JPH06316877A - Production of flexible artificial leather having high abrasion resistance - Google Patents

Production of flexible artificial leather having high abrasion resistance

Info

Publication number
JPH06316877A
JPH06316877A JP12465093A JP12465093A JPH06316877A JP H06316877 A JPH06316877 A JP H06316877A JP 12465093 A JP12465093 A JP 12465093A JP 12465093 A JP12465093 A JP 12465093A JP H06316877 A JPH06316877 A JP H06316877A
Authority
JP
Japan
Prior art keywords
emulsion
artificial leather
water
woven sheet
abrasion resistance
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
Application number
JP12465093A
Other languages
Japanese (ja)
Other versions
JP3047951B2 (en
Inventor
Meiji Muraoka
明治 村岡
Sadahiko Yasui
貞彦 安居
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.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
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
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Application filed by Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP5124650A priority Critical patent/JP3047951B2/en
Publication of JPH06316877A publication Critical patent/JPH06316877A/en
Application granted granted Critical
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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

PURPOSE:To obtain a flexible artificial leather having high abrasion resistance by mixing a specific inorganic neutral salt to a forcedly emulsified aqueous polyurethane emulsion having a specific particle diameter and applying the obtained treating liquid to a nonwoven sheet composed of a layer of ultrafine fibers. CONSTITUTION:A flexible artificial leather having excellent abrasion resistance can be produced by applying (A) a treating liquid produced by mixing an inorganic neutral salt (preferably Glauber's salt (Na2SO4.10H2O)) to a forcedly emulsified aqueous polyurethane emulsion having emulsion particle diameter of 0.1-2mum to (B) a nonwoven sheet produced e.g. by laminating and interlocking a nonwoven sheet made of ultrafine fibers having a single fiber fineness of <=0.5d as a surface fiber layer to a woven fabric made of a polyester fiber and heating and drying the applied emulsion.

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、柔軟で耐摩耗性良好な
人工皮革の製造方法に関する。より詳しくは本発明は、
少くとも表面繊維層として単繊維繊度0.5デニール以
下の極細繊維を主体としてなる不織シート状物に水系ポ
リウレタンエマルジョンを付与し、加熱乾燥して柔軟で
耐摩耗性良好な人工皮革を製造する方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing artificial leather which is soft and has good wear resistance. More specifically, the present invention is
A water-based polyurethane emulsion is applied to a non-woven sheet material composed mainly of ultrafine fibers having a single fiber fineness of 0.5 denier or less as at least a surface fiber layer, and dried by heating to produce an artificial leather which is soft and has good abrasion resistance. Regarding the method.

【0002】[0002]

【従来の技術】極細繊維を主体とする不織シート状物に
各種の高分子化合物を附与加工して人工皮革を得ること
は一般に広く知られており、この場合の高分子化合物は
人工皮革としての柔軟で且つ弾性のある風合及び耐久
性、寸法安定法などの物性を得るために、ポリウレタン
等の弾性高分子化合物が多く使われる。
2. Description of the Related Art It is generally known that artificial leather is obtained by adding various polymer compounds to a non-woven sheet material composed mainly of ultrafine fibers, and the polymer compound in this case is artificial leather. In order to obtain a soft and elastic texture and durability, and physical properties such as a dimensional stability method, an elastic polymer compound such as polyurethane is often used.

【0003】しかも、これらの弾性高分子化合物は有機
溶剤溶液として不織シート状物に附与し、湿式凝固され
る場合が非常に多い。しかしながら、この際使用される
有機溶剤が非常に引火性の強い且つ毒性の強い物質であ
ることが多く、火災や毒性危険防止のため溶剤回収に際
して非常に多くの注意を払う必要がある。又、溶剤も高
価であり、水の希薄液からの回収に多大のコストがかか
るという問題点がある。
In addition, these elastic polymer compounds are often applied as an organic solvent solution to a non-woven sheet material and wet-solidified. However, the organic solvent used at this time is often a highly flammable and highly toxic substance, and it is necessary to pay great attention to the recovery of the solvent in order to prevent the risk of fire and toxicity. Further, the solvent is also expensive, and there is a problem that it takes a lot of cost to recover the water from the dilute solution.

【0004】これら種々の問題点のために、不織シート
状物に附与する弾性高分子化合物を有機溶剤タイプから
水系エマルジョンタイプへ移行すべく種々検討がなされ
ているが、未だ水系エマルジョンタイプを使って満足す
べき風合と物性を有し且つ立毛品位に優れた人工皮革は
得られていない。
Due to these various problems, various studies have been made to shift the elastic polymer compound added to the non-woven sheet material from the organic solvent type to the water-based emulsion type, but the water-based emulsion type is still used. An artificial leather which has a satisfactory texture and physical properties when used and is excellent in nap quality has not been obtained.

【0005】その理由は、水系高分子エマルジョンを不
織シート状物に附与し加熱乾燥すると、水中に分散して
いた高分子エマルジョンの粒子が、水の移動に引き連ら
れて不織シート状物の表面層に集中的に付着する現象、
所謂マイグレーション現象を起すためである。即ち、こ
のマイグレーション現象によって、エマルジョン物質は
シート状物の表面層に多量に付着し内層には殆んど付着
してない状態となるため、その結果として、物性(例え
ば耐摩耗性)が低く、非常に皺の付き易い硬い風合の人
工皮革しか得られない。
The reason for this is that when an aqueous polymer emulsion is applied to a non-woven sheet material and dried by heating, the particles of the polymer emulsion dispersed in water are linked to the movement of water, and the non-woven sheet material is formed. Phenomenon that adheres intensively to the surface layer of an object,
This is because a so-called migration phenomenon occurs. That is, due to this migration phenomenon, a large amount of the emulsion substance adheres to the surface layer of the sheet-like material and hardly adheres to the inner layer, resulting in low physical properties (for example, abrasion resistance). Only artificial leather with a hard texture that is extremely wrinkled can be obtained.

【0006】又、表面層に多量のエマルジョン物質が付
着するため、表面層をバフィング等により起毛を行なっ
ても立毛形成が難しく、良好な立毛品位が得られない等
の問題があった。従来、上記問題を解決するためにマイ
グレーション現象を抑制する試みが種々なされている。
例えば、特開昭52−28904号公報に開示されてい
るようなゲル化剤及び感熱促進剤を添加した合成エマル
ジョンを45℃以下の感熱温度に調整し、繊維基布に含
浸し90℃以上の熱水浴中でゲル化させる方法がある。
Further, since a large amount of the emulsion substance adheres to the surface layer, it is difficult to form naps even if the surface layer is raised by buffing or the like, and there is a problem that a good nap quality cannot be obtained. Conventionally, various attempts have been made to suppress the migration phenomenon in order to solve the above problems.
For example, a synthetic emulsion containing a gelling agent and a heat-sensitive accelerator as disclosed in JP-A-52-28904 is adjusted to a heat-sensitive temperature of 45 ° C. or lower, impregnated into a fiber base cloth and heated to 90 ° C. or higher. There is a method of gelling in a hot water bath.

