JP2005171451A - Method for producing grain leather-like sheet - Google Patents
Method for producing grain leather-like sheet Download PDFInfo
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- JP2005171451A JP2005171451A JP2003416305A JP2003416305A JP2005171451A JP 2005171451 A JP2005171451 A JP 2005171451A JP 2003416305 A JP2003416305 A JP 2003416305A JP 2003416305 A JP2003416305 A JP 2003416305A JP 2005171451 A JP2005171451 A JP 2005171451A
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- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 229920001410 Microfiber Polymers 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 229920000515 polycarbonate Polymers 0.000 abstract description 7
- 239000004417 polycarbonate Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 239000004745 nonwoven fabric Substances 0.000 description 7
- 230000037303 wrinkles Effects 0.000 description 7
- 238000009987 spinning Methods 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Description
本発明は、銀付調皮革様シート状物の製造方法に関し、さらに詳しくは高い曲率で使用する場合においても耐摩耗性に優れた、表面に銀面を有する皮革様シート状物の製造方法に関する。 The present invention relates to a method for producing a silvered leather-like sheet material, and more particularly, to a method for producing a leather-like sheet material having a silver surface on the surface, which is excellent in wear resistance even when used with a high curvature. .
近年、天然皮革代替物として、繊維複合シート表面に高分子弾性体からなる表皮層および接着層を積層した皮革様シートが、軽さ、イージーケアー、低価格などの特徴から、家具・車輌およびスポーツ分野などに幅広く利用されている。 In recent years, as a substitute for natural leather, a leather-like sheet with a surface layer and an adhesive layer made of a polymer elastic body laminated on the surface of a fiber composite sheet has been characterized by its lightness, easy care, low price, etc. Widely used in fields.
しかしボールや自動車のハンドルカバーのように人の皮膚に直接接することの多い分野においては、質感においてまだまだ満足のいくものではなかった。また、皮革様シート状物を使用する際に形状が立体的で曲率が大きい場合には、折れしわが発生しやすくその部分から磨耗が進行するという問題があった。 However, in a field that often comes into direct contact with human skin, such as balls and car handle covers, the texture is still not satisfactory. Further, when a leather-like sheet-like material is used, if the shape is three-dimensional and the curvature is large, there is a problem in that creases and wrinkles are likely to occur and wear proceeds from that portion.
例えば特許文献１には、編物からなる繊維質基材上にシリコーン変性ポリカーボネート系ポリウレタン樹脂からなる表皮を有する合成皮革が開示されている。しかしこのものは摩擦こそ減少するものの、繊維質基材を構成する単糸繊度が大きく、高い曲率で曲げた際にしわが発生しその部分から磨耗が発生するという問題があった。 For example, Patent Document 1 discloses a synthetic leather having a skin made of a silicone-modified polycarbonate polyurethane resin on a fibrous base material made of knitted fabric. However, although this reduces friction, there is a problem that the single yarn fineness constituting the fibrous base material is large, and wrinkles are generated when bending with a high curvature, and wear occurs from that portion.
また特許文献２にはポリイソシアネート系硬化剤により架橋されたシリコーン変性ポリウレタンを表皮に有する皮革様シートが開示されているが、架橋したために表面が硬くなり屈曲性、風合いが悪くなるという問題があった。 Patent Document 2 discloses a leather-like sheet having a silicone-modified polyurethane cross-linked with a polyisocyanate-based curing agent on the skin. However, there is a problem that the surface becomes hard due to the cross-linking, resulting in poor flexibility and texture. It was.
本発明は、上記従来技術を背景になされたもので、その目的は表面質感に優れ、曲率が大きい使用状態においても耐磨耗性に優れた銀付調皮革様シート状物を提供することにある。 The present invention has been made against the background of the above-described prior art, and its purpose is to provide a silver-coated leather-like sheet-like material having excellent surface texture and excellent wear resistance even in a use state with a large curvature. is there.
