TW201016923A - Leather sheet and process for manufacturing the same - Google Patents

Leather sheet and process for manufacturing the same Download PDF

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Publication number
TW201016923A
TW201016923A TW098128752A TW98128752A TW201016923A TW 201016923 A TW201016923 A TW 201016923A TW 098128752 A TW098128752 A TW 098128752A TW 98128752 A TW98128752 A TW 98128752A TW 201016923 A TW201016923 A TW 201016923A
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TW
Taiwan
Prior art keywords
polyurethane
layer
sheet
polyurethane layer
leather
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Application number
TW098128752A
Other languages
Chinese (zh)
Inventor
Hisao Yoneda
Kazumasa Inoue
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Kuraray Co
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Publication of TW201016923A publication Critical patent/TW201016923A/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial 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
    • D06N3/14—Artificial 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1276—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives water-based adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0292—Thermoplastic elastomer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/18—Fabrics, textiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2479/00—Furniture

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention is to provide a process for manufacturing leather sheet 10 which is characterized in that comprises the following steps: Primary polyurethane layer formation step, which a first polyurethane layer 2 is formed by coating heated and fused hot-melt type moisture cured polyurethane 2 on the base cloth or the surface of mold releasing paper; Porosity sheet pasting step, which a porosity sheet 3 is pasted on the primary polyurethane layer 2; and Secondary polyurethane formation step, which a secondary polyurethane layer 4 is formed on the exterior surface of said porosity sheet 3.

Description

201016923 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種由聚胺基甲酸酯積層物所形成的皮 革樣片及其製法。 【先前技術】 以往，由聚胺基甲酸酯積層物所形成的皮革樣片被廣 泛地使用作爲鞋類、衣服類、皮包、家具等之表面原料》 該皮革樣片之典型的構成，例如以在不織布、織布、 ❹ 編布等之纖維質基材中含浸有聚胺基甲酸酯等的複合纖維 基材作爲基布，在該基布之表面上積層由聚胺基甲酸酯所 形成的中間層後，在所形成的中間層表面上再形成由聚胺 基甲酸酯或丙烯酸樹脂等所形成的粒面層之構成。該中間 層係使用在基布之表面上塗布溶劑型聚胺基甲酸酯或水系 聚胺基甲酸酯後、予以乾燥的方法，或在基布之表面上藉 由黏合劑黏合預先在脫模紙之表面上成膜的聚胺基甲酸酯 φ 膜的方法，予以形成。 可是近年來，爲了減低環境負荷，在聚胺基甲酸酯製 品之產領域中，企求使用沒有大量使用有機溶劑之水性聚 胺基甲酸酯或無溶劑型聚胺基甲酸酯之製程。於製造皮革 樣片中’使用水系聚胺基甲酸酯之製程亦部分被實用化。 然而’水系聚胺基甲酸酯就耐水性或耐久性不佳，或乾燥 效率低等而言，無法達成充分地取代溶劑型聚胺基甲酸酯。 201016923 例如，於下述專利文獻1中揭示，使用熱熔融型濕份 硬化聚胺基甲酸酯的方法作爲減低有機溶劑之使用量的皮 革樣片之製法。具體而言，於專利文獻1之「第3圖」中 記載，在基材上以由熱熔融型濕份硬化聚胺基甲酸酯所形 成的黏合劑黏合由熱熔融型濕份硬化聚胺基甲酸酯所形成 的皮膜層之方法。於下述中，詳細地說明該方法。 第1圖係表示引用專利文獻1所記載的「第3圖」之 圖面。第1圖中，30爲剝離紙（脫模紙）301之送出捲軸， ❹ 36爲基材37之送出捲軸，38爲製品之皮革樣片的捲取捲 軸，31、32、33a、33b、34，35 爲滾筒，303 及 305 爲塗 布熱熔融型濕份硬化聚胺基甲酸酯312、314時之刮刀塗布 機，3 04爲水蒸氣噴霧器。 於第1圖中，使捲附於送出捲軸30之剝離紙301承載 於滾筒31、32予以搬送。其次，以刮刀塗布機303藉由在 剝離紙301之表面上塗布熔融狀態之熱熔融型濕份硬化聚 e 胺基甲酸酯312，形成皮膜層。繼續，在由熱熔融型濕份 硬化聚胺基甲酸酯312所形成的皮膜層上，以水蒸氣噴霧 器304吹附水蒸氣。然後，使其承載於滾筒33a、33b上且 送至滾筒34，再以刮刀塗布機3 0 5在由熱熔融型濕份硬化 聚胺基甲酸酯312所形成的皮膜層上，塗布作爲黏合劑之 熔融狀態的熱熔融型濕份硬化聚胺基甲酸酯314。然後， 自送出捲軸36供應給基材37，且以滾筒35貼合基材37 201016923 於熱熔融型濕份硬化聚胺基甲酸酯之黏合層上，以製造皮 革樣片》 先前專利文獻 專利文獻1日本特開2000-54272號公報 使用專利文獻1中記載的無溶劑型之熱熔融型濕份硬 化聚胺基甲酸酯，以形成皮膜層或黏合劑層時，確實地實 現無溶劑化。然而，使用上述之方法，在工業上連續生產 皮革樣片時，會有下述的問題。 熱熔融型濕份硬化聚胺基甲酸酯係在塗布時經加熱熔 融，而被塗布於基材或脫模紙上。然後，藉由於塗布後冷 卻至所定的溫度予以再固化。如此藉由熱熔融性發揮優異 的塗布作業。而且，由於經再固化後，沒有充分地進行硬 化反應，故在表面上殘留黏合性（黏性）。其次，藉由空氣 中之水分或步驟中所噴射的水蒸氣進行硬化反應予以高分 子量化，藉由硬化反應完成時使黏性消失。 φ 第1圖所示之製程中，在剝離紙3 0 1之表面上以熔融 狀態所塗布的熱熔融型濕份硬化聚胺基甲酸酯3 1 2所形成 的皮膜層，以水蒸氣噴霧器304吹附水蒸氣後，承載於滾 筒33a、33b，送入滾筒34中。於該步驟中，藉由吹附水 蒸氣以促進硬化反應。其次，藉由促進硬化反應以抑制黏 性，可確保順利的搬送性。然而，由沒有充分進行硬化的 熱熔融型濕份硬化聚胺基甲酸酯312所形成的皮膜層，接 觸滾筒33a、33b之表面時，因在熱熔融型濕份硬化聚胺基 201016923 甲酸酯312之表面上所殘留的黏性，導致熱熔融型濕份硬 化聚胺基甲酸酯312之皮膜層附著於滾筒33a、33b上，捲 附於滾筒33a、33b上，而產生阻害順利進行搬送的問題。 而且，由熱熔融型濕份硬化聚胺基甲酸酯312所形成的皮 膜層’被充分地交聯硬化後，積層形成聚胺基甲酸酯層時， 雖可改善搬送性，惟無法得到與所積層的由熱熔融型濕份 硬化聚胺基甲酸酯所形成的層之充分黏合性。 該使用熱熔融型濕份硬化聚胺基甲酸酯，於工業製程 中連續生產皮革樣片時，會有無法使塗布後之積層中間物 使用滾筒等順利地進行搬送，且使積層物之黏合強度達到 充分高強度的問題。 【發明內容】 本發明係爲解決上述課題，以提供一種使用熱熔融型 濕份硬化聚胺基甲酸酯，在基布之表面或脫模紙之表面上 形成塗布層時，可藉由具有黏性之熱熔融型濕份硬化聚胺 G 基甲酸酯膜直接接觸滾筒等，以抑制生產性降低情形，且 使用積層間之黏合性高的熱熔融型濕份硬化聚胺基甲酸酯 之皮革樣片的製法爲目的。 本發明之一局面，係有關一種皮革樣片之製法，其特 徵爲具備藉由在基布或脫模紙之表面上塗布經加熱熔融的 熱熔融型濕份硬化聚胺基甲酸酯以形成第1聚胺基甲酸酯 層的第1聚胺基甲酸酯層形成步驟，在前述第1聚胺基甲 酸酯層上貼合多孔性薄片之多孔性薄片貼合步驟，及在前201016923 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a leather skin sample formed of a polyurethane laminate and a process for producing the same. [Prior Art] Conventionally, a leather plaque formed of a polyurethane laminate is widely used as a surface material of footwear, clothes, leather bags, furniture, etc., a typical composition of the leather swatch, for example, A fibrous base material such as a non-woven fabric, a woven fabric, or a woven fabric is impregnated with a composite fiber base material such as polyurethane as a base fabric, and a layer of a polyurethane is formed on the surface of the base fabric. After the intermediate layer, a grain layer formed of a polyurethane or an acrylic resin or the like is further formed on the surface of the formed intermediate layer. The intermediate layer is obtained by applying a solvent-type polyurethane or a water-based polyurethane on the surface of the base fabric, or drying it on the surface of the base fabric by bonding with a binder. A method of forming a film of a polyurethane film on the surface of a molded paper is carried out. However, in recent years, in order to reduce the environmental load, in the field of production of polyurethane products, a process of using an aqueous polyurethane or a solventless polyurethane which does not use a large amount of an organic solvent has been demanded. The process of using aqueous polyurethanes in the manufacture of leather samples has also been partially put into practical use. However, the water-based polyurethane has insufficient water resistance or durability, or has low drying efficiency, and the like, and it has not been possible to sufficiently replace the solvent-type polyurethane. For example, Patent Document 1 discloses a method of using a hot-melt type moisture-cured polyurethane as a method for producing a leather-like sheet which reduces the amount of use of an organic solvent. Specifically, in the "Fig. 3" of Patent Document 1, it is described that a binder formed of a hot-melt type moisture-cured polyurethane is bonded to a substrate by a hot-melt type moisture-curing polyamine. A method of forming a film layer of a urethane. This method will be described in detail below. Fig. 1 is a view showing a drawing of "Fig. 3" described in Patent Document 1. In the first drawing, 30 is a delivery reel of the release paper (release paper) 301, ❹ 36 is a delivery reel of the substrate 37, and 38 is a take-up reel of the leather