂固形分 30重量部 この樹脂溶液を離型紙の面にドクタ−ナイフコ−ティン
グ法により0.008mm の厚さで塗着し、これを乾燥した後
に該離型紙より剥ぎとって厚さ0.008mm のフィルム状の
皮膜を作った。又、この皮膜を引き剥すことなく1.5mm
厚の不織布の面に接着しながら前記離型紙を剥ぎとって
不織布の面に皮膜スキン層を作り出した。そして、この
不織布を60℃の温水中に漬け込んで15分間湯洗いしたと
ころ皮膜中に含まれている絹粉の一部が溶出し、柔かい
感触の皮膜面とされた。尚、前記の絹粉の混入量を3重
量部〜30重量部の間で各5重量部づつ増しながら皮膜を
作ったところ、前記例3の割合で絹粉を3重量部とした
ところ作り出された皮膜面の光沢が良好で、充分な耐摩
性を有している反面、接触時のベタつき感があった。
又、35重量部の絹粉を配合した皮膜面は絹特有の滑らか
な接触抵抗と良好な光沢及び風合いがある反面、耐摩耗
性に難があり、皮膜面に強い力が作用した場合に、この
皮膜面にシワよれを生じ、又前記の皮膜をラミネ−トし
た製品では、表面がヨレた状態で下地の生地面が一部露
出することがあった。従って、前記の絹粉の配合量は3
〜30重量部が最適である。しかしながら、皮膜の成形樹
脂の種別、使用溶剤の配合量及び成形条件等によって前
記の絹粉の配合量を更に変更することもできる。
Silk powder finer than 6 μm 15 parts by weight Toluene 70 parts by weight Polyurethane resin solid content 30 parts by weight This resin solution is applied on the surface of a release paper by a doctor knife coating method to a thickness of 0.008 mm, After this was dried, it was peeled off from the release paper to form a film-like film having a thickness of 0.008 mm. Also, 1.5mm without peeling off this film
The release paper was peeled off while adhering to the surface of the thick non-woven fabric to create a film skin layer on the non-woven fabric surface. When this non-woven fabric was dipped in warm water at 60 ° C. and washed with hot water for 15 minutes, a part of the silk powder contained in the film was eluted and the film surface had a soft feel. A film was prepared by increasing the amount of the above-mentioned silk powder by 5 to 5 parts by weight from 3 to 30 parts by weight. The coating surface had a good gloss and had sufficient abrasion resistance, but on the other hand, there was a sticky feeling upon contact.
Also, the coating surface containing 35 parts by weight of silk powder has smooth contact resistance and good gloss and texture peculiar to silk, but on the other hand, it has poor abrasion resistance and when a strong force acts on the coating surface, This film surface wrinkled, and in the product obtained by laminating the film, the base material surface was partially exposed in a state where the surface was distorted. Therefore, the blending amount of the above-mentioned silk powder is 3
~ 30 parts by weight is optimal. However, the blending amount of the above-mentioned silk powder can be further changed depending on the type of the molding resin of the film, the blending amount of the solvent used, the molding conditions and the like.

【0050】例4 トルエン 70重量部 6μm よりも微細な絹粉 15重量部 ポリ塩化ビニル樹脂 30重量部 この例4で作り出された塩ビ皮膜では光沢と絹特有の風
合があり、しかも柔軟性が増し、通例の塩ビ皮膜に比し
良好な肌触り感があり伸縮性が著しく増すと共に吸湿機
能がもたらされた。又前記配合量によって、皮膜の形成
がされた。
Example 4 Toluene 70 parts by weight Silk powder finer than 6 μm 15 parts by weight Polyvinyl chloride resin 30 parts by weight The PVC film produced in this example 4 has luster and a texture unique to silk, and has flexibility. As compared with the usual vinyl chloride film, it had a good feel to the touch, significantly increased stretchability, and provided a moisture absorption function. Further, a film was formed according to the above blending amount.

【0051】例5 トルエン 70重量部 6μm よりも微細な絹粉 15重量部 アクリル樹脂 30重量部 この例5の配合比率からなる樹脂溶液で皮膜を形成した
ところ同様に例4で作られた皮膜に比べて耐摩耗性に優
れ、且つ吸湿機能を有する皮膜とされた。
Example 5 Toluene 70 parts by weight Silk powder finer than 6 μm 15 parts by weight Acrylic resin 30 parts by weight When a film was formed with a resin solution having the compounding ratio of this example 5, the film similarly prepared in example 4 was obtained. Compared with this, the film was superior in abrasion resistance and had a moisture absorption function.