本発明の銀付調皮革様シート状物の製造方法は、極細繊維および高分子弾性体からなる繊維質基材上に、ポリウレタン樹脂からなる被覆層を形成し、次いでニトロセルロース誘導体を含む溶剤系塗料を塗布することを特徴とする。 The method for producing a silver-finished leather-like sheet according to the present invention comprises forming a coating layer made of a polyurethane resin on a fibrous base material made of ultrafine fibers and a polymer elastic body, and then a solvent system containing a nitrocellulose derivative It is characterized by applying a paint.
さらには、極細繊維が、２種以上の高分子弾性体からなる混合紡糸繊維から１成分以上を抽出除去して得たものであることや、０．０００１〜０．２ｄｔｅｘであること、被覆層を形成するポリウレタン樹脂がシリコーンを共重合したものであること、被覆層の形成面が、繊維質基材をスライスしたスライス面であること、あるいは被覆層の形成方法がラミネート法であることが好ましい。 Further, the ultrafine fiber is obtained by extracting and removing one or more components from a mixed spun fiber composed of two or more kinds of polymer elastic bodies, or a coating layer of 0.0001 to 0.2 dtex. It is preferable that the polyurethane resin for forming the resin is a copolymer of silicone, the coating layer forming surface is a sliced surface obtained by slicing a fibrous base material, or the coating layer forming method is a laminate method. .
本発明の製造方法によれば、表面質感に優れているとともに、曲率が大きい使用状態においても耐磨耗性に優れた銀付調皮革様シート状物が提供される。 According to the production method of the present invention, a silver-finished leather-like sheet-like material having excellent surface texture and excellent wear resistance even in a use state with a large curvature is provided.
以下、本発明を詳細に説明する。
本発明の製造方法は、極細繊維および高分子弾性体からなる繊維質基材上に、ポリウレタン樹脂からなる被覆層を形成し、次いでニトロセルロース誘導体を含む溶剤系塗料を塗布する製造方法である。
Hereinafter, the present invention will be described in detail.
The production method of the present invention is a production method in which a coating layer made of a polyurethane resin is formed on a fibrous base material made of ultrafine fibers and a polymer elastic body, and then a solvent-based paint containing a nitrocellulose derivative is applied.
本発明で用いられる極細繊維および高分子弾性体からなる繊維質基材としては、従来公知の人工皮革用の基材などが用いられる。繊維質基材を構成する繊維としては、例えばナイロン−６、ナイロン−６６、ナイロン−６１０、ナイロン−１１、ナイロン−１２等のポリアミド繊維、ポリエチレンテレフタレート、ポリトリエチレンテレフタレート、ポリブチレンテレフタレート及びこれらを主成分とする共重合ポリエステル等のポリエステル繊維、あるいはこれらの数種の混合繊維等があげられる。中でもポリエチレンテレフタレートあるいはナイロン−６が生産安定性、コスト等の面から好ましい。また、これらの繊維は極細繊維であることが必要であり、通常０．０００１ｄｔｅｘ〜０．２ｄｔｅｘが一般的に用いられている。風合いと強度の点とのバランスからは０．００１〜０．１ｄｔｅｘであることが好ましい。極細繊維でない通常繊度の繊維の場合、曲率を高く折り曲げた際にしわが発生しやすい傾向にあり、その部分での磨耗性が低下する傾向にある。 As the fibrous base material composed of the ultrafine fibers and the polymer elastic body used in the present invention, conventionally known base materials for artificial leather and the like are used. Examples of fibers constituting the fibrous base material include polyamide fibers such as nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, polyethylene terephthalate, polytriethylene terephthalate, polybutylene terephthalate, and the like. Examples thereof include polyester fibers such as copolymerized polyester as a main component, and several kinds of mixed fibers thereof. Among these, polyethylene terephthalate or nylon-6 is preferable from the viewpoints of production stability and cost. Further, these fibers need to be ultrafine fibers, and generally 0.0001 dtex to 0.2 dtex are generally used. From the balance between texture and strength, it is preferably 0.001 to 0.1 dtex. In the case of a fiber having a normal fineness that is not an ultrafine fiber, wrinkles tend to occur easily when bent at a high curvature, and the wear resistance at that portion tends to decrease.