sample of the product, 31, 32, 33a, 33b, 34, 35 is a roller, and 303 and 305 are blade coaters for applying hot-melt type moisture-cured polyurethane 312, 314, and 304 is a steam atomizer. In Fig. 1, the release paper 301 attached to the take-up reel 30 is carried by the rollers 31, 32 and conveyed. Next, the film coater 303 forms a film layer by applying a hot-melt type moisture-cured polyurethane 312 in a molten state on the surface of the release paper 301. Further, on the film layer formed of the hot-melt type moisture-cured polyurethane 312, water vapor is blown by the water vapor atomizer 304. Then, it is carried on the drums 33a, 33b and sent to the drum 34, and then coated on the film layer formed by the hot-melt type moisture-curing polyurethane 312 by the knife coater 305. A hot-melt type moisture-cured polyurethane 314 in a molten state of the agent. Then, the self-feeding reel 36 is supplied to the substrate 37, and the substrate 35 is attached to the adhesive layer of the hot-melt type moisture-hardening polyurethane by the roller 35 to manufacture a leather sample. In the case of the solvent-free hot-melt type moisture-curing polyurethane described in Patent Document 1, when the film layer or the adhesive layer is formed, the solventlessness is surely achieved. However, when the leather samples are continuously produced industrially using the above method, the following problems occur. The hot-melt type moisture-hardening polyurethane is applied to a substrate or a release paper by heat fusion at the time of coating. Then, it is re-solidified by cooling to a predetermined temperature after coating. Thus, the coating operation is excellent by the thermal meltability. Further, since the hardening reaction is not sufficiently performed after re-solidification, the adhesion (viscosity) remains on the surface. Next, the hardening reaction is carried out by the moisture in the air or the water vapor sprayed in the step to quantify the viscosity, and the viscosity disappears when the hardening reaction is completed. φ In the process shown in Fig. 1, the film layer formed by the hot-melt type moisture-curing polyurethane 3 1 2 coated on the surface of the release paper 30 1 in a molten state is a water vapor atomizer. After the water vapor is blown into the 304, it is carried on the drums 33a and 33b and fed into the drum 34. In this step, the hardening reaction is promoted by blowing water vapor. Secondly, by promoting the hardening reaction to suppress the viscosity, smooth conveyance can be ensured. However, the film layer formed of the hot-melt type moisture-curing polyurethane 312 which is not sufficiently hardened contacts the surface of the rolls 33a, 33b due to the hot-melt type moisture-hardening polyamine base 201016923 formic acid The adhesiveness remaining on the surface of the ester 312 causes the film layer of the hot-melt type moisture-hardening polyurethane 312 to adhere to the rollers 33a and 33b, and is wound on the rollers 33a and 33b, thereby causing a smooth resistance. The problem of transportation. Further, when the film layer ' formed of the hot-melt type moisture-cured polyurethane 312 is sufficiently cross-linked and hardened, and the polyurethane layer is formed by lamination, the conveyability can be improved, but the film is not obtained. Adhesion to the layer formed by the hot-melt moisture-curing polyurethane. When the hot-melt type moisture-cured polyurethane is used to continuously produce a leather sample in an industrial process, the laminated intermediate material after coating cannot be smoothly conveyed by using a roller or the like, and the bonding strength of the laminate is made. Achieve full strength problems. SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and provides a method for forming a coating layer on a surface of a base fabric or a surface of a release paper by using a hot-melt type moisture-curing polyurethane. The viscous hot-melt type moisture-curing polyamine G urethane film is in direct contact with a roller or the like to suppress the decrease in productivity, and the heat-melt type moisture-hardening polyurethane having high adhesion between the laminates is used. The method of making leather samples is for the purpose. One aspect of the present invention relates to a method for producing a leather swatch, which is characterized in that it is provided by coating a surface of a base fabric or a release paper with a heat-melted hot-melt type moisture-curing polyurethane to form a first a first polyurethane coating layer forming step of the polyurethane layer, a porous sheet bonding step of laminating the porous sheet on the first polyurethane layer, and before

201016923 述多孔性薄片之外表面上形成第2聚胺基甲酸酯層的第2 聚胺基甲酸酯層形成步驟。 本發明之另一局面，係有關一種皮革樣片，其特徵爲 具備基布、在前述基布表面上積層的由熱熔融型濕份硬化 聚胺基甲酸酯所形成的第1聚胺基甲酸酯層、在前述第1 聚胺基甲酸酯層上積層的多孔性薄片、與在前述多孔性薄 片上積層的第2聚胺基甲酸酯層。 本發明之目的、特徵、局面及優點，藉由下述之詳細 參 說明及附加圖面，更爲明白地說明。 實施發明之形態 〔第1形態〕 本實施形態之皮革樣片之製法，其特徵爲具備藉由在 基布或脫模紙之表面上塗布經加熱熔融的熱熔融型濕份硬 化聚胺基甲酸酯（以下簡稱爲濕份硬化聚胺基甲酸酯）以形 成第1聚胺基甲酸酯層的第1聚胺基甲酸酯層形成步驟， Q 在前述第1聚胺基甲酸酯層上貼合多孔性薄片之多孔性薄 片貼合步驟，及在前述多孔性薄片之外表面上形成第2聚 胺基甲酸酯層的第2聚胺基甲酸酯層形成步驟。 於下述中，參照第2圖且說明有關該第一實施形態。 第2圖係說明本實施形態之皮革樣片之製法的典型步 驟圖。於第2圖中，1爲基布，2爲第1濕份硬化聚胺基甲 酸酯，3爲多孔性薄片，4爲第2濕份硬化聚胺基甲酸酯， 5爲脫模紙。而且，11爲基布1之送出捲軸，12爲多孔性 201016923 薄片3之送出捲軸，13爲脫模紙5之送出捲軸，14爲以脫 模紙5被覆的皮革樣片10之捲取捲軸。另外，20、22、23、 24a、2 4b、25、27，28爲搬送滾筒。此外，100及101爲 壓延滾筒。而且，21及26爲具備加熱輥之可逆式輥塗布 器，102、104爲具備圖中省略的加熱器之樹脂塡料機。 於第2圖之步驟中，首先由送出捲軸11、經由滾筒20、 22、23、24a、24b、27，朝捲取捲軸14送出基布1，形成 基布1之線路。 然後，一邊使收容於樹脂塡料機1 02中之經加熱熔融 的第1濕份硬化聚胺基甲酸酯2維持熔融狀態、一邊朝線 路上之基布1予以流下。其次，第1濕份硬化聚胺基甲酸 酯2藉由加熱狀態之可逆式輥塗布器21，以均勻的厚度、 熔融狀態塗布於基布1之表面上（第1聚胺基甲酸酯層形成 步驟）。 本實施形態所使用的基布1之具體例，如不織布或織 Q 布、編布等一般皮革樣片所使用的纖維基材；在上述纖維 基材中含浸有溶劑系、水系、乳液系或無溶劑系聚胺基甲 酸酯樹脂、丙烯酸樹脂、及丁二烯系樹脂（SBR、NBR、MBR) 等之複合纖維基材等。於此等中，就製得具有柔軟質感與 更爲優異的機械強度之皮革樣片而言，以使用在由極細纖 維所形成的不織布中含浸有聚胺基甲酸酯樹脂之複合纖維 基材更佳。 201016923 其次，說 化聚胺基甲酸 熱熔融型 氰酸酯進行反 熱熔融性與濕 濕份硬化 不爲固體，係 熱熔融變成用 ❹ 性•該濕份硬 基布或脫模紙 予以再固化。 另一方面 性，係藉由胺 (水）進行反應 而且，所形成 φ 於系內之異氟 經由該硬化反 械特性及耐濕 具有濕份 在短時間內產 例如花約2 0〜 融予以塗布， 明有關本實施形態所使用的熱熔融型濕份硬 酯。 濕份硬化聚胺基甲酸酯，係含有多醇與聚異 應所得的胺基甲酸酯預聚物爲主成分，具備 氣硬化性之聚胺基甲酸酯形成成分。 聚胺基甲酸酯所具有的熱熔融性，在常溫下 具有不容易塗布程度之黏稠性者，惟藉由加 塗布的黏度，藉由冷卻再固化而具有黏合 化聚胺基甲酸酯，可以加熱熔融狀態塗布於 等上，於塗布後藉由冷卻使黏度急速上昇， ，濕份硬化聚胺基甲酸酯所具有的濕氣硬化 基甲酸酯預聚物中之異氰酸酯基末端與濕氣 ，形成胺基甲酸酯鍵或尿素鍵之硬化反應。 的胺基甲酸酯鍵或尿素鍵，可再藉由與存在 酸酯基進行反應，亦可藉由交聯反應。因此， 應及交聯反應，藉由高分子量化，以形成機 性等優異的聚胺基甲酸酯硬化物。 硬化聚胺基甲酸酯之濕氣硬化反應，對照於 生的冷卻固化，係在較長時間內、具體而言 5 0小時以進行完全硬化。因此，進行加熱熔 再進行冷卻固化後，在表面上殘留有顯著的 -10- 201016923 黏合性（黏性）。所以，藉由進行硬化及交聯反應予以高分 子量化，可使黏性消失。 熱熔融型濕份硬化聚胺基甲酸酯中之胺基甲酸酯預聚 物的數量平均分子量，以500〜30000之範圍較佳，更佳者 爲1 000〜1 0000之範圍。胺基甲酸酯預聚物之數量平均分 子量在該範圍內時，可形成具有優異的柔軟性、機械強度、 耐摩擦性、耐水解性之聚胺基甲酸酯層。 而且，熱熔融型濕份硬化聚胺基甲酸酯之熔融黏度， 以錐形摻混黏度計測定的1 25 °c之熔融黏度，以1 00〜 lOOOOmPa· s之範圍較佳，以1000〜8000mPa. s之範圍更 佳。 本發明之濕份硬化聚胺基甲酸酯，通常使用以聚胺基 甲酸酯預聚物爲主成分之樹脂成分外，配合有胺基甲酸酯 化觸媒、顔料等之著色劑、增黏劑、交聯劑、交聯促進劑、 抗氧化劑等添加劑的樹脂組成物。此外，以第1聚胺基甲 φ 酸酯層作爲發泡聚胺基甲酸酯層予以形成時，配合有發泡 劑。