【0007】この方法は確かにマイグレーションの抑制
には有効で実験室的スケールでは実施出来るが、実際の
生産スケールでは熱水浴中へのエマルジョンの脱落が無
視出来ず、特に低濃度エマルジョン程脱落が激しく起
り、熱水浴内の汚染度が継時的に変化し、ゲル化性が微
妙に変わり、安定な品質のものをつくることが出来な
い。更に、感熱温度が低いために、年間を通じて変化す
る室温や水温の影響を受けエマルジョンが不安定になり
易く、一定の品質のものが出来ない。
This method is certainly effective in suppressing migration and can be carried out on a laboratory scale, but on an actual production scale, the loss of the emulsion in the hot water bath cannot be ignored, and in particular, the lower the concentration of the emulsion, the more likely it is. It occurs violently, the degree of contamination in the hot water bath changes over time, and the gelling property changes subtly, making it impossible to produce stable quality. Furthermore, since the heat-sensitive temperature is low, the emulsion tends to become unstable under the influence of room temperature and water temperature, which change throughout the year, and a product of constant quality cannot be produced.

【0008】また、感熱促進剤としてのノニオン系界面
活性剤は樹脂と繊維との接着力を弱める作用があり、エ
マルジョン濃度が10%以下の低濃度でその影響が顕著
に表われ、人工皮革とした場合繊維の交絡だけでは耐え
られず、スリップ現象が起り耐摩耗性が極端に低下した
り、編織物により補強布のない不織シートの場合に、染
色中に切断することもしばしば起る。又、この接着の弱
さに起因すると思えるが、樹脂自体が染色中に脱落し、
染色機壁に付着したり製品表面に再付着するなど大きな
問題が起る。
Further, the nonionic surfactant as the heat-sensitive accelerator has an action of weakening the adhesive force between the resin and the fiber, and its effect is remarkable when the emulsion concentration is as low as 10% or less. In such a case, the fiber cannot be endured only by the entanglement of the fibers, a slip phenomenon occurs, the abrasion resistance is extremely reduced, and in the case of a non-woven sheet without a reinforcing cloth due to a knitted fabric, cutting often occurs during dyeing. Also, it seems that this is due to the weak adhesion, but the resin itself fell off during dyeing,
There are major problems such as adhesion to the dyeing machine wall and redeposition on the product surface.

【0009】このような感熱剤添加の弊害を取り除くた
めにポリウレタンエマルジョン自体に感熱凝固能をもた
せた特開昭57−39286号公報が開示されている。
しかし、この方法は凝固の際の熱雰囲気の設定が重要で
あり、実施例に示されるように熱水処理でのゲル化であ
れば可能であるが、加熱乾燥では熱伝達が悪いため、ゲ
ル化性が悪くマイグレーションを抑制することは難かし
い。
Japanese Unexamined Patent Publication (Kokai) No. 57-39286 discloses that the polyurethane emulsion itself has a heat-sensitive coagulation ability in order to eliminate such a harmful effect of the addition of the heat-sensitive agent.
However, in this method, it is important to set the hot atmosphere during solidification, and as shown in the examples, it is possible if it is gelation by hot water treatment, but heat transfer is poor in heat drying, so gel It is difficult to suppress migration because of poor chemicalization.

【0010】又、これら従来技術は単糸2.0〜8.0
d程度の比較的太い繊維の領域にのみ有効であり、本発
明のような0.5d以下の極細繊維層を有す領域では毛
管現象が激しくエマルジョン粒子のマイグレーションが
一層起り易く満足すべきものは得られない。 まして
や、不織シートが高目付けになると、その影響は顕著で
ある。更に、これら従来技術に共通していえることは、
20%以上の高濃度エマルジョンの含浸を前提とした技
術思想であるため、得られる人工皮革の風合は全体的に
硬いものとなる。このようにいずれの方法においても、
工程性がよくしかも、品質、特に耐摩耗性や風合を同時
に満たすことは容易ではなかった。
Further, in these prior arts, single yarn 2.0 to 8.0 is used.
It is effective only in the region of relatively thick fibers of about d, and in the region having an ultrafine fiber layer of 0.5d or less as in the present invention, capillarity is severe and migration of emulsion particles is more likely to occur. I can't. In addition, when the non-woven sheet has a high basis weight, the effect is remarkable. Furthermore, what can be said in common with these conventional techniques is that
Since the technical idea is premised on the impregnation with a high-concentration emulsion of 20% or more, the texture of the obtained artificial leather becomes hard as a whole. Thus, in either method,
It has not only been easy to process, but it has not been easy to simultaneously satisfy quality, especially wear resistance and texture.

【0011】[0011]

【発明が解決しようとする課題】本発明者らは、かかる
課題を解決すべく鋭意検討の結果、本発明に達した。即
ち、本発明の目的は、水系ポリウレタンエマルジョンを
使用して、柔軟で耐摩耗性良好な人工皮革を工業的に安
定に製造する方法を提供することにある。
DISCLOSURE OF THE INVENTION The inventors of the present invention have achieved the present invention as a result of extensive studies to solve the above problems. That is, an object of the present invention is to provide a method for industrially producing artificial leather that is flexible and has good wear resistance, using an aqueous polyurethane emulsion.

【0012】[0012]

【課題を解決するための手段】本発明の目的は、少くと
も表面繊維層として単繊維繊度0.5デニール以下の極
細繊維を主体としてなる繊維層を含んでなる不織シート
状物に、強制乳化された非イオン性のエマルジョンで、
それを構成するエマルジョン粒子の平均粒径が0.1〜
2.0μmである水系ポリウレタンエマルジョンに無機
塩類を溶解、混合した処理液を付与し、加熱乾燥するこ
とにより達成される。
The object of the present invention is to force a non-woven sheet-like article comprising a fiber layer mainly containing ultrafine fibers having a single fiber fineness of 0.5 denier or less as a surface fiber layer. An emulsified nonionic emulsion,
The average particle size of the emulsion particles constituting it is 0.1
This is accomplished by dissolving and mixing inorganic salts in a water-based polyurethane emulsion having a thickness of 2.0 μm, applying a treatment liquid, and heating and drying.