これらの繊維は、公知の紡糸方法で得ることができ、繊度を細くするためには例えば混合紡糸繊維、海島紡糸繊維、剥離分割繊維の製造方法を適用できる。さらに風合い面や物性からはさらには繊維質基材を構成する繊維が、２種以上の高分子重合体からなる混合紡糸繊維から１成分以上を抽出除去して得たものであることが好ましく、このような多成分繊維としては、島成分がナイロン６、ナイロン６６等のポリアミドであり、海成分がポリエチレン、ポリスチレン等である海島繊維であることが好ましい。海成分がポリエチレンである場合には、この海成分はトルエンによって抽出除去することができる。 These fibers can be obtained by a known spinning method. In order to reduce the fineness, for example, a mixed spinning fiber, a sea-island spinning fiber, or a peeled split fiber manufacturing method can be applied. Furthermore, it is preferable that the fiber constituting the fibrous base material is obtained by extracting and removing one or more components from a mixed spun fiber composed of two or more kinds of polymer from the texture and physical properties, As such a multicomponent fiber, it is preferable that the island component is a polyamide such as nylon 6 or nylon 66, and the sea component is a sea island fiber such as polyethylene or polystyrene. When the sea component is polyethylene, the sea component can be extracted and removed with toluene.
繊維質基材中での繊維は繊維集合体として存在しており、繊維集合体としては、従来公知の織物、編物、不織布等が挙げられるが、皮革様シート状物としての風合を向上させるためには不織布が主体であり、織編物は補強用として一部に含むか、全く含まないことが好ましい。さらに繊維集合体の繊維が海島繊維であり、海成分の融点が島成分の融点より低い場合には、繊維集合体を熱プレスすることが好ましく、得られるシート状物の表面平滑性を高め、折り曲げ時のしわを微小なものとすることができる。 The fibers in the fibrous base material exist as a fiber aggregate, and examples of the fiber aggregate include conventionally known woven fabrics, knitted fabrics, nonwoven fabrics, etc., but improve the texture as a leather-like sheet. Therefore, it is preferable that the nonwoven fabric is mainly used, and the knitted or knitted fabric is partially included or not included for reinforcement. Furthermore, when the fibers of the fiber assembly are sea-island fibers, and the melting point of the sea component is lower than the melting point of the island component, it is preferable to heat-press the fiber assembly, increasing the surface smoothness of the resulting sheet-like material, The wrinkle at the time of bending can be made minute.
また、繊維質基材の一部を構成する高分子弾性体としては、例えばＳＢＲ、ＮＢＲ、ポリウレタン、ポリエステルエラストマー、ポリアクリル酸エステル系エラストマー等があげられる。中でも、ポリウレタンが好ましく、さらにはポリカーボネート／ポリエーテル系のポリウレタンが好ましい。例えばより具体的には分子量５００〜３０００のポリアルキレンカーボネートジオールとポリアルキレンエーテルジオール、イソシアネート、及び低分子鎖伸張剤など反応させて得られるポリカーボネート／ポリエーテル系のポリウレタン系エラストマーである。特に風合い面からはこの高分子弾性体は多孔質であることが好ましく、例えばジメチルホルムアミド溶解性の湿式凝固用ポリウレタンなどが好ましい。 Examples of the polymer elastic body that constitutes a part of the fibrous base material include SBR, NBR, polyurethane, polyester elastomer, and polyacrylate ester elastomer. Among these, polyurethane is preferable, and polycarbonate / polyether polyurethane is more preferable. For example, more specifically, it is a polycarbonate / polyether polyurethane elastomer obtained by reacting a polyalkylene carbonate diol having a molecular weight of 500 to 3000, a polyalkylene ether diol, an isocyanate, and a low molecular chain extender. In particular, the polymer elastic body is preferably porous in terms of texture, for example, dimethylformamide-soluble polyurethane for wet coagulation.