該樹脂組成物，可藉由以聚胺基甲酸酯預聚物爲主成 分之樹脂成分與其他成份在加熱熔融狀態下均勻地混合而 製得。 使熱熔融型濕份硬化聚胺基甲酸酯加熱熔融，塗布於 基布1之表面的裝置之具體例，除上述可逆式輥塗布器 外，例如可使用刮刀塗布機、可逆式塗布器、接觸輥塗布 器、輥塗布器、噴霧式塗布器、τ塑模塗布器、或豎立型 -11 - 201016923 塗布器等。特別是就維持熱熔融型濕份硬化聚胺基甲酸酯 之熔融狀態而言，以具備加熱輥之可逆式輥塗布器或輥塗 布器較佳。 塗布時之熔融黏度，就塗裝作業性優異而言，以1000 〜15000mPa. s之範圍較佳，以2000〜lOOOOmPa. s之範圍 更佳。 而且，所形成的第1聚胺基甲酸酯層2之厚度，就可 製得柔軟性與機械強度優異的皮膜樣片而言，硬化後之厚 ❹ 度以5〜80〇vm之範圍較佳，以10〜500 之範圍更佳。 其次，朝熔融或軟化狀態的第1濕份硬化聚胺基甲酸 酯2的塗布層之表面，自送出捲軸12送出多孔性薄片3。 然後，多孔性薄片3藉由壓延輥100貼合於第1濕份硬化 聚胺基甲酸酯 2的塗布層之表面上（多孔性薄片貼合步 驟）。如此藉由以多孔性薄片3被覆濕份硬化聚胺基甲酸酯 2之塗布層的表面，可抑制未硬化的濕份硬化聚胺基甲酸 φ 酯2具有的黏性對步驟所產生的不良影響。 . 多孔性薄片3，只要是使用藉由習知的紡黏法或熔噴 法等之習知方法所得的不織布、織布、編布等之纖維基材 薄片；發泡聚胺基甲酸酯薄片等之發泡性樹脂薄片即可， 沒有特別的限制。特別是使用纖維基材薄片時，就藉由使 熔融狀態之濕份硬化聚胺基甲酸酯沉入於纖維基材中，該 聚胺基甲酸酯使纖維固定後，藉由增黏效果（anchor effect) 可使第1濕份硬化聚胺基甲酸酯層與第2濕份硬化聚胺基 -12- 201016923 甲酸酯層的黏合性優異而言較佳。而且，藉由使用不織布， 由於在皮革樣片之表面上不易發現如織物或編物之規則圖 案’可容易維持如天然皮革之不規則的平滑感，故較佳。 形成作爲多孔性薄片3所使用的不織布之纖維的具體 例，如聚胺基甲酸酯纖維、聚對苯二甲酸乙二酯（PET)纖 維、各種聚醯胺系纖維、各種聚烯烴系纖維、聚乙烯醇系 纖維等。於此等之中，就第1聚胺基甲酸酯層與第2聚胺 基甲酸酯層之黏合性與一體感優異而言，以聚胺基甲酸酯 ❹ 纖維較佳。 形成不織布之纖維，以纖維直徑爲0.1〜50// m(更佳者 爲1〜15# m)之極細纖維較佳。該極細纖維由於剛性低、 柔軟，就可製得具有柔軟質感之皮革樣片而言較佳。 不織布亦可爲於形成纖維網後，藉由使數張纖維網重 疊’進行針刺處理等予以交絡而得者。 不織布之單位面積重量，就可得柔軟質感之皮革樣片 φ 及步驟通過性優異而言，以10〜100g/tn2之範圍較佳，以 20〜60g/m2之範圍更佳。 另一方面，發泡性樹脂薄片，只要是使用具有發泡構 造之樹脂薄片即可，沒有特別的限制。其具體例如發泡聚 胺基甲酸酯薄片、發泡性丙烯酸薄片、發泡性聚酯薄片、 發泡性烯烴系薄片、發泡性聚醯胺系薄片等。於此等之中， 就第1聚胺基甲酸酯層及第2聚胺基甲酸酯層之黏合性與 一體感優異而言，以發泡性聚胺基甲酸酯薄片較佳。 -13- 201016923 發泡性樹脂薄片之厚度，以5〜100/zm較佳 5 0 // m更佳。 於熔融或軟化狀態的第1濕份硬化聚胺基甲 塗布層之表面上貼合多孔性薄片3的方法，以使 延輥較佳。 而且，使用如聚胺基甲酸酯不織布之熱可塑 織布作爲多孔性薄片時，於第1濕份硬化聚胺基 的塗布層之表面上貼合熱可塑性樹脂不織布時， ❹ 用加熱壓延輥，使熱可塑性樹脂不織布進行加熱 邊予以平滑化且一邊貼合較佳。由於不織布具有 部空間，故表觀密度低。因此，藉由使熱可塑性 布加熱壓押且貼合於第1聚胺基甲酸酯層，在使 空間之熱可塑性樹脂不織布予以平滑化，於形成 空隙的薄片下予以壓縮。藉此，由於可適度地調整 故可提高強度。而且，可提高第1聚胺基甲酸酯 Φ 性薄片之黏合性。 其次，貼合多孔性薄片3所形成的積層中間 滾筒23、24a、24b及25，朝收容第2濕份硬化 酸酯4之樹脂塡料機104的正下方搬送。然後， 料機104中所收容的第2濕份硬化聚胺基甲酸酿 融狀態流下於積層中間物之多孔性薄片3的表面 可逆式輥塗布器26以均勻的厚度予以塗布（第2 酸酯層形成步驟）。 、以10〜 酸酯2的 用前述壓 性樹脂不 甲酸酯2 以藉由使 壓押、一 較多的內 樹脂不織 具有很多 具有適度 ί空隙率， 層與多孔 物，經由 聚胺基甲 在樹脂塡 丨4，以熔 上，藉由 聚胺基甲 -14- 201016923 第2濕份硬化聚胺基甲酸酯4，係使用與前述: 份硬化聚胺基甲酸酯2所使用相同者。而且，第2 化聚胺基甲酸酯4形成皮革樣片之表皮時，使用可 求的表皮功能之配合組成的濕份硬化聚胺基甲酸酯 方法或塗裝條件亦使用與第1濕份硬化聚胺基甲酸 使用相同者。 其次，自送出捲軸13送出脫模紙5，藉由壓延 以熔融或軟化的狀態貼合經塗布的第2濕份硬化聚 ❿ 酸酯4與脫模紙5 (薄片貼合步驟）。如此形成皮革樣 然後，所得的皮革樣片1 0，在以脫模紙5被覆的狀 藉由捲取捲軸14予以捲取。繼後，在經捲取的狀態 由所定時間的熟成處理，進行第1濕份硬化聚胺基 2及第2濕份硬化聚胺基甲酸酯4的濕份硬化反應 脫模紙5除使用表面平滑的脫模紙外，以賦予 意性爲目的時，亦可使用具有壓花圖案之脫模紙。 φ 所得的皮革樣片10之熟成條件，以在溫度20 - 相對濕度50〜80%之條件下進行熟成約20〜50小_ 藉由在該熟成條件下進行熟成處理，使濕份硬化聚 酸酯進行濕氣硬化、濕氣交聯，製得機械強度或耐 異的皮革樣片。而且，皮革樣片10係剝離被覆於表 脫模紙5者。 如上述說明的步驟中，第1濕份硬化聚胺基弓 的塗布層之表面，與滾筒2 4a、24b之表面接觸前， 第1濕 濕份硬 賦予企 。塗裝 酯2所 :輥 101 胺基甲 片10。 態下， 下，藉 甲酸酯 〇 表面創 ^ 40°c、 Ϊ較佳。 胺基甲 水性優 面上之 I酸酯2 藉由多 -15- 201016923 孔性薄片3予以被覆。因此，以多孔性薄片3予以被覆後 的步驟中，因未硬化的第1濕份硬化聚胺基甲酸酯2的黏 性，不會對製造線路產生不良的影響。所以，藉由各滾筒 順利地搬送等，可使連續生產予以安定化。 藉由該步驟所得的皮革樣片10之截面典型圖如第3圖 所示。 第3圖所示之皮革樣片10，係藉由剝離被覆於表面之 脫模紙5予以完成。於該皮革樣片10中，第1濕份硬化聚 胺基甲酸酯層2及第2濕份硬化聚胺基甲酸酯4，經由多 孔性薄片3予以貼合。因此，藉由因多孔性薄片3之空隙 的增黏效果，可提髙第1濕份硬化聚胺基甲酸酯層2及第 2濕份硬化聚胺基甲酸酯層4的黏合力。 〔第2實施形態〕 其次，參照第4圖且說明有關第2實施形態。 而且，與第1實施形態相同符號的部分，由於與第1 φ 實施形態爲共通的部分，故省略詳細說明。 第4圖係說明第2實施形態之皮革樣片50的製法之典 型步驟圖。於第2實施形態之步驟中，直至第1濕份硬化 聚胺基甲酸酯2的塗布層之表面上貼合有多孔性薄片3的 多孔性薄片貼合步驟，皆與第1實施形態之步驟相同。另 外，在多孔性薄片3之外表面上，藉由水性聚胺基甲酸酯 黏合劑44黏合預先在脫模紙5表面上所形成的聚胺基甲酸 酯膜42，以形成第2聚胺基甲酸酯層之點有所不同。 -16- 201016923 第4圖中，44爲水性聚胺基甲酸酯黏合劑，45爲在脫 模紙表面上形成有聚胺基甲酸酯膜42之附脫模紙的聚胺 基甲酸酯膜。另外，43爲附有脫模紙之聚胺基甲酸酯45 之送出捲軸。此外，20、 22、 23、 24a、 24b、 25、 26、 27、 28爲搬送滾筒。而且，21爲具備加熱輥之可逆式輥塗布 器，154爲刮刀塗布機。 於第4圖中，直至多孔性薄片貼合步驟爲止，與第2 圖所示之步驟相同。其次，貼合多孔性薄片3所形成的積 參 層中間物，經由滾筒23、24a、24b、25，朝收容水性聚胺 基甲酸酯黏合劑44之樹脂塡料機144正下方予以搬送。繼 後，於積層中間物之表層的多孔性薄片3之表面上流下樹 脂塡料機144中所收容的水性聚胺基甲酸酯黏合劑44,在 多孔性薄片3之表面上藉由刮刀塗布機154、以均勻的厚 度予以塗布。然後，藉由乾燥爐46進行乾燥，以形成黏合 劑層47。其次，與自送出捲軸43送出的附有脫模紙之聚 φ 胺基甲酸酯膜45予以合流，在黏合劑層47與附有脫模紙 之聚胺基甲酸酯膜45的表面之聚胺基甲酸酯膜42對向 下，藉由壓延輥101予以貼合（第2聚胺基甲酸酯層形成步 驟）。藉此，形成皮革樣片50。 於第2實施形態之步驟中，在多孔性薄片3之外表面 上，藉由黏合劑層47黏合附有脫模紙之聚胺基甲酸酯膜 45的表面之聚胺基甲酸酯膜42,以形成第2聚胺基甲酸酯 層。於該步驟中，由於預先以多孔性薄片3被覆濕份硬化 -17- 201016923 聚胺基甲酸酯2之塗布層的表面，故未硬化的濕份硬化聚 胺基甲酸酯2所具有的黏性不會妨礙順利地滾筒搬送。 形成黏合劑層47時所使用的水性聚胺基甲酸酯，以使 用習知製造皮革樣片時於層間黏合所使用的聚胺基甲酸酯 水系分散液或聚胺基甲酸酯乳液等較佳。而且，於本實施 形態中，以抑制有機溶劑之使用量爲目的時，使用水性聚 胺基甲酸酯，惟亦可使用溶劑型聚胺基甲酸酯取代水性聚 胺基甲酸酯。黏合劑層47之厚度，就可製得柔軟性與機械 ❿ 特性優異的皮革樣片而言，以10〜100 之範圍較佳，以 20〜60//m之範圍更佳。 此外，附有脫模紙之聚胺基甲酸酯45,只要是使用在 脫模紙之表面上預先形成有爲形成第2聚胺基甲酸酯層時 之聚胺基甲酸酯膜42者即可，沒有特別的限制。脫模紙表 面之聚胺基甲酸酯膜42，例如由熱熔融型（濕份硬化）聚胺 基甲酸酯、水性聚胺基甲酸酯、溶劑型聚胺基甲酸酯等所 φ 形成的膜等。於此等之中，由熱熔融型聚胺基甲酸酯及水 性聚胺基甲酸酯所形成的膜，就可抑制有機溶劑之使用量 而言較佳，特別是由熱熔融型濕份硬化聚胺基甲酸酯所形 成的膜時，就機械特性或耐濕性等優異而言較佳。聚胺基 甲酸酯膜42之厚度，就可製得柔軟性與機械特性優異的皮 革樣片而言，以10〜500#111之範圍較佳’以20〜200//m 之範圍更佳。 -18- 201016923 其次，所得的皮革樣片50係藉由捲取捲軸14予以捲 取。然後，在經捲取的狀態下，藉由所定時間予以熟成， 進行第1聚胺基甲酸酯2之濕份硬化反應。 如此所得的皮革樣片50之截面典型圖如第5圖所示。 〔第3實施形態〕 然後，參照第6圖且說明有關第3實施形態。 而且’與第1實施形態相同符號的部分，由於與第1 實施形態爲共通的部分，故省略詳細說明。 第6圖係說明第3實施形態之皮革樣片之製法的典型 步驟圖。於第3實施形態之步驟中，第1實施形態之第1 聚胺基甲酸酯層形成步驟中，除自送出捲軸11送出脫模紙 5以取代送出基布1;於薄片貼合步驟中，自送出捲軸13 送出基布1以取代送出脫模紙5外，與第1實施形態相同。 換言之，僅變換基布1之供應與脫模紙5之供應順序。 所得的皮革樣片6 0，具有與第1實施形態所得的皮革 φ 樣片1〇相同的層構成。 〔第4實施形態〕 其次，參照第7圖、第8圖及第9圖說明有關第4實 施形態。 而且，與第1實施形態相同符號的部分，由於第1實 施形態爲共通的部分，故省略詳細說明。 第7圖係說明第4實施形態之聚胺基甲酸酯積層物中 之積層中間物140之製造步驟的典型步驟圖》 -19- 201016923 於第4實施形態之步驟中，如第7圖所示，使與第1 實施形態中所形成相同的多孔性薄片3予以加熱壓押、積 層的積層中間物140，藉由捲取捲軸74 —次捲取。然後， 使第1熱熔融型濕份硬化聚胺基甲酸酯予以熟成硬化。而 且，亦可使該積層中間物140之表面的多孔性薄片3進行 造面加工處理，且使用水性聚胺基甲酸酯樹脂、藉由習知 的方法進行乾式造面加工處理。 其次，多孔性薄片3爲熱可塑性不織布時，使第1熱 熔融型濕份硬化聚胺基甲酸酯予以熟成硬化後，再藉由使 其表面以加熱輥進行加熱壓押，予以平滑化，形成內部及 表面具有微細孔或連通孔之薄片。 然後，例如第8圖所示，在經平坦化的多孔性薄片3 之表面上，藉由噴霧塗裝機200進行噴霧塗布水性聚胺基 甲酸酯，藉由乾燥爐46進行乾燥處理，形成第2聚胺基甲 酸酯層。另外，亦可使用照相凹版塗布取代噴霧塗布。而 〇 且，使用噴霧塗布或照相凹版塗布形成第2聚胺基甲酸酯 層時，可形成薄的表皮層。如此所得的皮革樣片，特別是 可使微細的黏性與平滑性兼具。 而且，亦可使用第9圖所示、在脫模紙5上藉由可逆 式輥塗布器21塗布第2熱熔融型濕份硬化聚胺基甲酸酯 2，且貼合經捲取的積層中間物140之多孔性薄片3的步 驟，取代第8圖所示之步驟。 -20- 201016923 如上述本實施形態之製法的一例作爲第1實施形態〜 第4實施形態例示，本發明不受上述之製程所限制，於聚 胺基甲酸酯積層物之製造中，只要是藉由在基布或脫模紙 上塗布熱熔融型濕份硬化聚胺基甲酸酯後，積層多孔性薄 片，可使未硬化狀態之濕份硬化聚胺基甲酸酯的黏性之影 響消失的製程即可，沒有特別的限制。 如此所得的聚胺基甲酸酯積層物，特別是藉由多孔性 薄片之空隙的增黏效果，可維持第1聚胺基甲酸酯層及第 2聚胺基甲酸酯層之高黏合性。因此，於皮革樣片中，亦 可提髙黏性之外觀性。 而且，對所得的皮革樣片而言，另外爲賦予表面創意 性時，亦可藉由習知慣用的方法適當地塗布溶劑系、水系、 乳液系或無溶劑系聚胺基甲酸酯樹脂或丙烯酸樹脂，或進 行拋光加工或壓花加工等之後加工處理。 如此所得的皮革樣片，以使用作爲鞋類、衣服類、皮 包、家具等之表面原料的皮革樣片較隹。 【實施方式】 於下述中，藉由實施例具體地說明本發明，惟本發明 不受實施例所限制。 實施例 首先，於下述中說明本實施例所使用的原材料。 (基布1、37) -21- 201016923 使用水溶性熱可塑性聚乙烯醇系樹脂作爲海成分，使 用異苯二甲酸改性度6莫耳％之聚對苯二甲酸乙二酯作爲 島成分’使用每一條纖維中島數爲25島之熔融複合紡紗用 噴嘴’在260 °C下自噴嘴熔融吐出以使得海成分/島成分之 質量比爲3 0/70。在紡速爲4500m/分下調整噴射器壓力， 以網子捕集由平均纖度爲2.Odtex之極細纖維產生型纖維 所成的長纖維’製得單位面積重量爲30g/m2之長纖維纖維 _ 網。使相當8張前述之長纖維纖維網的份量藉由交叉積層 予以重合，賦予紡紗油劑。然後，自兩面以織針進行 3 600P/cm2之針刺處理，使長纖維纖維網予以交絡。使該薄 片進行壓延處理，製得單位面積重量爲510g/m2、比重爲 〇·45之長纖維交絡不織布。在該長纖維交絡不織布中，使 作爲水系胺基甲酸酯乳液原液之Evafanol AP-12(日華化學 股份有限公司）調整爲樹脂固體成分20%，使感熱凝膠化劑 相對於樹脂調整爲15份。使該乳液含浸於前述長纖維交絡 Ο 不織布中，予以乾燥、及硬化後，在95 °c之溫水中溶解除 去極細纖維產生型纖維中之水溶性熱可塑性聚乙烯醇系樹 脂，製得具有島成分所成的極細纖維束之厚度1.0mm的基 布1。 (聚胺基甲酸酯不織布3) 使平均分子量1150之聚3-甲基-1,5-甲基己二酸乙二 醇酯與二異氤酸4,4-二苯基甲烷酯及1，4-丁二醇以1:4:3 之莫耳比添加，使用螺旋式混練型聚合機，以熔融聚合法 -22- 201016923 使聚胺基甲酸酯聚合。所得的聚胺基甲酸酯在熔融狀態 下，以熔噴法、在溫度260 °C下、於加熱爲溫度260 °C之高 速空氣流中自加熱的模孔兩端之窄口以微細纖維狀搬送纖 維狀熔融聚胺基甲酸酯，且於以2m/分鐘移動的金網上、 在捕集距離4〇cm之位置捕集，形成無規纖維網。藉由該方 法，製得由平均直徑之微細纖維所成，平均單位面積 重量25 g/m2的聚胺基甲酸酯不織布3。 (熱熔融型濕份硬化聚胺基甲酸酯2、312) 使Taskforce KMM-100(DIC(股）製之熱熔融型濕份硬 化聚胺基甲酸酯）1 00質量份、顏料 15質量份、發泡劑 2 份，在120 °C下熔融混合，製得 125 °C之熔融黏度爲 3 OOOmPa· s之發泡型的熱熔融型濕份硬化聚胺基甲酸酯2。 (熱熔融型濕份硬化聚胺基甲酸酯4、314) 使Taskforce KMM-100(DIC(股）製之熱熔融型濕份硬 化聚胺基甲酸酯）1〇〇質量份、顏料 15質量份，在120°C φ 下進行熔融混合，製得125 °C之熔融黏度爲3 OOOmPa . s之 發泡型的熱熔融型濕份硬化聚胺基甲酸酯2。 (水性聚胺基甲酸酯黏合劑44) 以Hydran WLA-4 04(DIC (股）製）爲樹脂成分，配合有交 聯劑、交聯促進劑、著色劑、添加劑之水性聚胺基甲酸酯 分散液》 (附有脫模紙之聚胺基甲酸酯膜45) -23- 201016923 以水性聚胺基甲酸酯之Hydran ULK-003(DIC(股）製） 爲樹脂成分，配合有交聯劑、交聯促進劑、著色劑、添加 劑之水性聚胺基甲酸酯分散液，塗布於脫模紙（Lintec(股） 製之R-70N)之表面上且予以乾燥，形成厚度30//m之聚胺 基甲酸酯膜42者。 (脫模紙5、301)201016923 A second polyurethane layer forming step of forming a second polyurethane layer on the outer surface of the porous sheet. Another aspect of the present invention relates to a leather plaque characterized by comprising a base fabric and a first polyamine group formed of a hot-melt type moisture-cured polyurethane on a surface of the base fabric. An acid ester layer, a porous sheet laminated on the first polyurethane layer, and a second polyurethane layer laminated on the porous sheet. The objects, features, aspects and advantages of the present invention will become more apparent from MODE FOR CARRYING OUT THE INVENTION [First Aspect] The method for producing a leather sample according to the present embodiment is characterized in that it comprises a hot-melt type moisture-cured polyurethane which is heated and melted by coating on the surface of a base fabric or a release paper. An ester (hereinafter referred to as a moisture-cured polyurethane) to form a first polyurethane layer forming step of the first polyurethane layer, Q in the first polyurethane A porous sheet bonding step of laminating a porous sheet on a layer, and a second polyurethane layer forming step of forming a second polyurethane layer on the outer surface of the porous sheet. In the following, the first embodiment will be described with reference to Fig. 2 . Fig. 2 is a view showing a typical step of the method for producing a leather piece of the present embodiment. In Fig. 2, 1 is a base fabric, 2 is a first moisture-hardening polyurethane, 3 is a porous sheet, 4 is a second moisture-hardening polyurethane, and 5 is a release paper. . Further, 11 is a delivery reel of the base fabric 1, 12 is a porous 201016923 delivery reel of the sheet 3, 13 is a delivery reel of the release paper 5, and 14 is a take-up reel of the leather swatch 10 covered with the release paper 5. Further, 20, 22, 23, 24a, 2 4b, 25, 27, and 28 are transport rollers. In addition, 100 and 101 are calender rolls. Further, 21 and 26 are reversible roll coaters having a heating roll, and 102 and 104 are resin spreaders having heaters omitted from the drawings. In the step of Fig. 2, the base fabric 1 is first fed from the take-up spool 11 to the take-up reel 14 via the rollers 20, 22, 23, 24a, 24b, 27 to form a line of the base fabric 1. Then, while the first moisture-hardening polyurethane 2 which is heated and melted in the resin crucible 102 is maintained in a molten state, it flows down toward the base fabric 1 on the line. Next, the first moisture-hardening polyurethane 2 is applied to the surface of the base fabric 1 in a uniform thickness and in a molten state by a reversible roll coater 21 in a heated state (first polyurethane) Layer formation step). The specific example of the base fabric 1 used in the present embodiment is a fibrous base material used for a general leather sample such as a non-woven fabric, a woven Q cloth, or a knitted fabric; and the fibrous base material is impregnated with a solvent system, a water system, an emulsion system, or no The solvent is a composite fiber base material such as a polyurethane resin, an acrylic resin, and a butadiene resin (SBR, NBR, MBR). In this case, in order to obtain a leather sample having a soft texture and more excellent mechanical strength, the composite fiber substrate impregnated with the polyurethane resin in the nonwoven fabric formed of the ultrafine fibers is more good. 201016923 Secondly, it is said that the hot-melt type cyanate of polycarbamic acid is anti-heat-melting and wet-wet hardening is not solid, and it is heat-melted to become sturdy. • The moisture-based hard base fabric or release paper is used for re-solidification. . On the other hand, the reaction is carried out by an amine (water), and the iso-fluorine formed in the system is produced by the hardening property and moisture resistance in a short period of time, for example, about 20% to the melt. Coating, the hot-melt type wet hard ester used in the present embodiment is clarified. The moisture-cured polyurethane is a polyurethane-based prepolymer obtained by containing a polyol and a poly-component, and has a gas-hardening polyurethane-forming component. The thermal meltability of the polyurethane has a viscosity which is not easily applied at a normal temperature, but has a viscosity of the applied coating, and has a viscous polyurethane by cooling and re-solidification. It can be applied to the film in a heated and molten state, and the viscosity is rapidly increased by cooling after coating, and the isocyanate group terminal in the moisture-hardening urethane prepolymer which the moisture-hardening polyurethane has is wet. Gas, a hardening reaction that forms a urethane bond or a urea bond. The urethane bond or the urea bond can be further reacted by the presence of an acid ester group or by a crosslinking reaction. Therefore, the crosslinking reaction is carried out by high molecular weight to form an excellent polyurethane cured product which is excellent in properties. The moisture hardening reaction of the hardened polyurethane is carried out in a solidified manner for a longer period of time, specifically 50 hours, for complete hardening. Therefore, after heating and melting and then cooling and solidifying, a remarkable -10-201016923 adhesiveness (viscosity) remains on the surface. Therefore, by performing high-molecular quantification by hardening and cross-linking reaction, the viscosity disappears. The number average molecular weight of the urethane prepolymer in the hot-melt type moisture-cured polyurethane is preferably in the range of 500 to 30,000, more preferably in the range of 1,000 to 10,000. When the number average molecular weight of the urethane prepolymer is within this range, a polyurethane layer having excellent flexibility, mechanical strength, abrasion resistance, and hydrolysis resistance can be formed. Further, the melt viscosity of the hot-melt type moisture-hardening polyurethane is a melt viscosity of 1 25 ° C measured by a cone-blending viscometer, preferably in the range of 100 to 100 mPa·s, to 1000~ The range of 8000mPa.s is better. The moisture-cured polyurethane of the present invention is usually a resin component containing a polyurethane prepolymer as a main component, and a coloring agent such as a urethane catalyst or a pigment. A resin composition of an additive such as a tackifier, a crosslinking agent, a crosslinking