【0013】以下、本発明を詳細に説明する。本発明に
用いる不織シート状物は、表面繊維層として単繊維繊度
0.5デニール以下の極細繊維を主体としてなる繊維層
を有すれば、前記表面繊維層につながる層としてはどの
ような構成シート状物を用いてもよい。例えば、表面繊
維層と同一構成の繊維層で不織シート状物全体を構成し
てもよく、また表面繊維層につながる層として、表面繊
維層で片面全体が覆われ、且つ三次元交絡している編織
物からなる層を配置してもよい。後者の場合には、前記
編織物の下層に任意の構成シート状物をつなげて配置し
てもよい。
The present invention will be described in detail below. If the non-woven sheet material used in the present invention has a fiber layer mainly composed of ultrafine fibers having a single fiber fineness of 0.5 denier or less as the surface fiber layer, what structure is used as the layer connected to the surface fiber layer? A sheet material may be used. For example, the entire non-woven sheet-like material may be constituted by a fiber layer having the same structure as the surface fiber layer, and as a layer connected to the surface fiber layer, one surface is entirely covered by the surface fiber layer and three-dimensionally entangled. You may arrange | position the layer which consists of the knitted fabric which exists. In the latter case, any constituent sheet-like material may be connected to the lower layer of the knitted fabric and arranged.

【0014】前記単繊維繊度0.5デニール以下の極細
繊維の繊維素材としては、通常の人工皮革に用いられる
ものなら特に制限はなく、例えばポリエチレンテレフタ
レート(P.E.T.)、ナイロン6、ナイロン66、
ポリアクリルニトリル等を用いることが出来る。極細繊
維としては、通常の湿式、乾式及び溶融紡糸法により直
接紡糸されたもの、更にメルトブローン法、海島型繊維
及びポリマープレンド繊維から一成分を抽出除去する方
法、及び割繊糸法等によって得られるものが使用出来
る。
The fiber material of the ultrafine fibers having a single fiber fineness of 0.5 denier or less is not particularly limited as long as it is used for ordinary artificial leather. For example, polyethylene terephthalate (PET), nylon 6, Nylon 66,
Polyacrylonitrile or the like can be used. As the ultrafine fibers, those obtained by direct spinning by ordinary wet, dry and melt spinning methods, and further by melt blown method, method of extracting and removing one component from sea-island type fiber and polymer blended fiber, split fiber method and the like can be obtained. Things can be used.

【0015】本発明においては、前記方法で得られる単
繊維繊度0.5デニール以下の極細繊維を主体としてな
る表面繊維層を有する不織シート状物が適用される。該
単繊維繊度が0.5デニール以上の場合は、繊維の剛性
が大きく表面立毛の腰が強いために、人工皮革特有の高
級な表面品位、手触り感、及びラィティング効果を得る
ことが出来ない。
In the present invention, a non-woven sheet material having a surface fiber layer mainly composed of ultrafine fibers having a single fiber fineness of 0.5 denier or less obtained by the above method is applied. When the monofilament fineness is 0.5 denier or more, the rigidity of the fiber is large and the nap of the surface is strong, so that it is not possible to obtain the high-grade surface quality, touch feeling, and lighting effect specific to artificial leather.

【0016】また、不織シート状物中に少量の温水可溶
性短繊維(例えばビニロン)を混合することは本発明の
目的を阻害しない範囲で構わない。その場合の混合率は
50%以下を目途とする。50%以上になるとポリウレ
タン樹脂の把持力の低下や染色時の泡の発生等悪影響が
クローズアップする。不織シート状物を得る方法として
は、上記各種極細繊維から、カード、クロスレイヤー、
ランダムウェーバー等の乾式法、及び水中に極細繊維を
分散させて湿式抄造法等により不織ウエブを製造し、ニ
ードルパンチ、流体交絡処理により交絡一体化すること
によって得られる。
Further, a small amount of warm water-soluble short fibers (for example, vinylon) may be mixed in the non-woven sheet material as long as the object of the present invention is not impaired. In that case, the mixing ratio is set to 50% or less. When it is 50% or more, adverse effects such as a reduction in the gripping force of the polyurethane resin and the occurrence of bubbles during dyeing are highlighted. As a method for obtaining a non-woven sheet, a card, a cross layer,
It can be obtained by producing a non-woven web by a dry method such as a random weber, or by dispersing ultrafine fibers in water by a wet papermaking method, and entangled and integrated by needle punching and fluid entanglement treatment.

【0017】本発明者らは、ある限定された条件の水系
ポリウレタンエマルジョンに感熱剤として無機塩類を溶
解し、混合することによって、従来加熱乾燥では熱伝達
効率が悪く、特に0.5d以下の極細繊維からなる高目
付けシートでは達成が困難とされていたマイグレーショ
ンを見事に抑制させることが出来るだけでなく、20%
未満の低濃度エマルジョンにおいてもゲル化による造膜
が可能であるという新しい知見を得て本発明を完成した
ものである。
By dissolving inorganic salts as a heat-sensitive agent in a water-based polyurethane emulsion under certain limited conditions and mixing them, the heat transfer efficiency in conventional heating and drying is poor, and the inventors of the present invention have an extremely fine particle size of 0.5 d or less. It is possible not only to suppress the migration, which was difficult to achieve with a high basis weight sheet made of fiber, but also to achieve 20%.
The present invention has been completed by obtaining new knowledge that a film can be formed by gelation even in a low-concentration emulsion having a concentration of less than 1.

【0018】本発明の方法によって得られた不織シート
状物の断面を電子顕微鏡で観察してみると、マイグレー
ションが抑制されたウレタン樹脂が無機塩類の結晶を介
することなく直接繊維に付着し、繊維同志を接着固定し
ている様子が観察された。結晶塩は、樹脂や繊維の表面
や更には、不織シート状物の表裏面へマイグレートして
付着していた。念のために、このゲル化させた不織シー
ト状物を水洗し塩を除去したものを再度電子顕微鏡で観
察したが、樹脂の付着状態に変化は見られなかった。
When the cross section of the non-woven sheet material obtained by the method of the present invention is observed by an electron microscope, the urethane resin whose migration is suppressed adheres directly to the fiber without interposing the crystals of the inorganic salt, It was observed that the fibers were bonded and fixed. The crystalline salt migrated and adhered to the surface of the resin or fiber, and further to the front and back surfaces of the non-woven sheet material. As a reminder, the gelled non-woven sheet-like product was washed with water and the salt was removed, and the product was observed again with an electron microscope, but no change was observed in the resin adhesion state.

【0019】このことより、ウレタン粒子がゲル化の過
程で結合し、樹脂膜を強固なものとしつつ固形化し、塩
は塩の水溶液となってマイグレートしているものと考え
られる。従って、樹脂のバインダーとしての性能は十分
であると考えられる。
From this, it is considered that the urethane particles are bonded in the process of gelation, solidify while solidifying the resin film, and the salt migrates as an aqueous solution of the salt. Therefore, the performance of the resin as a binder is considered to be sufficient.