【0052】例6 トルエン 70重量部 6μm よりも微細な絹粉 15重量部 ポリ塩化ビニル樹脂 15重量部 アクリル樹脂 15重量部 この例6の配合比率からなる樹脂溶液を用いて形成した
皮膜は吸湿性と、接触抵抗とが良好で適度の肌触り感が
あった。
Example 6 Toluene 70 parts by weight Silk powder finer than 6 μm 15 parts by weight Polyvinyl chloride resin 15 parts by weight Acrylic resin 15 parts by weight A film formed using the resin solution having the compounding ratio of Example 6 is hygroscopic. And the contact resistance was good, and there was an appropriate feeling of touch.

【0053】例7 トルエン中で絹粉を粉砕し、この粉砕絹粉を有するトル
エンに二液反応タイプのウレタン塗料のポリエステルを
配合し、その後イソシアネートを添加配合してスプレー
ガンで膜厚0.002mmの塗膜を得た。この塗膜は艶
消し効果に優れ、手に触れたときの風合いはベトつき感
がなく良好であった。この実施例では、二液反応型ウレ
タン樹脂塗料中のポリエステルと絹粉との合計重量に対
する絹粉の量を10〜40重量%の範囲とした。この塗
膜は艶消し効果に優れ、手に触れたときこの風合いはベ
トつき感がなく良好であった。この実施例では、二液反
応型ウレタン樹脂塗料中のポリエステルと絹分との合計
重量に対する絹粉の量を10〜40重量%の範囲とし
た。
Example 7 Silk powder was crushed in toluene. Toluene having the crushed silk powder was blended with polyester of a two-component reaction type urethane paint, and then isocyanate was added and blended, and a film thickness of 0.002 mm was obtained with a spray gun. A coating film of This coating film was excellent in matting effect, and the texture when touched by hand was good without stickiness. In this example, the amount of silk powder in the two-component reactive urethane resin coating material was in the range of 10 to 40% by weight based on the total weight of polyester and silk powder. This coating film had an excellent matte effect, and when touched with the hand, the texture was good without a sticky feeling. In this example, the amount of silk powder in the two-component reactive urethane resin coating material was in the range of 10 to 40% by weight based on the total weight of polyester and silk.

【0054】例8 液状ポリウレタン樹脂液(無黄変一液型ポリウレタン、
不揮発分30%)をメチルエチルケトンの混合材を用い
て20〜50poise(25℃)に調整し、このウレ
タン樹脂100重量部中に絹粉50重量部をトルエンと
共に混合し、100poise(25℃)となるように
撹拌配合した。この混合物をPIV板にスプレーガンで
吹きつけ100℃で1分間乾燥したところ吸湿性の良好
な、しかも艶消し効果の高い塗膜が得られた。
Example 8 Liquid polyurethane resin liquid (yellowing-free one-component polyurethane,
Nonvolatile content (30%) is adjusted to 20 to 50 poise (25 ° C.) using a mixture of methyl ethyl ketone, and 100 parts by weight of this urethane resin is mixed with 50 parts by weight of silk powder together with toluene to obtain 100 poise (25 ° C.). The mixture was mixed with stirring. When this mixture was sprayed on a PIV plate with a spray gun and dried at 100 ° C. for 1 minute, a coating film having good hygroscopicity and high matting effect was obtained.

【0055】例9 ウレタン樹脂100 重量部中に絹粉40重量部を含む溶剤を
配合して得られた混合液を離型紙上にコーティングし、
乾燥後得られた0.006mm の厚さのフィルム状の皮膜を織
物基材に転写して張り合せた。このようにして作り出さ
れた織物の表面はベトつき感がなく、感触にも優れ絹特
有の風合を有していた。
Example 9 A release paper was coated with a mixed solution obtained by blending 100 parts by weight of a urethane resin with a solvent containing 40 parts by weight of silk powder,
The 0.006 mm-thick film-like film obtained after drying was transferred to a woven fabric substrate and laminated. The surface of the woven fabric thus produced was not sticky, had a good feel, and had a feeling unique to silk.