accelerator, or an antioxidant. Further, when the first polyaminomethyl phthalate layer is formed as a foamed polyurethane layer, a foaming agent is blended. The resin composition can be obtained by uniformly mixing a resin component containing a polyurethane prepolymer as a main component and other components in a heated and molten state. A specific example of an apparatus for heat-melting a hot-melt type moisture-cured polyurethane to be applied to the surface of the base fabric 1 may be, for example, a blade coater or a reversible coater, in addition to the above-described reversible roll coater. Contact roll applicator, roll coater, spray coater, τ mold applicator, or erect type -11 - 201016923 applicator, and the like. In particular, in order to maintain the molten state of the hot-melt type moisture-cured polyurethane, a reversible roll coater or roll coater having a heating roll is preferred. The melt viscosity at the time of coating is preferably in the range of 1,000 to 15,000 mPa·s in terms of excellent coating workability, and more preferably in the range of from 2000 to 100 mPa·s. Further, the thickness of the first polyurethane layer 2 formed can be obtained by obtaining a film sample excellent in flexibility and mechanical strength, and the thickness after hardening is preferably in the range of 5 to 80 Å. It is better in the range of 10 to 500. Next, the porous sheet 3 is sent out from the take-up reel 12 toward the surface of the coating layer of the first moisture-cured polyurethane urethane 2 in a molten or softened state. Then, the porous sheet 3 is bonded to the surface of the coating layer of the first moisture-curing polyurethane 2 by the calender roll 100 (porous sheet bonding step). By coating the surface of the coating layer of the moisture-cured polyurethane 2 with the porous sheet 3, the viscosity of the uncured moisture-curing polyurethane phthalate 2 can be suppressed from occurring in the step. influences. The porous sheet 3 is a fibrous base sheet of a nonwoven fabric, a woven fabric, a braided fabric or the like obtained by a conventional method such as a conventional spunbonding method or a meltblowing method; a foamed polyurethane; The foamable resin sheet such as a sheet is not particularly limited. In particular, when a fibrous base sheet is used, the polyurethane is fixed in a molten state by embedding the wet-hardened polyurethane in the fibrous base material, and the polyurethane is fixed by the tackifying effect. (anchor effect) It is preferable that the first moisture-hardening polyurethane layer and the second moisture-curing polyamino-12-201016923 formate layer have excellent adhesion. Further, by using a non-woven fabric, it is preferable that a regular pattern such as a woven fabric or a knitted fabric is hardly found on the surface of the leather swatch, and the irregular smoothness of the natural leather can be easily maintained. Specific examples of the fibers which are used as the nonwoven fabric used for the porous sheet 3, such as polyurethane fibers, polyethylene terephthalate (PET) fibers, various polyamide fibers, various polyolefin fibers. , polyvinyl alcohol-based fibers, and the like. Among these, in view of excellent adhesion and uniformity of the first polyurethane layer and the second polyurethane layer, a polyurethane phthalate fiber is preferred. The fibers forming the nonwoven fabric are preferably fine fibers having a fiber diameter of 0.1 to 50 / / m (more preferably 1 to 15 # m). Since the ultrafine fibers are low in rigidity and soft, it is preferable to obtain a leather sheet having a soft texture. The non-woven fabric may be obtained by entanglement by forming a plurality of fiber webs after the formation of the fiber web by needle punching or the like. The weight per unit area of the non-woven fabric can be obtained in a range of 10 to 100 g/tn2, more preferably in the range of 20 to 60 g/m2, in terms of the soft texture of the leather sample φ and the step passability. On the other hand, the foamable resin sheet is not particularly limited as long as it is a resin sheet having a foamed structure. Specific examples thereof include a foamed polyurethane sheet, a foamable acrylic sheet, a foamable polyester sheet, an expandable olefin sheet, and a foamable polyamide sheet. Among these, the foamable polyurethane sheet is preferable in that the first polyurethane layer and the second polyurethane layer are excellent in adhesion and uniformity. -13- 201016923 The thickness of the expandable resin sheet is preferably 5 to 100 / zm, preferably 5 0 / m. The method of bonding the porous sheet 3 to the surface of the first moisture-curing polyimide coating layer in a molten or softened state is preferred to make the roll. Further, when a thermoplastic woven fabric such as a polyurethane nonwoven fabric is used as the porous sheet, when a thermoplastic resin nonwoven fabric is bonded to the surface of the first moisture-curing polyamine-based coating layer, a heating calender roll is used. It is preferable to smooth the thermoplastic resin non-woven fabric while heating and to bond it. Since the non-woven fabric has a space, the apparent density is low. Therefore, by heating and pressing the thermoplastic sheet and bonding it to the first polyurethane layer, the thermoplastic resin non-woven fabric in the space is smoothed and compressed under the sheet forming the void. Thereby, the strength can be improved because it can be appropriately adjusted. Further, the adhesion of the first polyurethane Φ sheet can be improved. Then, the laminated intermediate rolls 23, 24a, 24b, and 25 formed by bonding the porous sheets 3 are conveyed directly under the resin spreader 104 in which the second moisture-saturated acid ester 4 is accommodated. Then, the second moisture-hardening polyurethane contained in the hopper 104 is flowed down to the surface of the porous sheet 3 of the laminated intermediate, and the surface of the porous sheet 3 is coated with a uniform thickness (second acid ester). Layer formation step). The use of the above-mentioned pressure-sensitive resin non-formate 2 with 10 to acid ester 2 is carried out by pressing, a large amount of internal resin is not woven, and has a moderate degree of void ratio, the layer and the porous substance, via the polyamine group. A is used in the resin crucible 4 to be melted, and the second moisture-curing polyurethane 4 is used by the polyamine-methyl-14-201016923, which is used in combination with the above: a portion of the hardened polyurethane 2 The same. Further, when the second urethane 4 is formed into the skin of the leather swatch, the moisture-hardening urethane method using the composition of the desired skin function or the coating conditions are also used and the