【0020】本発明によれば、水系ポリウレタンエマル
ジョンを低濃度で含浸しても、物性、特に耐摩耗性を大
巾に低下させることがないという大きな特徴を有する。
これは、恐らく、先の樹脂の付着状態によるところが大
きいと考えられ、感熱剤を界面活性剤に代えたり、熱水
ゲル化させる従来の方式のものとは樹脂の接着状態が本
質的に異なると考えてる。
According to the present invention, even if the water-based polyurethane emulsion is impregnated at a low concentration, the physical properties, especially abrasion resistance, are not significantly deteriorated.
It is considered that this is largely due to the adhesion state of the resin, and that the resin adhesion state is essentially different from that of the conventional method in which the heat sensitive agent is replaced with a surfactant or hot water gelation is performed. Thinking.

【0021】本発明により水系ポリウレタンエマルジョ
ンの低濃度含浸が可能となったので、風合の柔軟化が一
気に達成出来た。更に、不織シート状物の内部に織編物
を封入して補強した基布に本発明の方法を適用すれば、
3〜5%の極低濃度エマルジョンでも実用に十分耐える
耐摩耗性能を付与することができ、しかも、該水系ポリ
ウレタンエマルジョンが低濃度であるために、極細繊維
の保有する独得な柔軟な風合を保持することが出来る。
According to the present invention, it is possible to impregnate a water-based polyurethane emulsion at a low concentration, so that the softening of the texture can be achieved at a stretch. Furthermore, if the method of the present invention is applied to a base fabric in which a woven or knitted material is enclosed and reinforced inside a non-woven sheet material,
Even with an extremely low concentration emulsion of 3 to 5%, abrasion resistance performance that can withstand practical use can be imparted. Moreover, since the aqueous polyurethane emulsion has a low concentration, the unique soft texture possessed by the ultrafine fibers can be obtained. Can hold.

【0022】勿論、10%以上の高濃度エマルジョンを
含浸しても風合は固くならずむしろ充実感が付与された
ものが得られる。又、家具用途等資材分野においては、
200g/m2 以上の高目付が要求されるがその場合で
も広い範囲の濃度条件が適用でき、特に10%以上の高
濃度条件と組み合わせれば高度の耐摩耗性が付与され、
その割には風合は柔軟で腰があり、決してペーパーライ
クなものとはならない。
Of course, even if a high-concentration emulsion of 10% or more is impregnated, the texture does not become hard, but rather a solid feeling is obtained. In the field of furniture and other materials,
A high basis weight of 200 g / m 2 or more is required, but even in that case, a wide range of concentration conditions can be applied, and particularly when combined with a high concentration condition of 10% or more, a high degree of wear resistance is imparted,
For that reason, the texture is flexible and chewy, and it is never paper-like.

【0023】本発明の構成条件について更に詳しく説明
する。本発明の水系ポリウレタンエマルジョンは、乳化
剤、例えば非イオン系乳化剤、アニオン性乳化剤の存在
下で高い機械的剪断力で水中により強制乳化した非イオ
ン性エマルジョンであり、そのエマルジョン粒子の平均
粒子径が0.1〜2.0μmという通常のウレタンエマ
ルジョン粒子にしてはやや大きめであることが最大の特
徴である。
The constituent conditions of the present invention will be described in more detail. The water-based polyurethane emulsion of the present invention is a nonionic emulsion that is forcibly emulsified in water with high mechanical shearing force in the presence of an emulsifier such as a nonionic emulsifier or anionic emulsifier, and the average particle diameter of the emulsion particles is 0. The most distinctive feature is that the urethane emulsion particles of 1 to 2.0 μm are rather large.

【0024】本発明の水系ポリウレタンエマルジョンを
得る強制乳化法としては、例えば反応の完了した液状ポ
リウレタンポリマーを該乳化剤でエマルジョン化する転
相乳化法、末端イソシアネートプレポリマーを乳化分散
すると同時に/又はその後にアミン類等の鎖伸長剤で鎖
伸長反応を完結させ、高分子量化して得られるプレポリ
マー法が挙げられ、特に良好な摩粍性のシートを得るた
めにはプレポリマー法が特に好ましい。
Examples of the forced emulsification method for obtaining the water-based polyurethane emulsion of the present invention include, for example, a phase inversion emulsification method in which a liquid polyurethane polymer of which the reaction is completed is emulsified with the emulsifier, and at the same time when the terminal isocyanate prepolymer is emulsified and / or thereafter. Examples thereof include a prepolymer method obtained by completing the chain extension reaction with a chain extender such as amines to obtain a high molecular weight, and the prepolymer method is particularly preferable in order to obtain a sheet having particularly good abrasion properties.

【0025】また、乳化分散性を向上させるために、ポ
リウレタンのポリマー分子骨格に、エチレンオキサイド
又はプロピレンオキサイド等の高分子付加物のようなノ
ニオン性の親水基をを側鎖に導入したり、耐熱性、耐熱
水性を向上させる目的で、トリメチロールプロパン等の
三官能グリコール、三官能アミン等を反応させ、架橋構
造を形成するなどのポリウレタン自体の変性による改質
手段も本発明に好適に用いられる。
In order to improve the emulsification dispersibility, a nonionic hydrophilic group such as a polymer adduct such as ethylene oxide or propylene oxide is introduced into the side chain of the polymer molecular skeleton of polyurethane, or heat resistance is improved. In order to improve the properties and hot water resistance, modification means by modifying the polyurethane itself such as by reacting a trifunctional glycol such as trimethylolpropane, a trifunctional amine or the like to form a crosslinked structure is also suitably used in the present invention. .

【0026】しかしながら、ポリマー分子骨格にカルボ
ン酸基等のアニオン性の親水基を導入して乳化分散性を
向上せしめた、アニオン性の水系ポリウレタンエマルジ
ョンは逆に耐熱性、耐熱水性が低下するばかりか、乾燥
時のエマルジョン粒子のマイグレーションを十分に抑制
できず、本発明の効果が得られない。
However, an anionic water-based polyurethane emulsion in which an anionic hydrophilic group such as a carboxylic acid group is introduced into the polymer molecular skeleton to improve the emulsification dispersibility, on the contrary, not only lowers heat resistance and hot water resistance, However, the migration of emulsion particles during drying cannot be sufficiently suppressed, and the effect of the present invention cannot be obtained.