繊維質基材中の極細繊維と高分子弾性体の比率は、高分子弾性体／繊維（以下Ｒ／Ｆとする）が１５〜５０％、さらには３０〜４０％であることが好ましい。 The ratio of the ultrafine fiber to the polymer elastic body in the fibrous base material is preferably 15 to 50%, more preferably 30 to 40% of the polymer elastic body / fiber (hereinafter referred to as R / F).
このような繊維質基材を得るには、従来公知のいずれの方法を用いることもできる。特に好ましくは例えばつぎのような方法である。まず、溶剤溶解性の異なる２成分以上の重合体組成物から複合紡糸法により海島型多成分繊維等の極細化可能な繊維を紡糸する。この繊維をカード、クロスラッパー、ニードルロッカーなどの手段で不織布化する。次いでポリウレタン樹脂などの高分子弾性体をジメチルホルムアミド、ジメチルアセトアミド、テトラヒドロフラン、などの有機溶剤溶液又は水性エマルジョンなどとして不織布に含浸し、ポリウレタン樹脂を凝固処理することによってシート状物は得ることができる。 Any conventionally known method can be used to obtain such a fibrous base material. Particularly preferred is, for example, the following method. First, fibers that can be made ultrafine, such as sea-island type multicomponent fibers, are spun from a polymer composition of two or more components having different solvent solubility by a composite spinning method. This fiber is made into a non-woven fabric by means of a card, a cross wrapper, a needle locker or the like. Next, a sheet-like material can be obtained by impregnating a nonwoven fabric with a polymer elastic body such as polyurethane resin as an organic solvent solution such as dimethylformamide, dimethylacetamide, tetrahydrofuran, or an aqueous emulsion and coagulating the polyurethane resin.
ここでポリウレタン樹脂を凝固する方法は、ポリウレタン樹脂の非溶剤で溶剤に混和性の液体で処理する湿式法、溶媒を加熱して蒸発させる乾式法など任意に選択できるが風合い、挫屈性など得られるシートの性能から湿式凝固法を採用することがもっとも好ましい。得られたシートから海島繊維の海成分を溶解除去して極細繊維と高分子弾性体からなる複合シートを作成する。 Here, the polyurethane resin can be solidified by any method such as a wet method in which a polyurethane resin is treated with a non-solvent liquid miscible with a solvent and a dry method in which the solvent is heated to evaporate. It is most preferable to employ a wet coagulation method in view of the performance of the obtained sheet. The sea component of sea-island fibers is dissolved and removed from the obtained sheet to create a composite sheet composed of ultrafine fibers and a polymer elastic body.
このような繊維質基材としては厚さが０．５〜２ｍｍであることが好ましい。また厚さを調節するために厚さ方向にスライスすることも好ましい。 Such a fibrous base material preferably has a thickness of 0.5 to 2 mm. It is also preferable to slice in the thickness direction in order to adjust the thickness.
本発明の製造方法では、繊維質基材上に、ポリウレタン樹脂からなる被覆層を形成する。さらには被覆層を形成する面がスライス面であることが好ましい。スライス面に塗布した場合には、その面の平滑性が高いために被覆層も均一となり、折れしわを微小な均一なものにすることができる。ポリウレタン樹脂は、ポリマージオールとポリイソシアネートと低分子の鎖伸長剤とを反応させたものであるが、この被覆層のポリウレタン樹脂としてはシリコーンを共重合したものであることが好ましく、ポリウレタン樹脂の分子鎖にオルガノポリシロキシル基を中間または末端に有するものであることが好ましい。さらには無黄変型のポリカーボネート系ポリウレタンであることが好ましい。皮革様シート状物の表面としての耐久性や柔軟性に優れている。 In the production method of the present invention, a coating layer made of a polyurethane resin is formed on a fibrous base material. Further, the surface on which the coating layer is formed is preferably a slice surface. When applied to the slice surface, the smoothness of the surface is high, so that the coating layer is also uniform, and the creases can be made minute and uniform. The polyurethane resin is obtained by reacting a polymer diol, polyisocyanate, and a low molecular chain extender, and the polyurethane resin of this coating layer is preferably a copolymer of silicone, The chain preferably has an organopolysiloxyl group at the middle or terminal. Further, a non-yellowing type polycarbonate-based polyurethane is preferable. It has excellent durability and flexibility as the surface of leather-like sheets.