first moisture is used. The same applies to the hardened polyamic acid. Then, the release sheet 13 is fed out of the release paper 5, and the coated second moisture-swellable polycarbonate 4 and the release paper 5 are bonded together by rolling in a molten or softened state (sheet bonding step). The leather sample was thus formed. Then, the obtained leather piece 10 was taken up by the take-up reel 14 in the form of being coated with the release paper 5. Then, in the wound state, the moisture-hardening reaction release paper 5 of the first moisture-curing polyurethane 2 and the second moisture-curing polyurethane 4 is used in addition to the aging treatment for a predetermined period of time. In addition to the release paper having a smooth surface, it is also possible to use a release paper having an embossed pattern for the purpose of imparting an intention. The aging condition of the leather sample 10 obtained by φ is tempered at a temperature of 20 - a relative humidity of 50 to 80%, and is aged to about 20 to 50 Å. The sterilized hard acid acrylate is cured by the aging treatment under the aging conditions. A moisture-hardening, moisture-crosslinking is carried out to obtain a leather sample of mechanical strength or resistance. Further, the leather piece 10 is peeled off and coated on the release paper 5. In the step described above, the surface of the coating layer of the first moisture-curing polyamino-based bow is hardened by the first wet-wet portion before being brought into contact with the surfaces of the rolls 24a and 24b. Coating Ester 2: Roll 101 Amino sheet 10. In the state, the surface of the formate is preferably 40 ° C, preferably Ϊ. The acid ester 2 of the amino-based water-based surface is coated with a porous sheet 3 of -15-201016923. Therefore, in the step of coating the porous sheet 3, the viscosity of the first moisture-hardened polyurethane 2 which is not cured does not adversely affect the production line. Therefore, continuous production can be stabilized by smoothly transporting the respective rollers. A typical cross-sectional view of the leather piece 10 obtained by this step is shown in Fig. 3. The leather piece 10 shown in Fig. 3 is completed by peeling off the release paper 5 coated on the surface. In the leather sample sheet 10, the first moisture-hardening polyurethane layer 2 and the second moisture-curing polyurethane 4 are bonded together via the porous sheet 3. Therefore, the adhesion of the first moisture-hardening polyurethane layer 2 and the second moisture-hardening polyurethane layer 4 can be improved by the viscosity-increasing effect of the voids of the porous sheet 3. [Second Embodiment] Next, a second embodiment will be described with reference to Fig. 4 . In addition, the same reference numerals as in the first embodiment are common to the first φ embodiment, and thus detailed description thereof will be omitted. Fig. 4 is a view showing a typical procedure for manufacturing the leather sample piece 50 of the second embodiment. In the step of the second embodiment, the porous sheet bonding step in which the porous sheet 3 is bonded to the surface of the coating layer of the first moisture-hardening polyurethane 2 is the same as that of the first embodiment. The steps are the same. Further, on the outer surface of the porous sheet 3, the polyurethane film 42 previously formed on the surface of the release paper 5 is adhered by an aqueous polyurethane adhesive 44 to form a second polymerization. The points of the urethane layer are different. -16- 201016923 In Fig. 4, 44 is an aqueous polyurethane adhesive, and 45 is a polylactic acid with a release paper having a polyurethane film 42 formed on the surface of the release paper. Ester film. Further, 43 is a delivery reel having a release paper-containing polyurethane 45. Further, 20, 22, 23, 24a, 24b, 25, 26, 27, and 28 are transport rollers. Further, 21 is a reversible roll coater having a heating roll, and 154 is a blade coater. In the fourth drawing, the steps up to the porous sheet bonding step are the same as those shown in Fig. 2 . Next, the intermediate layer formed by bonding the porous sheet 3 is conveyed directly under the resin crucible 144 containing the aqueous polyurethane adhesive 44 via the rolls 23, 24a, 24b, and 25. Thereafter, the aqueous polyurethane adhesive 44 contained in the resin crucible 144 is discharged onto the surface of the porous sheet 3 of the surface layer of the laminated intermediate, and is coated on the surface of the porous sheet 3 by a doctor blade. Machine 154 is applied in a uniform thickness. Then, it is dried by a drying furnace 46 to form an adhesive layer 47. Next, the polyφ urethane film 45 with release paper fed from the take-up reel 43 is joined to form a surface of the adhesive layer 47 and the surface of the polyurethane film 45 to which the release paper is attached. The polyurethane film 42 is bonded downward by the calender roll 101 (the second polyurethane layer forming step). Thereby, the leather piece 50 is formed. In the step of the second embodiment, on the outer surface of the porous sheet 3, the polyurethane film having the surface of the release film-attached polyurethane film 45 is adhered by the adhesive layer 47. 42 to form a second polyurethane layer. In this step, since the surface of the coating layer of the -17-201016923 polyurethane 2 is wet-coated with the porous sheet 3 in advance, the uncured moisture-hardening polyurethane 2 has Stickiness does not prevent smooth roller transport. The aqueous polyurethane used in forming the adhesive layer 47 is a polyurethane aqueous dispersion or a polyurethane emulsion which is used for bonding between layers when a leather sample is conventionally produced. good. Further, in the present embodiment, an aqueous polyurethane is used for the purpose of suppressing the amount of the organic solvent to be used, but a solvent-type polyurethane may be used instead of the aqueous polyurethane. The thickness of the adhesive layer 47 is preferably in the range of 10 to 100, more preferably in the range of 20 to 60 / / m, in the case of a leather sample excellent in flexibility and mechanical properties. Further, the polyurethane 45 to which the release paper is attached is used as long as the polyurethane film 42 is formed in advance on the surface of the release paper to form the second polyurethane layer. Yes, there are no special restrictions. The polyurethane film 42 on the surface of the release paper is, for example, a hot-melt type (moisture-hardening) polyurethane, an aqueous polyurethane, a solvent-type polyurethane, or the like. Formed film, etc. Among these, the film formed of the hot-melt type polyurethane and the aqueous polyurethane can suppress the use amount of the