【0027】本発明の水系ポリウレタンエマルジョンに
おいて、エマルジョン粒子の平均粒子径が0.1μm未
満では乾燥時のマイグレーションを抑制出来ず、本発明
の柔軟で耐磨耗性の良好な人工皮革は得られないし、ま
た本発明の方法を工業的に且つ安定に実施することが困
難である。又、2.0μmを越えると、エマルジョンの
安定も悪くなるが、樹脂としての造膜性も劣り、染色時
の脱落、耐摩耗性を満たすことが出来ない。
In the water-based polyurethane emulsion of the present invention, if the average particle size of the emulsion particles is less than 0.1 μm, migration during drying cannot be suppressed and the soft and abrasion-resistant artificial leather of the present invention cannot be obtained. Moreover, it is difficult to carry out the method of the present invention industrially and stably. On the other hand, if it exceeds 2.0 μm, the stability of the emulsion is deteriorated, but the film-forming property as a resin is poor, and the drop-off at the time of dyeing and the abrasion resistance cannot be satisfied.

【0028】該エマルジョンに混合添加する無機塩類と
しては、アルカリ金属又はアルカリ土類金属からなる中
性塩で一価又は二価の硫酸塩、硝酸塩、塩化物である。
例えば、NaCl、Na2 SO4 、NaNO3 、CaS
4 、CaCl2 、MgCl2 などが挙げられる。工程
管理、原料の入手のし易さ、経済性、公害など総合的に
考えると、Na2 SO4 が最も有効である。
The inorganic salts mixed and added to the emulsion are neutral salts of alkali metals or alkaline earth metals, which are monovalent or divalent sulfates, nitrates and chlorides.
For example, NaCl, Na 2 SO 4 , NaNO 3 , CaS
O 4 , CaCl 2 , MgCl 2 and the like can be mentioned. In terms of process control, availability of raw materials, economic efficiency, and pollution, Na 2 SO 4 is most effective.

【0029】無機塩類の添加濃度は、塩の種類によって
ゲル化性が異なるので一概にいえないが、エマルジョン
に対して1〜10%が望ましい。本発明の水系ポリウレ
タンエマルジョンを加温しても、20%未満では感熱凝
固しないが、該無機塩類を添加することで80℃以下の
温度に加温した時に感熱ゲル化を生じるように調整すべ
きである。多量に無機塩類を添加するとエマルジョンが
室温でゲル化を起すことがある。
The addition concentration of the inorganic salt cannot be generally determined because the gelation property varies depending on the type of salt, but it is preferably 1 to 10% with respect to the emulsion. Even if the water-based polyurethane emulsion of the present invention is heated, it does not heat-coagulate at less than 20%, but it should be adjusted by adding the inorganic salts so that heat-sensitive gelation occurs when heated to a temperature of 80 ° C. or less. Is. Addition of a large amount of inorganic salts may cause the emulsion to gel at room temperature.

【0030】本発明の水系ポリウレタンエマルジョンを
構成するポリウレタン成分の組成としては、以下のもの
が例示される。ポリオール成分としてポリエチレンアジ
ペートグリコール、ポリブチレンアジペートグリコール
などのポリエステルジオール類;ポリエチレングリコー
ル、ポリテトラメチレングリコールなどのポリエーテル
グリコール類;ポリカーボネートジオール類等が挙げら
れる。イソシアネート成分としては、ジフェニルメタン
−4,4’−ジイソシアネート等の芳香族ジイソシアネ
ート;ジシクロヘキシルメタン−4,4’−ジイソシア
ネート等の脂環族ジイソシアネート;ヘキサメチレンジ
イソシアネート等の脂肪族ジイソシアネート等が挙げら
れる。
The following are examples of the composition of the polyurethane component constituting the water-based polyurethane emulsion of the present invention. Examples of the polyol component include polyester diols such as polyethylene adipate glycol and polybutylene adipate glycol; polyether glycols such as polyethylene glycol and polytetramethylene glycol; and polycarbonate diols. Examples of the isocyanate component include aromatic diisocyanates such as diphenylmethane-4,4′-diisocyanate; alicyclic diisocyanates such as dicyclohexylmethane-4,4′-diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate.

【0031】また、鎖伸長剤としては、エチレングリコ
ール等のグリコール類;エチレンジアミン、4,4’−
ジアミノジフェニルメタン等のジアミン類などを挙げる
ことができる。そして、上記各種成分を適宜組合せて原
料ポリウレタンとすることができる。
As the chain extender, glycols such as ethylene glycol; ethylenediamine, 4,4'-
Examples thereof include diamines such as diaminodiphenylmethane. Then, a raw material polyurethane can be obtained by appropriately combining the above-mentioned various components.

【0032】また、エマルジョン中に必要に応じて紫外
線吸収剤、酸化防止剤等の安定剤、顔料等の着色剤、浸
透剤などの界面活性剤、防黴剤、増粘剤、ポリビニルア
ルコール、CMC等の水溶性高分子化合物、ポリビニル
メチルエーテル系などの熱感促進剤などを添加すること
ができる。無機塩類を添加した水系ウレタンエマルジョ
ンの不織シート状物への付与方法は、従来の含浸法、ス
プレー法、コーティング法等任意の方法によって行なう
ことが出来る。
In the emulsion, if necessary, a UV absorber, a stabilizer such as an antioxidant, a coloring agent such as a pigment, a surfactant such as a penetrant, an antifungal agent, a thickener, polyvinyl alcohol, CMC. A water-soluble polymer compound such as the above, a heat sensation accelerator such as a polyvinyl methyl ether type, and the like can be added. The water-based urethane emulsion to which the inorganic salt is added can be applied to the non-woven sheet material by any method such as a conventional impregnation method, a spray method and a coating method.

【0033】水系ポリウレタンエマルジョンを構成する
ポリウレタン樹脂の付与量(固形分)は、目的に応じて
任意の値が採用される。一般的には不織シート状物10
0重量部に対し3〜100重量部である。更に、加熱乾
燥の具体的方法としては、熱風乾燥、赤外線加熱、高周
波加熱等任意の加熱手段を適用出来るが、設備投資額、
維持管理の容易さ等から考えると、ピンテンターやクリ
ップテンターなどの熱風乾燥機が一般的である。
The applied amount (solid content) of the polyurethane resin constituting the water-based polyurethane emulsion may be any value depending on the purpose. Non-woven sheet material 10
It is 3 to 100 parts by weight with respect to 0 parts by weight. Further, as a specific method of heating and drying, any heating means such as hot air drying, infrared heating, and high frequency heating can be applied.
Hot air dryers such as pin tenters and clip tenters are generally used in consideration of the ease of maintenance.