【0056】例10 離型紙上に絹粉を含む一液型ウレタン樹脂(絹粉含有の
メチルエチルケトンを溶剤とした不揮発分30重量%の混
合液)をコンマロールで塗布、乾燥し、更に、このコー
ティング層の上に、絹粉を含む二液型ウレタン樹脂(絹
粉含有のメチルエチルケトンを溶剤とした不揮発分50重
量%の混合液)を塗布、乾燥して積層皮膜を作り、この
積層皮膜を離型紙から引き剥すようにして、不織布の面
にラミネート接着した。このフィルム状のラミネート皮
膜の面を有する不織布の表面のベトつき感はなく、又絹
粉を含まないラミネート接着と同様の接着強度が得られ
た。
Example 10 A one-pack type urethane resin containing silk powder (a liquid mixture containing 30% by weight of non-volatile content in a solvent containing methyl ethyl ketone containing silk powder) was coated on a release paper with a comma roll, dried, and further coated. A two-component urethane resin containing silk powder (mixed liquid containing 50% by weight of non-volatile content of silk powder-containing methyl ethyl ketone as a solvent) is applied on the layer and dried to form a laminated film. The laminate was adhered to the surface of the non-woven fabric by peeling it off. The non-woven fabric having the film-like laminate coating surface did not have a sticky feeling, and the same adhesive strength as that obtained by laminating without silk powder was obtained.

【0057】[0057]

【発明の効果】本発明では、絹粉が溶剤によって夫々に
分離された状態で粉砕されることから、絹粉相互が直接
々触して融着し合うことがなく、粉砕に伴って絹粉に多
毛状の繊毛を生ずることがない。
According to the present invention, since the silk powder is crushed in the state of being separated by the solvent, the silk powders do not directly touch each other and are fused with each other. Does not cause hairy cilia.

【0058】このことから絹素材の粉砕が容易になさ
れ、しかも粉砕粉が粒状とされた。
From this fact, the silk material was easily crushed, and the crushed powder was made granular.

【0059】又、絹粉の粉砕に際して磨砕あるいは衝撃
粉砕に伴う熱の発生が無く、熱変化に伴う絹粉相互の融
着あるいは品質劣化の不都合を生ずることがない。
Further, when crushing the silk powder, no heat is generated due to grinding or impact crushing, and there is no inconvenience of fusion between silk powders or deterioration of quality due to heat change.

【0060】更に、溶剤で覆われた状態で絹が粉砕され
ることから、粉砕の過程において絹粉が乾燥したり、膨
潤したりすることがない。このことから絹粉の乾燥に伴
う親水性の阻害が無く、又膨潤に伴って絹粉が粘性を帯
びて粉砕が阻害される不都合もない。これらのことから
粒径が6μm よりも微細な範囲に属する絹粉を確実に、
しかも短時間で効率良く作り出すことができた。
Furthermore, since the silk is crushed while being covered with the solvent, the silk powder does not dry or swell in the crushing process. From this, there is no inconvenience that the hydrophilicity is not hindered by the drying of the silk powder, and the silk powder is viscous with the swelling and the pulverization is hindered. From these facts, it is possible to make sure that the silk powder belonging to the finer range than 6 μm is
Moreover, we were able to produce it efficiently in a short time.

【0061】更に、この微細な粒状に粉砕された絹粉が
溶剤中に懸濁状に分散されていることからこれらの絹粉
が綿状に絡み合うことが無く、皮膜の成形樹脂との配合
が円滑、容易とされ、これらの樹脂混合液中に絹粉が均
一に分散される特長を有している。従って、叙上の6μ
m よりも微細な範囲に属する絹粉を含む樹脂混合液を用
いて皮膜を形成した場合、この皮膜中に絹粉が均一に分
散された状態で、この皮膜が形成される。このことか
ら、この皮膜に絹特有の吸放湿性、光沢及び風合と適度
の接触抵抗、及び強伸性がもたらされると共に静電気の
帯電が防止される特長を有している。
Furthermore, since the finely pulverized silk powder is dispersed in a solvent in a suspended state, these silk powders do not become entangled in a cotton shape, and the film is blended with the molding resin. It has the characteristics that it is smooth and easy and that the silk powder is uniformly dispersed in these resin mixture liquids. Therefore, the above 6μ
When a film is formed using a resin mixed solution containing silk powder belonging to a range finer than m, the film is formed in a state in which the silk powder is uniformly dispersed in the film. From this fact, this film has a characteristic that moisture absorption and desorption characteristic of silk, luster and texture, appropriate contact resistance, and strong elongation are brought and electrostatic charging is prevented.

【0062】又、この皮膜に含まれる絹粉の粒径が6μ
m よりも微細であることから、この皮膜を薄く形成する
ことが可能とされた。特に皮膜としては0.006mm の厚さ
のものが作られ、形成された皮膜の面から混入絹粉が浮
き出したり、突き出したりすることがなく、肌触りが良
好で絹素材様の滑らかな面とされた。
The particle size of the silk powder contained in this film is 6 μm.
Since it is finer than m, it was possible to form this thin film. In particular, a film with a thickness of 0.006 mm was created, and the mixed silk powder did not rise or stick out from the surface of the formed film, and it had a good feel and a smooth surface similar to a silk material. .