被覆層の形成方法としては、上記繊維質基材の作成時に繊維集合体に高分子弾性体としてのポリウレタン樹脂を含浸する際に樹脂を表面に残すことによる湿式コート方法や、繊維質基材が形成された後にポリウレタン樹脂をコートする方法等、従来公知のいずれの方法を採用することもできるが、最も好ましくは維質基材または被覆層の上に接着剤を塗布し繊維質基材と被覆層とを張り合わせ乾燥させる、いわゆるラミネート法による方法である。例えば離型紙の上に被覆層のフィルムを形成し、その上に接着剤を塗布し繊維質基材と貼り合せを行うことで得る方法である。 As a method for forming the coating layer, there is a wet coating method in which a resin is left on the surface when a fiber aggregate is impregnated with a polyurethane resin as a polymer elastic body when the fibrous base material is created, or a fibrous base material is used. Any conventionally known method such as a method of coating a polyurethane resin after forming can be used, but most preferably, an adhesive is applied on the fibrous base material or coating layer to cover the fibrous base material. This is a so-called laminating method in which the layers are laminated and dried. For example, it is a method obtained by forming a film of a coating layer on a release paper, applying an adhesive on the film, and laminating with a fibrous base material.
ラミネート法で用いられる接着剤としては、ウレタン系、オレフィン系等が挙げられるが、ウレタン系が最も好ましく、接着性とともに、柔軟性や耐磨耗性に優れる。ウレタン系の中でも、ポリカーボネート系のポリウレタンが好ましく、皮革様シート状物の表面としての耐久性や柔軟性に優れている。 Examples of the adhesive used in the laminating method include urethane-based and olefin-based adhesives, but urethane-based is most preferable, and is excellent in flexibility and wear resistance as well as adhesiveness. Among the urethane-based materials, polycarbonate-based polyurethane is preferable, and is excellent in durability and flexibility as the surface of the leather-like sheet-like material.
本発明の製造方法では上記ポリウレタン樹脂からなる被覆層のさらに表面側にニトロセルロース誘導体を含む溶剤系塗料を塗布することが必須である。本発明で用いるニトロセルロース誘導体は植物繊維素を硝化させたニトロセルロースから誘導されるものでありコーティング剤として一般に用いられているものを採用することができる。セルロース誘導体の好ましい分子量としては５００〜３０万程度である。セルロール誘導体と共に溶剤系塗料に含まれる樹脂成分としてはアクリル樹脂やポリウレタン樹脂が好ましい。また用いられる溶剤としてはアルコール類、多価アルコール類、ケトン類、エステル類、カーボネート類などの中から選ばれる１種または２種以上の組み合わせからなる溶剤が挙げられる。 In the production method of the present invention, it is essential to apply a solvent-based paint containing a nitrocellulose derivative on the surface side of the coating layer made of the polyurethane resin. The nitrocellulose derivative used in the present invention is derived from nitrocellulose obtained by nitrifying vegetable fiber, and those generally used as a coating agent can be employed. The preferred molecular weight of the cellulose derivative is about 500 to 300,000. As the resin component contained in the solvent-based paint together with the cellulose derivative, an acrylic resin or a polyurethane resin is preferable. Moreover, as a solvent used, the solvent which consists of 1 type, or 2 or more types of combinations chosen from alcohol, polyhydric alcohols, ketones, ester, carbonates, etc. is mentioned.