【0034】乾燥温度は感熱性を付与した水系ポリウレ
タンエマルジョンのゲル化温度以上である。一般的に
は、上記エマルジョンのゲル化温度は60〜80℃とす
るのが、加熱前にゲル化することがなく好ましい。ゲル
化した樹脂の性能を十分発揮させるために、最低でも1
10℃は必要で、望ましくは130℃以上である。しか
し、樹脂の耐熱性や繊維の劣化を考えると、180℃以
上は避けるべきである。
The drying temperature is equal to or higher than the gelation temperature of the water-based polyurethane emulsion having heat sensitivity. Generally, the gelling temperature of the emulsion is preferably 60 to 80 ° C., because it does not gel before heating. At least 1 in order to maximize the performance of the gelled resin
10 ° C. is necessary, and is preferably 130 ° C. or higher. However, considering the heat resistance of the resin and the deterioration of the fiber, 180 ° C or higher should be avoided.

【0035】本発明の方法が適用される不織シート状物
は、人工皮革用原反として直接染色機へ投入して製品と
して仕上げることが出来る。特に、液流揉布染色機を用
いると起毛のなびきの良さの他、柔軟性を更に高めるこ
とができ有効である。又、本発明の水系ポリウレタンエ
マルジョンを、不織シート状物に付与する前に、不織シ
ート状物を予め染色等で着色することは、エマルジョン
物質に吸尽される染料のロスを防ぐことが出来る点で好
ましい。
The non-woven sheet material to which the method of the present invention is applied can be directly put into a dyeing machine as an original fabric for artificial leather to be finished as a product. In particular, the use of a jet kneading machine is effective because the flexibility of the raised hair and the flexibility can be further increased. Further, prior to applying the water-based polyurethane emulsion of the present invention to the non-woven sheet material, coloring the non-woven sheet material in advance by dyeing or the like can prevent loss of dye exhausted to the emulsion substance. It is preferable because it can be done.

【0036】[0036]

【実施例】本発明を下記の実施例により説明するが、そ
れらは本発明の範囲を制限しない。なお、物性はそれぞ
れの試料をサーキュラー染色後に測定した。実施例の説
明中に用いられる各測定値の測定方法は下記の通りであ
る。 平均粒子径;堀場製作所製、自動粒径測定装置を用
い、分散媒を水とした光透過法遠心沈降法によりディス
ク回転速度3000rpmで測定する。 容積基準で測定したメジアン径で表わす。
The present invention is illustrated by the following examples, which do not limit the scope of the invention. The physical properties were measured after circular staining of each sample. The measuring method of each measured value used in the description of the examples is as follows. Average particle diameter: Measured at a disk rotation speed of 3000 rpm by an optical transmission method centrifugal sedimentation method using water as a dispersion medium using an automatic particle size measuring device manufactured by Horiba Ltd. It is represented by the median diameter measured on a volume basis.

【0037】 柔軟度 ;L1079−A法(45°
カンチレバー法) 摩耗強度;L1096法(マーチンデール法)
Flexibility; L1079-A method (45 °
Cantilever method) Abrasion strength; L1096 method (Martindale method)

【0038】(実施例1)直接紡糸法によって単繊維繊
度0.1デニールのPET極細繊維を製造し、長さ5m
mに切断した細短繊維を水中に分散せしめ抄造用スラリ
ーとした。このスラリーを抄造し、目付50g/m2
不織シートを製造した。75デニール/36フィラメン
トのPET繊維からなる目付量50g/m2 の平織物の
両面に上記不織シートを積層し、高速水流の噴射により
三次元的に交絡一体化させた。高速水流は孔径0.1m
mの直進流噴射ノズルから30kg/cm2 の圧力で噴
射した。
Example 1 A PET ultrafine fiber having a single fiber fineness of 0.1 denier was produced by the direct spinning method, and the length thereof was 5 m.
The short staple fibers cut into m were dispersed in water to obtain a papermaking slurry. This slurry was made into a paper to produce a nonwoven sheet having a basis weight of 50 g / m 2 . The above-mentioned non-woven sheets were laminated on both sides of a plain woven fabric made of PET fiber of 75 denier / 36 filaments and having a basis weight of 50 g / m 2 , and three-dimensionally entangled and integrated by jetting a high-speed water stream. High-speed water flow has a hole diameter of 0.1 m
It was jetted at a pressure of 30 kg / cm 2 from a straight-flow jet nozzle of m.

【0039】積層シートは下面に吸引装置を有する80
メッシュの金網にのせ、ノズルから30mmの位置で高
圧水流を衝突させた。積層シートの表裏両面からこの操
作を行ない目付量150g/m2 、厚さ0.55mmの
シート状物を製造した。このシート状物を#400のエ
メリーペーパーを用い、ペーパー速度700m/分で表
面をバフィングした。これに平均粒子径0.3μmのポ
リエーテル系水系ポリウレタンエマルジョン(第一工業
製薬社製「スーパーフレックス」強制乳化型、非イオン
系固形分45重量%)7%濃度で感熱剤としてNa2
4 5%を加えた調合液を作成した。
The laminated sheet has a suction device on the lower surface 80
It was placed on a wire mesh and a high-pressure water stream was made to collide at a position 30 mm from the nozzle. This operation was performed from both the front and back sides of the laminated sheet to produce a sheet-like material having a basis weight of 150 g / m 2 and a thickness of 0.55 mm. The surface of this sheet was buffed using # 400 emery paper at a paper speed of 700 m / min. To this, a polyether-based water-based polyurethane emulsion having an average particle size of 0.3 μm (Daiichi Kogyo Seiyaku Co., Ltd. “Superflex” forced emulsification type, nonionic solid content 45% by weight) was added at a concentration of 7% and Na 2 S as a heat-sensitive agent.
A mixed solution containing O 4 5% was prepared.

【0040】この調合液を攪拌しながら加温したところ
60℃でゲル化物が認められた(ちなみに、感熱剤を添
加しない7%濃度の同じエマルジョンは85℃まで加温
したが、全くゲル化物は認められなかった。)。この調
合液を先のシート状物に含浸し、マングルでピックアッ
プ率150%になるように絞った。次いで、130℃の
ピンテンター乾燥機で3分加熱乾燥した。
When this prepared solution was heated with stirring, a gelled product was observed at 60 ° C. (By the way, the same emulsion of 7% concentration without addition of the heat sensitive agent was heated to 85 ° C., but no gelled product was formed. I was not able to admit.). The above sheet-shaped material was impregnated with this prepared solution, and was squeezed with a mangle so that the pickup rate was 150%. Then, it was heated and dried for 3 minutes in a pin tenter dryer at 130 ° C.