organic solvent, particularly the hot-melt type moisture. When the film formed by curing the polyurethane is excellent, it is excellent in terms of mechanical properties, moisture resistance, and the like. The thickness of the polyurethane film 42 is such that a leather article having excellent flexibility and mechanical properties can be obtained preferably in the range of 10 to 500 #111, preferably in the range of 20 to 200 / /m. -18- 201016923 Next, the obtained leather piece 50 is taken up by the take-up reel 14. Then, in the coiled state, the moisture curing reaction of the first polyurethane 2 is carried out by aging for a predetermined period of time. A typical cross-sectional view of the leather piece 50 thus obtained is shown in Fig. 5. [Third Embodiment] Next, a third embodiment will be described with reference to Fig. 6 . In addition, the same reference numerals as in the first embodiment are common to the first embodiment, and thus detailed description thereof will be omitted. Fig. 6 is a view showing a typical procedure of a method for producing a leather piece of the third embodiment. In the step of forming the third embodiment, in the first polyurethane layer forming step of the first embodiment, the release paper 5 is sent out from the delivery reel 11 instead of the base fabric 1; in the sheet bonding step. The self-feeding reel 13 is fed out of the base fabric 1 in place of the release paper 5, and is the same as in the first embodiment. In other words, only the supply order of the base fabric 1 and the release order of the release paper 5 are changed. The obtained leather piece 60 has the same layer constitution as the leather φ piece 1〇 obtained in the first embodiment. [Fourth Embodiment] Next, a fourth embodiment will be described with reference to Figs. 7, 8 and 9. In the first embodiment, the same portions as those in the first embodiment are common portions, and thus detailed description thereof will be omitted. Fig. 7 is a view showing a typical procedure for producing a layered intermediate 140 in the polyurethane laminate of the fourth embodiment. -19- 201016923 In the step of the fourth embodiment, as shown in Fig. 7 The laminated intermediate member 140 which is heated and pressed and laminated in the same manner as the porous sheet 3 formed in the first embodiment is wound up by the take-up reel 74. Then, the first hot-melt type moisture-cured polyurethane is cured and cured. Further, the porous sheet 3 on the surface of the laminated intermediate 140 may be subjected to a surface finishing treatment, and a dry granulation treatment may be carried out by a known method using an aqueous polyurethane resin. When the porous sheet 3 is a thermoplastic nonwoven fabric, the first hot-melt type moisture-cured polyurethane is cured and then heated, and then heated and pressed by a heating roll to be smoothed. A sheet having micropores or communicating pores inside and on the surface is formed. Then, for example, as shown in Fig. 8, on the surface of the flattened porous sheet 3, the aqueous polyurethane is spray-coated by the spray coater 200, and dried by the drying furnace 46 to form The second polyurethane layer. Alternatively, gravure coating may be used instead of spray coating. Further, when the second polyurethane layer is formed by spray coating or gravure coating, a thin skin layer can be formed. The leather sample thus obtained is particularly excellent in both fineness and smoothness. Further, the second hot-melt type moisture-curing polyurethane 2 can be applied to the release paper 5 by the reversible roll coater 21 as shown in Fig. 9, and the laminated layer can be laminated. The step of the porous sheet 3 of the intermediate 140 is replaced by the step shown in Fig. 8. -20- 201016923 As an example of the above-described production method of the present embodiment, the first embodiment to the fourth embodiment are exemplified, and the present invention is not limited to the above-described process, and in the production of the polyurethane laminate, as long as it is By applying a hot-melt type moisture-cured polyurethane on a base fabric or release paper, and laminating the porous sheet, the influence of the viscosity of the unhardened moisture-hardening polyurethane can be eliminated. The process can be, there is no special limit. The polyurethane laminate thus obtained can maintain high adhesion of the first polyurethane layer and the second polyurethane layer, in particular, by the viscosity-increasing effect of the voids of the porous sheet. Sex. Therefore, in leather samples, the appearance of viscous properties can also be improved. Further, in the case of imparting surface creativity to the obtained leather plaque, a solvent-based, aqueous, emulsion-based or solvent-free polyurethane resin or acrylic acid may be appropriately applied by a conventional method. Resin, or after processing such as polishing or embossing. The leather swatch thus obtained is relatively sturdy using a leather swatch which is a surface material of shoes, clothes, bags, furniture, and the like. [Embodiment] The present invention will be specifically described by way of Examples, but the present invention is not limited by the Examples. EXAMPLES First, the raw materials used in the examples were described below. (Base cloth 1, 37) -21- 201016923 A water-soluble thermoplastic polyvinyl alcohol-based resin is used as a sea component, and an ethylene terephthalate having a degree of modification of 6 mol% of isophthalic acid is used as an island component. Using a nozzle for molten composite spinning having a number of islands of 25 islands per fiber, it was melted from the nozzle at 260 ° C so that the mass ratio of the sea component/island component was 3 0/70. The ejector pressure was adjusted at a spinning speed of 4,500 m/min, and a long fiber made of a very fine fiber-producing fiber having an average fineness of 2.Odtex was collected by a net to obtain a long fiber fiber having a basis weight of 30 g/m2. _ network. A portion of the above-mentioned eight long fiber webs was superposed by cross-lamination to impart a spinning oil. Then, a needle punching treatment of 3 600 P/cm 2 was performed with knitting needles on both sides to entangle the long fiber web. The sheet was subjected to calendering treatment to obtain a long-fiber entangled nonwoven fabric having a basis weight of 510 g/m 2 and a specific gravity of 〇·45. In the long-fiber entangled nonwoven fabric, Evafanol AP-12 (Rihua Chemical Co., Ltd.) as a water-based urethane emulsion stock solution was adjusted to a resin solid content of 20%, and the sensible gelling agent was adjusted to the resin. 