この溶剤系塗料の塗布量としてはｗｅｔで５〜５０ｇ／ｍ２の範囲で塗布することが好ましい。また塗布方法はメッシュを有したグラビアロールで塗布することが好ましい。本発明の製造方法では、表面の全面ではなくドット状に塗布することが好ましく、皮革様シート状物を柔軟にし、大きな折れしわの発生を防止する傾向にある。 The solvent-based paint is preferably applied in the range of 5 to 50 g / m 2 by wet. Moreover, it is preferable to apply | coat with the gravure roll which has a mesh the coating method. In the production method of the present invention, it is preferable to apply in the form of dots instead of the entire surface, and the leather-like sheet-like material tends to be soft and prevent the occurrence of large creases.
以下、実施例により、本発明を更に具体的に説明する。
なお、実施例における各項目は次の方法で測定した。
（１）耐摩耗性
表面に測定する皮革様シート状物を巻き付けた、ハンドルの半径１７ｃｍ、把持部分の直径１７ｍｍの円形ハンドルを水平に設置する。次に綿帆布（６号）を巾４ｃｍに切り取りハンドルに掛け、ハンドルの外側の綿帆布の端に１ｋｇの重りを取り付け、ハンドルの内側の端を把持してストローク１０ｃｍ、速度２０サイクル／分で１０万回の往復運動をさせる磨耗テストを行い、試験片の表面状態を下記に示す判定により評価した。
優 ：光沢、表面状態に変化が認められない
良 ：光沢、表面状態がわずかに変化したもの
可 ：しぼが無くなる
不可：表面が剥離してきているもの
Hereinafter, the present invention will be described more specifically with reference to examples.
In addition, each item in an Example was measured with the following method.
(1) Abrasion resistance A circular handle having a handle radius of 17 cm and a gripping portion having a diameter of 17 mm, in which a leather-like sheet material to be measured is wound, is horizontally installed. Next, cut the cotton canvas (No. 6) to a width of 4 cm, hang it on the handle, attach a 1 kg weight to the end of the cotton canvas outside the handle, hold the inner end of the handle, stroke 10 cm, and speed 20 cycles / min. A wear test for 100,000 reciprocating motions was performed, and the surface condition of the test piece was evaluated by the following judgment.
Excellent: Gloss, no change in surface condition is observed Good: Gloss, surface condition slightly changed Possible: No wrinkle disappeared: Surface has peeled off
［実施例１］
ナイロン６と低密度ポリエチレンとを配合比５０：５０でチップブレンドし、混合紡糸により繊度７．７ｄｔｅｘ、繊維長５１ｍｍの海島型混合紡糸繊維を得た。得られた海島型繊維をカードとクロスレーヤーによってウェブにした後、バーブ貫通パンチング本数１０００本／ｃｍ２でニードルパンチングを行い、６３０ｇ／ｍ２の繊維集合体である絡合不織布を作成した。
[Example 1]
Nylon 6 and low-density polyethylene were chip-blended at a compounding ratio of 50:50, and a sea-island mixed spun fiber having a fineness of 7.7 dtex and a fiber length of 51 mm was obtained by mixed spinning. The obtained sea-island fiber was made into a web by a card and a cross layer, and then needle punching was performed at a barb penetration punching number of 1000 / cm 2 to prepare an entangled nonwoven fabric as a fiber aggregate of 630 g / m 2 .
この絡合不織布を１６０℃の熱風オーブン中で予備加熱した後、９０℃の加熱ロールで見掛け密度が０．２９ｇ／ｃｍ３、厚さが２．１ｍｍとなるようにプレスした。 The entangled nonwoven fabric was preheated in a hot air oven at 160 ° C., and then pressed with a heating roll at 90 ° C. so that the apparent density was 0.29 g / cm 3 and the thickness was 2.1 mm.