【0041】この不織シートを染色前にその一部を水洗
乾燥し、断面を電子顕微鏡で観察したところ、中心層迄
均一に樹脂が付着している様子が見られた。上記不織シ
ートを水洗なしにサーキュラー染色し、乾燥仕上げを行
なったところ、満足すべき物性と風合を有し、立毛品位
の優れたスエード調人工皮革が得られた。このスエード
調人工皮革の物性を表1に示す。
A part of this non-woven sheet was washed with water and dried before dyeing, and the cross section was observed with an electron microscope. As a result, it was found that the resin was evenly attached to the central layer. When the above-mentioned non-woven sheet was circularly dyed without washing with water and dried, a suede-like artificial leather having satisfactory physical properties and texture and excellent nap quality was obtained. The physical properties of this suede-like artificial leather are shown in Table 1.

【0042】(実施例2)実施例1で使用した不織シー
ト状物に、平均粒子径の異なる次の3種のポリエーテル
系水系ポリウレタンエマルジョン(0.08μm、1.
4μm、2.2μm)(第一工業製薬社製、「スーパー
フレックス」強制乳化型、非イオン系、固形分45重量
%)を各々7%濃度に調合し、感熱剤としてNa2 SO
4 5%で一定とした調合液を前記不織シートを含浸し、
実施例1と同様にしてスエード調人工皮革を得た。これ
ら人工皮革の物性を実施例2−1、2−2、2−3とし
て表1に示す。
Example 2 The non-woven sheet material used in Example 1 was prepared by adding the following three types of polyether-based water-based polyurethane emulsions (0.08 μm, 1.
4 μm, 2.2 μm) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., “Superflex” forced emulsification type, nonionic, solid content 45% by weight) were each mixed to a concentration of 7%, and Na 2 SO 4 was used as a heat-sensitive agent.
The non-woven sheet is impregnated with a fixed solution of 45%,
A suede-like artificial leather was obtained in the same manner as in Example 1. The physical properties of these artificial leathers are shown in Table 1 as Examples 2-1, 2-2 and 2-3.

【0043】(比較例1)実施例1,2で用いたそれぞ
れ平均粒子径0.3、1.4μmの水系ポリウレタンエ
マルジョンの7%濃度に、感熱剤としてNa2 SO4
添加せず、実施例1と同様な調合として不織シートに適
合したが、いずれも硬くてシワの付き易い風合であり、
摩耗強度も極端に悪く、表面立毛は全く発現しなかっ
た。この人工皮革の物性を表1に示す。
(Comparative Example 1) The experiment was carried out without adding Na 2 SO 4 as a heat-sensitive agent to 7% concentration of the water-based polyurethane emulsions having average particle diameters of 0.3 and 1.4 μm used in Examples 1 and 2, respectively. The same composition as in Example 1 was applied to the non-woven sheet, but all had a hard and wrinkle-prone texture,
The abrasion strength was also extremely poor and no surface nap was developed. The physical properties of this artificial leather are shown in Table 1.

【0044】[0044]

【表1】 [Table 1]

【0045】(比較例2)実施例1で使用した不織シー
ト状物に平均粒子径0.3、1.4μmのアニオン性水
系ポリウレタンエマルジョン(第一工業製薬(株)製
「スーパーフレクッスシリーズ、固形分40%)の7%
濃度に、感熱剤としてNa2 SO4 5%で調合、含浸
し、ピックアップ率150%で絞り、130℃のピンテ
ンター乾燥機で3分加熱乾燥した後、水洗なしでサーキ
ュラー染色して仕上げた。
(Comparative Example 2) An anionic water-based polyurethane emulsion having an average particle diameter of 0.3 and 1.4 μm was added to the non-woven sheet material used in Example 1 (“Superflex series, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.”). , Solid content 40%) 7%
The mixture was prepared and impregnated with Na 2 SO 4 5% as a heat-sensitive agent to a concentration, squeezed at a pick-up rate of 150%, heat-dried for 3 minutes in a pin tenter dryer at 130 ° C., and then circular dyed without washing to finish.

【0046】しかし、いずれの粒径のものも、感熱ゲル
化が不充分で表面立毛は全く発現せず、ダンボール状の
硬い風合いであった。また、感熱剤をMgCl2 5%に
変えて同様な実験をしたが、結果は同じであった。
However, in any of the particle sizes, the heat-sensitive gelation was insufficient, surface naps did not appear at all, and the cardboard-like hard texture was obtained. Further, the same experiment was conducted by changing the heat sensitive agent to 5% of MgCl 2 , but the result was the same.

【0047】(実施例3)実施例1と同様の抄造用スラ
リーを用いて目付120g/m2 の不織シートを製造し
た。75デニール/36フィラメントのPET繊維から
なる目付量50g/m2 の平織物の両面に前記不織シー
トを積層し、実施例1と同様な方法で290g/m2
不織シートを製造し、#400のエメリーペーパーで表
面をバフィングした。
(Example 3) Using the same papermaking slurry as in Example 1, a nonwoven sheet having a basis weight of 120 g / m 2 was produced. The non-woven sheet of 290 g / m 2 was produced in the same manner as in Example 1 by laminating the non-woven sheet on both sides of a plain weave fabric made of PET fiber of 75 denier / 36 filament and having a basis weight of 50 g / m 2 . The surface was buffed with # 400 emery paper.

【0048】これに平均粒径0.3μmのポリエーテル
系水系ポリウレタンエマルジョン(第一工業製薬社製
「スーパーフレックス」強制乳化型、非イオン系、固形
分45重量%)7%濃度に感熱剤としてNa2 SO4
%を加えた調合液を含浸し、マングルでピックアップ率
170%になるように絞った。次いで、150℃のピン
テンター乾燥機で4分加熱乾燥した。この不織シートを
水洗なしにサーキュラー染色機で染色し乾燥仕上げを行
ない、厚み1.00mmの厚手タイプのスエード調人工
皮革を得た。風合、耐摩耗性、表面立毛品位いずれも申
し分ないものであった。
To this, a polyether-based water-based polyurethane emulsion having an average particle size of 0.3 μm (“Superflex” forced emulsification type manufactured by Daiichi Kogyo Seiyaku Co., nonionic, solid content 45% by weight) was added as a heat-sensitive agent at a concentration of 7%. Na 2 SO 4 5
%, And the solution was impregnated with a mangle to squeeze the pick-up rate to 170%. Then, it was heated and dried for 4 minutes by a pin tenter dryer at 150 ° C. This non-woven sheet was dyed with a circular dyeing machine without washing with water and dried to obtain a thick type suede-like artificial leather having a thickness of 1.00 mm. The feeling, abrasion resistance and surface nap quality were all satisfactory.