【0063】又、形成される皮膜の面に絹粉が均一に露
呈していることから、この皮膜の面に吸着性が効果的に
もたらされ、良好な肌触り感がもたらされる。
Further, since the silk powder is uniformly exposed on the surface of the film to be formed, adsorptivity is effectively brought to the surface of this film, and a good feeling of touch is brought about.

【0064】更に、形成される皮膜の面から絹素材の一
部を溶出させた場合、この皮膜の面に数ミクロンの微少
な孔が無数に設けられることゝなり、形成されるフィル
ム等の面に特有の吸放湿機能、特に耐水透湿機能がもた
らされる特長を有している。
Furthermore, when a part of the silk material is eluted from the surface of the film to be formed, the surface of the film is innumerably provided with innumerable microscopic holes of several microns, and thus the surface of the film or the like to be formed. It has a characteristic that it has a moisture absorption and desorption function peculiar to, especially a water and moisture permeation function.

【0065】又、叙上で形成された皮膜の面にサンディ
ング処理を施した場合、皮膜に含まれている絹粉の有す
る吸湿機能、耐水透湿機能と、良好な肌触り感及び絹様
の風合いが更に助長される。
Further, when the surface of the film formed above is subjected to a sanding treatment, the silk powder contained in the film has a moisture-absorption function, a water-moisture-proof function, a good feel and a silky texture. Is further promoted.

【0066】本発明に係る絹粉を用いた皮膜は叙上にお
ける特長ある内容から絹様の表装材として各種の衣料
品、家具あるいは鞄等の身の回り用品ないしは自動車の
内装材等に用いられる他、静電気を帯びない特性をいか
して各種の電子機器と、これらのオペレーター用のキー
ボード等に用いられる。又、叙上の絹粉を有する皮膜
は、絹粉を含まない通例の皮膜の形成方法と同一の方法
ないしは手法で作り出したり、用いたりすることがで
き、日常身の回りにある全ての商品、特に衣料品類の表
面化粧材等の手段として用いることができる。
The film using the silk powder according to the present invention is used for various clothing, personal belongings such as furniture or bags, interior materials for automobiles, etc. as a silk-like surface material because of its characteristic content in the above. It is used in various electronic devices and keyboards for these operators by taking advantage of its static-free characteristics. Further, the film having silk powder on the surface can be created and used by the same method or method as the method for forming a film not containing silk powder, and can be used for all commodities in everyday life, especially clothing. It can be used as a means for surface cosmetics of goods.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 粉又は粒又は短繊維状をなす絹素材がジ
メチルフォルムアミド、トルエン等の溶剤を媒体とした
湿式粉砕により粉砕され、この粉砕絹粉が6ミクロンよ
りも微細な粒径とされていると共に、この溶剤に含まれ
た粉砕絹粉が形成樹脂皮膜組成分の一部とされているこ
とを特徴とする樹脂皮膜。
1. A silk material in the form of powder, granules or short fibers is pulverized by wet pulverization using a solvent such as dimethylformamide or toluene as a medium, and the pulverized silk powder has a particle size finer than 6 microns. In addition, the resin film is characterized in that the crushed silk powder contained in this solvent is a part of the resin film composition to be formed.
JP8220742A 1996-08-05 1996-08-05 Resin film Pending JPH09118846A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8220742A JPH09118846A (en) 1996-08-05 1996-08-05 Resin film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8220742A JPH09118846A (en) 1996-08-05 1996-08-05 Resin film

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP12302488A Division JP2599287B2 (en) 1988-05-21 1988-05-21 Silk crushing method

Publications (1)

Publication Number Publication Date
JPH09118846A true JPH09118846A (en) 1997-05-06

Family

ID=16755826

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8220742A Pending JPH09118846A (en) 1996-08-05 1996-08-05 Resin film

Country Status (1)

Country Link
JP (1) JPH09118846A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210387383A1 (en) * 2020-06-16 2021-12-16 Seiko Epson Corporation Silk thread molded body, method for manufacturing silk thread molded body, and method for manufacturing cellulose fiber regenerated molded body

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210387383A1 (en) * 2020-06-16 2021-12-16 Seiko Epson Corporation Silk thread molded body, method for manufacturing silk thread molded body, and method for manufacturing cellulose fiber regenerated molded body

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