次に、分子量１８００のポリヘキサメチレンカーボネートと、分子量２０５０のポリテトラメチレンエーテルグリコール、４，４’−ジフェニルメタンジイソシアネート、エチレングリコールとを反応させて得た、イソシアネートにもとづく窒素含有量が４．５％のポリウレタンエラストマーのジメチルホルムアミド溶液（濃度１５％）を、上記プレスした絡合不織布に含浸させ、１０％ジメチルホルムアミド水溶液中に浸漬して、湿式凝固させた。この後４０℃の温水中で十分に洗浄し、繊維とポリウレタンエラストマーとの比が７５：２５の高分子弾性体含浸基材を得た。 Next, the nitrogen content based on isocyanate obtained by reacting polyhexamethylene carbonate having a molecular weight of 1800 with polytetramethylene ether glycol having a molecular weight of 2050, 4,4′-diphenylmethane diisocyanate and ethylene glycol is 4.5%. The polyurethane elastomer dimethylformamide solution (concentration 15%) was impregnated into the pressed entangled nonwoven fabric, immersed in a 10% dimethylformamide aqueous solution, and wet coagulated. Thereafter, the substrate was thoroughly washed in warm water at 40 ° C. to obtain a polymer elastic material-impregnated base material having a fiber to polyurethane elastomer ratio of 75:25.
次いで８０℃のトルエン中でこの基材にディップとニップを繰り返して、海島繊維中のポリエチレンを溶解除去し、海島繊維の極細化を行った。その後１１０℃の蒸気スチーム中で基材に含まれているトルエンを除去し、１２０℃の熱風乾燥機中で乾燥し、平面方向にスライスして２枚に分割した極細繊維と高分子弾性体からなる０．９ｍｍの繊維質基材を得た。得られた極細繊維の平均繊度は０．００５ｄｔｅｘであった。 Next, dip and nip were repeated on this substrate in toluene at 80 ° C. to dissolve and remove the polyethylene in the sea-island fibers, and the sea-island fibers were made ultrafine. Thereafter, toluene contained in the base material is removed in steam steam at 110 ° C., dried in a hot air dryer at 120 ° C., sliced in the plane direction, and divided into two pieces from the ultrafine fiber and the polymer elastic body. A 0.9 mm fibrous substrate was obtained. The average fineness of the obtained ultrafine fibers was 0.005 dtex.
次いで、離型紙上にシリコーン変性無黄変型ポリカーボネート系ポリウレタン樹脂（レザミンＮＥＳ９９５０−３、大日精化社製、不揮発分１０ｗｔ％）を１５０ｇ／ｍ２の目付けで２回塗布および乾燥し、被覆層とし、さらにその上に架橋剤、架橋促進剤を添加したポリウレタン系樹脂（ＵＤ８３５３、大日精化社製、不揮発分４０ｗｔ％）を１５０ｇ／ｍ２塗布、乾燥して、前記のスライスした繊維質基材のスライス面にラミネート法により転写した。 Next, a silicone-modified non-yellowing polycarbonate polyurethane resin (Rezamin NES9950-3, manufactured by Dainichi Seika Co., Ltd., nonvolatile content 10 wt%) is applied twice on a release paper at a basis weight of 150 g / m 2 and dried to form a coating layer. Furthermore, 150 g / m 2 of a polyurethane resin (UD 8353, manufactured by Dainichi Seika Co., Ltd., nonvolatile content 40 wt%) to which a crosslinking agent and a crosslinking accelerator are added is applied and dried, and the above-mentioned sliced fibrous base material It was transferred to the sliced surface by a laminating method.
４８時間の熟成後、離型紙を分離し、次いでニトロセルロース誘導体を含む溶剤系塗料（コリアルマットラッカーＮＷ、ビーエスエフジャパン株式会社製）を１１０メッシュのグラビアロールで被覆層の最表面に塗布し、乾燥を行い、銀付調の皮革様シート状物を得た。Ｗｅｔでの塗布量は１５ｇ／ｍ２であった。 After aging for 48 hours, the release paper is separated, and then a solvent-based paint (corial mat lacquer NW, manufactured by BSF Japan Ltd.) containing a nitrocellulose derivative is applied to the outermost surface of the coating layer with a 110 mesh gravure roll. Then, drying was carried out to obtain a leather-like sheet-like material with silver. The coating amount with Wet was 15 g / m 2 .