【0049】(実施例4)実施例1で用いた不織シート
に平均粒径0.6μmのポリエーテル系水系ポリウレタ
ンエマルジョン(第一工業製薬社製「スーパーフレック
ス」固形分43重量%)を3%及び15%濃度に調合
し、感熱剤としてNaCl6%を加えた調合液を含浸
し、マングルでピックアップ率140%に絞った。次い
で、140℃のピンテンター乾燥機で3分加熱乾燥し
た。この不織シートを水洗なしにサーキュラー染色機で
染色し、乾燥仕上げを行ない、0.50mm厚みのスエ
ード調人工皮革を得た。
Example 4 To the non-woven sheet used in Example 1, 3 parts of a polyether-based water-based polyurethane emulsion having an average particle size of 0.6 μm (“Superflex” solid content of 43% by weight manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used. % And 15% concentration, and impregnated with a preparation liquid containing 6% NaCl as a heat-sensing agent, and the pick-up rate was reduced to 140% with a mangle. Then, it was heated and dried for 3 minutes by a pin tenter dryer at 140 ° C. This non-woven sheet was dyed with a circular dyeing machine without washing with water and dried to obtain a suede-like artificial leather having a thickness of 0.50 mm.

【0050】表2に示す物性の通りであり、3%濃度で
含浸したものは風合は極めて柔軟で、耐摩耗性も500
0回で軽衣料としては申し分ないものであった。又、1
5%濃度で含浸したものは、製品の見掛け密度も高く充
実感がありペーパーな風合いを全く感じない仕上りで張
りを要求される衣料分野に好適であった。
The physical properties shown in Table 2 are as follows. The one impregnated at a concentration of 3% has an extremely soft texture and wear resistance of 500.
It was perfect for light clothing at 0 times. Again 1
The product impregnated at a concentration of 5% had a high apparent density of the product and had a feeling of fulfillment, and was suitable for a clothing field where a finish was required without feeling a paper texture at all.

【0051】[0051]

【表2】 [Table 2]

【0052】(実施例5)直接紡糸法によって単繊維繊
度0.1デニールのPET極細繊維を製造し、長さ5m
mにカットし、水中に分散させ抄造用スラリーとし、目
付75g/m2 のシートを製造してこれを表層成分とし
た。
Example 5 A PET ultrafine fiber having a single fiber fineness of 0.1 denier was produced by the direct spinning method, and the length was 5 m.
It was cut into m pieces and dispersed in water to prepare a slurry for papermaking, and a sheet having a basis weight of 75 g / m 2 was produced, which was used as a surface layer component.

【0053】裏層成分として、ナイロン66単繊維繊度
1.0デニールを10mmにカットしたものを同様に水
分散させ、目付100g/m2 のシートを製造した。こ
の二成分の不織シートを積層し、孔径0.1mの高速水
流で水圧40kg/m2 で処理し、三次元的に交絡一体
化させた。このシート状物を#400のエメリーペーパ
ーでペーパー速度900m/分で表面の極細系層をバフ
ィングした。
As the back layer component, nylon 66 monofilament fineness 1.0 denier cut into 10 mm was similarly dispersed in water to prepare a sheet having a basis weight of 100 g / m 2 . The two-component non-woven sheets were laminated, treated with a high-speed water stream having a pore diameter of 0.1 m at a water pressure of 40 kg / m 2 , and three-dimensionally entangled and integrated. The sheet-like material was buffed with # 400 emery paper at a paper speed of 900 m / min for the ultrafine system layer on the surface.

【0054】この不織シート状物に平均粒子径0.8μ
mのポリエーテル系水系ポリウレタンエマルジョン(第
一工業製薬社製「スーパーフレックス」固形分45重量
%)を9%濃度で感熱剤としてNaCl6%を加えた調
合液を含浸し、マングルでピックアップ率130%にな
るよう絞った。次いで、130℃のピンテンター乾燥機
で3分加熱乾燥した。
This non-woven sheet material had an average particle size of 0.8 μm.
m Polyether water-based polyurethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., "Superflex" solid content 45% by weight) was impregnated with a preparation solution containing 9% concentration of NaCl 6% as a heat-sensitive agent, and picked up with a mangle of 130%. I narrowed it down to become. Then, it was heated and dried for 3 minutes in a pin tenter dryer at 130 ° C.

【0055】このものを水洗なしに分散・酸性染料の混
合浴で120℃でサーキュラー染色した。染色に切断す
ることなく仕上った製品は、表面品位、風合い、耐摩耗
性含めた機械物性は良好であった。このものは靴資材に
は好適であった。
This was subjected to circular dyeing at 120 ° C. in a mixed bath of dispersion / acid dye without washing with water. The finished product without cutting for dyeing had good mechanical properties including surface quality, texture and abrasion resistance. This was suitable as a shoe material.

【0056】[0056]

【発明の効果】以上の通り、極細繊維を主体としてなる
不織シート状物に特定の水系ポリウレタンエマルジョン
を付与し、加熱乾燥したので、柔軟で耐摩耗性良好な人
工皮革を提供できる。
As described above, since a specific water-based polyurethane emulsion is applied to a non-woven sheet material mainly composed of ultrafine fibers and heated and dried, it is possible to provide an artificial leather which is soft and has good abrasion resistance.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 D06M 15/564 // D06M 101:32 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location D06M 15/564 // D06M 101: 32

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 少くとも表面繊維層として単繊維繊度
0.5デニール以下の極細繊維を主体としてなる繊維層
を含んで成る不織シート状物に、強制乳化された非イオ
ン性のエマルジョンで、それを構成するエマルジョン粒
子の平均粒径が0.1〜2.0μmである水系ポリウレ
タンエマルジョンに無機塩類を溶解、混合した処理液を
付与し、加熱乾燥してなることを特徴とする、柔軟で耐
摩耗性良好な人工皮革の製造方法。
1. A non-ionic emulsion forcibly emulsified in a non-woven sheet material comprising a fiber layer mainly comprising ultrafine fibers having a single fiber fineness of 0.5 denier or less as a surface fiber layer, It is characterized in that it is obtained by applying a treatment liquid in which inorganic salts are dissolved and mixed to an aqueous polyurethane emulsion having an average particle diameter of emulsion particles constituting the same of 0.1 to 2.0 μm, and heating and drying the same. A method for producing artificial leather having good wear resistance.
【請求項2】 前記無機塩類がアルカリ金属又はアルカ
リ土類金属からなる中性塩で一価又は二価の硫酸塩、硝
酸塩、塩化物であることを特徴とする、請求項1に記載
の柔軟で耐摩耗性良好な人工皮革の製造方法。
2. The softener according to claim 1, wherein the inorganic salt is a neutral salt composed of an alkali metal or an alkaline earth metal and is a monovalent or divalent sulfate, nitrate or chloride. A method for producing artificial leather with good wear resistance.
JP5124650A 1993-04-30 1993-04-30 Manufacturing method of artificial leather with good soft abrasion resistance Expired - Lifetime JP3047951B2 (en)

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