得られたシート状物をハンドル形状の摩擦試験にかけたところ「優」の評価であり、折り曲げた際の大きなしわも無く、手触りにも優れたものであった。 When the obtained sheet-like material was subjected to a handle-shaped friction test, it was evaluated as “excellent”, and there was no large wrinkle when folded and it was excellent in touch.
［比較例１］
実施例１のニトロセルロース誘導体を含む溶剤系塗料の塗布を行わなかった以外は、実施例１と同様にしてシート状物を得た。
[Comparative Example 1]
A sheet-like material was obtained in the same manner as in Example 1 except that the solvent-based paint containing the nitrocellulose derivative of Example 1 was not applied.
得られたシート状物は、折り曲げた際の大きなしわこそ無かったものの、ハンドル形状の摩擦試験にかけたところ「不可」の評価であり、手触りにも粘着性の感覚があった。 Although the obtained sheet-like material did not have a large wrinkle when it was bent, it was evaluated as “impossible” when subjected to a handle-shaped friction test, and the touch also had a sticky sensation.
本発明の製造方法により得られた銀付調の皮革様シート状物は、高い曲率で使用する場合においても耐摩耗性に優れたものであり、ボールや自動車のハンドルカバー等の曲率が高く直接手が触れる用途に特に好ましく用いることができる。 The leather-like sheet-like material with a silver tone obtained by the production method of the present invention is excellent in wear resistance even when used at a high curvature, and has a high curvature such as a ball or a handlebar cover of an automobile. It can be particularly preferably used for applications where the hand touches.
Claims (7)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007084973A (en) * | 2005-09-26 | 2007-04-05 | Teijin Cordley Ltd | Grained artificial leather and method for producing the same |
| JP2014005564A (en) * | 2012-06-22 | 2014-01-16 | Kuraray Co Ltd | Grained artificial leather and method for producing the same |
| JP2014070312A (en) * | 2012-09-28 | 2014-04-21 | Kuraray Co Ltd | Artificial leather with silver tone |
| JP2015192869A (en) * | 2014-03-28 | 2015-11-05 | アキレス株式会社 | Deodorant sheet for floor mat |
| CN110144738A (en) * | 2019-05-13 | 2019-08-20 | 浙江禾欣新材料有限公司 | Folding is wear-resisting and the preparation method of the superior automotive seat leather of ageing-resistant performance |
| CN113544325A (en) * | 2019-04-05 | 2021-10-22 | 株式会社可乐丽 | Grain leather-like sheet |
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2003
- 2003-12-15 JP JP2003416305A patent/JP2005171451A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007084973A (en) * | 2005-09-26 | 2007-04-05 | Teijin Cordley Ltd | Grained artificial leather and method for producing the same |
| JP2014005564A (en) * | 2012-06-22 | 2014-01-16 | Kuraray Co Ltd | Grained artificial leather and method for producing the same |
| JP2014070312A (en) * | 2012-09-28 | 2014-04-21 | Kuraray Co Ltd | Artificial leather with silver tone |
| JP2015192869A (en) * | 2014-03-28 | 2015-11-05 | アキレス株式会社 | Deodorant sheet for floor mat |
| CN113544325A (en) * | 2019-04-05 | 2021-10-22 | 株式会社可乐丽 | Grain leather-like sheet |
| CN110144738A (en) * | 2019-05-13 | 2019-08-20 | 浙江禾欣新材料有限公司 | Folding is wear-resisting and the preparation method of the superior automotive seat leather of ageing-resistant performance |
| CN110144738B (en) * | 2019-05-13 | 2022-03-15 | 浙江禾欣新材料有限公司 | Preparation method of automobile seat leather with excellent folding resistance, wear resistance and aging resistance |
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