15 copies. The emulsion is impregnated into the long-fiber interlaced non-woven fabric, dried, and cured, and then the water-soluble thermoplastic polyvinyl alcohol-based resin in the ultrafine fiber-generating fiber is dissolved and removed in warm water of 95 ° C to obtain an island. A base fabric 1 having a thickness of 1.0 mm of a very fine fiber bundle formed of the components. (Polyurethane non-woven fabric 3) Poly(3-methyl-1,5-methyladipate ethylene glycol ester with an average molecular weight of 1150 and 4,4-diphenylmethane diisophthalic acid ester and 1 4-butanediol was added at a molar ratio of 1:4:3, and the polyurethane was polymerized by a melt polymerization method from 22 to 201016923 using a spiral kneading type polymerization machine. The obtained polyurethane is in a molten state, and is a microfiber at a narrow mouth of both ends of the self-heated die hole by a melt blow method at a temperature of 260 ° C in a high-speed air stream heated to a temperature of 260 ° C. The fibrous molten polyurethane was conveyed and collected on a gold mesh moving at 2 m/min at a collection distance of 4 〇cm to form a random fiber web. By this method, a polyurethane woven fabric 3 made of fine fibers having an average diameter and having an average basis weight of 25 g/m2 was obtained. (Hot-melt type moisture-hardening polyurethane, 2, 312) To make Taskforce KMM-100 (hot-melt type moisture-cured polyurethane made by DIC) 100 parts by mass, pigment 15 mass Two parts of the foaming agent and the foaming agent were melt-mixed at 120 ° C to obtain a foaming type hot-melt type moisture-curing polyurethane 2 having a melt viscosity of 125 ° C at 3 OOO mPa·s. (Hot-melt type moisture-hardening polyurethane 4, 314) Taskforce KMM-100 (hot-melt type moisture-hardening polyurethane made by DIC) 1 part by mass, pigment 15 The mass fraction was melt-mixed at 120 ° C φ to obtain a foaming type hot-melt type moisture-curing polyurethane 2 having a melt viscosity of 125 ° C of 3 OOO mPa·s. (Aqueous polyurethane adhesive 44) A water-based polyamine group containing Hydran WLA-4 04 (made by DIC) as a resin component, a crosslinking agent, a crosslinking accelerator, a coloring agent, and an additive. Ester dispersion (with polyurethane film 45 with release paper) -23- 201016923 Hydran ULK-003 (manufactured by DIC) of aqueous polyurethane is used as a resin component. An aqueous polyurethane dispersion having a crosslinking agent, a crosslinking accelerator, a coloring agent, and an additive, coated on a surface of a release paper (R-70N manufactured by Lintec Co., Ltd.) and dried to form a thickness 30 / / m of the polyurethane film 42. (release paper 5, 301)

Lintec (股）製之 R-70N ©〔實施例1〕 使用第2圖所示之製造製程，製造皮革樣片10。 具體而言，預先自送出捲軸11、經由滾筒20、22、23、 24a、24b、25、27，朝捲取捲軸14，以lm/分鐘之速度送 出基布1，形成線路。然後，朝線路上之基布1以熔融狀 態流下樹脂塡料機102中所收容的經加熱熔融的熱熔融型 濕份硬化聚胺基甲酸酯2。然後，使經流下的熱熔融型濕 份硬化聚胺基甲酸酯2藉由具備表面溫度11 0°C之加熱輥 〇 的可逆式輥塗布器21塗布於基布1之表面上。此時，使塗 布厚度調整爲2 0 0 /z m。 然後，朝熔融或軟化狀態之熱熔融型濕份硬化聚胺基 甲酸酯2的塗布層表面，自送出捲軸12送出聚胺基甲酸酯 不織布3»其次，聚胺基甲酸酯不織布3藉由加熱壓延輥 1〇〇貼合於第1濕份硬化聚胺基甲酸酯2的塗布層表面上， 同時使聚胺基甲酸酯不織布3進行加熱平滑處理，在表面 -24- 201016923 及內部形成微細孔或連通孔。而且，此時加熱壓延輥100 之表面溫度爲155 °c。 其次，貼合經加熱平滑處理的聚胺基甲酸酯不織布3 所形成的積層中間物，經由滾筒23、24a、24b及25，朝 收容熱熔融型濕份硬化聚胺基甲酸酯4之樹脂塡料機104 之正下方搬送。然後，使樹脂塡料機1〇4中所收容的熱熔 融型濕份硬化聚胺基甲酸酯4以熔融狀態流下於積層中間 物上，藉由具備表面溫度11 〇°C之加熱輥的可逆式輥塗布 器26塗布，形成第2聚胺基甲酸酯層。此時，使塗布厚度 調整爲40 # m。 繼後，自搬送捲軸13送出脫模紙5，藉由壓延輥1〇1 貼合於經塗布的熱熔融型濕份硬化聚胺基甲酸酯4上。如 此形成具有第3圖所示之層構造的皮革樣片1〇。其次，所 得的皮革樣片10，藉由捲取輥14以脫模紙5被覆的狀態 予以捲取。 G 於前述製程中，不會有引起積層中間物捲附於滾筒 24a、24b等之現象，爲連續生產性優異者。 然後，在捲取的狀態下，使皮革樣片10在溫度40 °C、 相對濕度60%之條件進行熟成35小時。於熟成後，使所得 的皮革樣片10切斷成所定的面積，且剝離脫模紙5，藉由 下述方法進行評估層間黏合性。 (層間黏合性） -25- 201016923 在脫模紙經剝離的皮革樣片10之第2聚胺基甲酸酯層 4的表面上，使布熱溶融膠帶[商標：Merco Tape、Sun化成（股） 製]在130 °C下進行壓熔5秒後，以20 0mm/分鐘之前端速 度、以JISK6854-2爲基準、使用Tensilon(島津製作所製） 測定剝離強度。而且，確認此時經剝離的部分之位置。 結果，皮革樣片10之剝離強度爲l〇.6kg/25mm，在基 布1層內有內部剝離情形。 〔實施例2〕 ❹ 使用如第4圖所示之製造製程，製造皮革樣片50。 具體而言，預先自送出捲軸U、經由滾筒20、22、23、 24a、24b、25、26、27，朝捲取捲軸14、以lm/分鐘之速 度送出基布1，形成線路。然後，朝線路上之基布1以熔 融狀態流下樹脂塡料機102中所收容的經加熱熔融的熱熔 融型濕份硬化聚胺基甲酸酯2。然後，使經流下的熱熔融 型濕份硬化聚胺基甲酸酯2藉由具備表面溫度110 °C之加 Q 熱輥的可逆式輥塗布器21塗布於基布1之表面上。此時， 使塗布厚度調整爲30/zm。 然後，自送出捲軸12之聚胺基甲酸酯不織布3，朝熔 融或軟化狀態之熱熔融型濕份硬化聚胺基甲酸酯2的塗布 層之表面送出，藉由加熱壓延輥100貼合於第1濕份硬化 聚胺基甲酸酯2的塗布層之表面上，同時使聚胺基甲酸酯 不織布3藉由加熱平滑處理，在表面及內部形成微細孔或 連通孔。而且，此時加熱壓延輥100之表面溫度爲155 °C。 -26- 201016923 其次，貼合經加熱平滑處理的聚胺基甲酸酯不織布3 所形成的積層中間物，經由滾筒23、24a、24b及25，朝 收容水性聚胺基甲酸酯黏合劑44之樹脂塡料機144的正下 方搬送。然後，於聚胺基甲酸酯不織布3之表面上流下樹 脂塡料機144中所收容的水性聚胺基甲酸酯黏合劑44，藉 由刮刀塗布機154、以均勻的厚度塗布於聚胺基甲酸酯不 織布3之表面上。此時，使塗布厚度調整爲50/zm。繼後， 藉由乾燥爐46進行乾燥，形成來自水性聚胺基甲酸酯黏合 劑44之黏合劑層47。然後’與自送出輥43所送出的附有 脫模紙之聚胺基甲酸酯膜45合流，使黏合劑層47與附有 脫模紙之聚胺基甲酸酯膜45表面之聚胺基甲酸酯膜42對 向下，藉由壓延輥101予以貼合。如此形成具有如第5圖 所示之層構成的皮革樣片50。然後，所得的皮革樣片50, 藉由捲取捲軸14以脫模紙5被覆的狀態予以捲取。 於前述步驟中，不會於製程中引起積層中間物捲附於 滚筒等之現象，爲連續生產性優異者。 其次，在捲取的狀態下，使皮革樣片50在溫度40°C、 相對濕度60%之條件下進行熟成處理35小時。 於熟成後，使所得的皮革樣片50切斷成所定的面積， 且剝離脫模紙5，藉由與實施例i相同的方法進行評估層 間黏合性。結果，皮革樣片50之剝離強度爲13.3 kg/2 5 mm， 在基布1層內有內部剝離情形。 〔實施例3〕 -27- 201016923 使用如第7及8圖所示之製造製程，製造聚胺基甲酸 酯積層物。 具體而言，如第7圖所示自送出捲軸11、經由滾筒20, 以lm/分鐘之速度朝捲取捲軸74送出基布1，形成線路。 然後，朝線路上之基布1以熔融狀態流下樹脂塡料機102 中所收容的經加熱熔融的熱熔融型濕份硬化聚胺基甲酸酯 2。然後，使經流下的熱熔融型濕份硬化聚胺基甲酸酯2藉 由具備表面溫度11 〇°C之加熱輥的可逆式輥塗布器21塗布 於基布1之表面上。此時，使塗布厚度調整爲200/zm。 然後，朝熔融或軟化狀態之熱熔融型濕份硬化聚胺基 甲酸酯2的塗布層之表面自送出捲軸12送出聚胺基甲酸酯 不織布3，藉由加熱壓延輥100貼合於第1濕份硬化聚胺 基甲酸酯2的塗布層之表面上，形成積層中間物140。然 後，使積層中間物140以捲取捲軸74予以捲取。其次，使 經捲取的積層中間物140在溫度40t、相對濕度60%之條 〇 件下進行熟成處理35小時。藉由使熟成後之積層中間物 140的聚胺基甲酸酯不織布3之表面，以溫度155 °C之壓延 輥進行加熱平滑化，使第1聚胺基甲酸酯層與聚胺基甲酸 酯不織布層之合計厚度爲125ym。在經加熱平滑化的聚胺 基甲酸酯不織布3之內部及表面上形成微細孔或連通孔。 然後，如第8圖所示，在積層中間物140之表層的聚胺基 甲酸酯不織布3之表面上，藉由噴霧塗裝機200進行噴霧 塗布以固體成分換算爲15 g/m2之水性聚胺基甲酸酯樹脂作 -28- 201016923 爲第2聚胺基甲酸酯層，以乾燥爐46進行乾燥，另外，藉 由加熱壓延輥101、以平板加熱壓花進行模具壓製處理， 製得微細皺摺與平滑性兼具的聚胺基甲酸酯積層物。使所 得的聚胺基甲酸酯積層物藉由與實施例1相同的方法，評 估層間黏合性。結果，聚胺基甲酸酯積層物之剝離強度爲 12.5kg/25mm，在基布1層內有內部剝離情形。 〔比較例1〕 除使用不具如第1圖所示之貼合聚胺基甲酸酯不織布 3之步驟的製程取代具有如第2圖所示之貼合聚胺基甲酸 酯不織布3的步驟之製程以製造皮革樣片外，與實施例！ 相同地製造皮革樣片。 具體而言，如第1圖所示，朝捲取捲軸38、以lm/分 鐘之速度自送出捲軸30送出脫模紙301，形成線路。然後， 使捲附於送出捲軸30之脫模紙301承載於滾筒31、32上， 予以搬送。然後，藉由在剝離紙3 0 1之表面上以刮刀塗布 機3 03塗布熔融狀態之熱熔融型濕份硬化聚胺基甲酸酯 312,形成摩膜層。此時，使塗布厚度調整爲40/zm。然後， 在由熱熔融型濕份硬化聚胺基甲酸酯312所形成的皮膜層 上以水蒸氣噴霧器304吹附水蒸氣。其次，承載於滾筒33a、 33b上，送入滾筒34，以刮刀塗布機305塗布熔融狀態之 熱熔融型濕份硬化聚胺基甲酸酯314»然後，自送出捲軸 36供應基布37,且使基布37以滾筒35貼合於熱熔融型濕 份硬化聚胺基甲酸酯之黏合層上，製造皮革樣片。 -29- 201016923 於前述步驟中，於製程中積層中間物捲附於第1圖所 示之滾筒33a、33b時，頻頻發生無法順利進行搬送的問 題，且不易連續生產。另外，使好不容易所得的皮革樣片 在溫度40°C、相對濕度60%之條件下進行熟成處理35小 時。於熟成後，使所得的皮革樣片切斷成所定的面積，且 剝離脫模紙，藉由與實施例1相同的方法進行評估層間黏 合性。結果，皮革樣片之剝離強度爲6.5kg/25mm，由濕份 ©硬化聚胺基甲酸酯3 1 2所形成的層與由濕份硬化聚胺基甲 酸酯314所成的層之界面有界面剝離情形。 〔比較例2〕 除使用具有如第10圖所示之以水蒸氣噴霧器304吹附 水蒸氣的步騾之製程取代具有如第4圖所示之貼合聚胺基 甲酸酯不織布3的步驟之製程，製造皮革樣片80外，與實 施例2相同地製造皮革樣片。 具體而言，朝捲取捲軸14，以1 m/分鐘之速度預先自 鬱 送出捲軸11、經由滾筒20、23、24a、24b、25、26、27, 送出基布1’形成線路。然後，朝線路上之基布1以熔融 狀態流下樹脂塡料機102中所收容的經加熱熔融的熱熔融 型濕份硬化聚胺基甲酸酯2。然後，使經流下的熱熔融型 濕份硬化聚胺基甲酸酯2藉由具備表面溫度no 〇c之加熱 輥的可逆式輥塗布器21塗布於基布1之表面上。此時，使 塗布厚度調整爲30;/m。然後，在由熱熔融型濕份硬化聚 胺基甲酸酯2所形成的皮膜層上以水蒸氣噴霧器3〇4吹附 -30- 201016923 水蒸氣。其次，經由滾筒23、24a、24b及25，朝收容水 性聚胺基甲酸酯黏合劑44之樹脂塡料機144的正下方搬 送。然後，於由熱熔融型濕份硬化聚胺基甲酸酯2所形成 的被膜之表面上流下樹脂塡料機144中所收容的水性聚胺 基甲酸酯黏合劑44，藉由刮刀塗布機154、以均勻的厚度 予以塗布。此時，使塗布厚度調整爲50//m。繼後，藉由 乾燥爐46進行乾燥，形成來自水性聚胺基甲酸酯黏合劑 44之黏合劑層47。然後，與自送出輥43所送出的附有脫 模紙之聚胺基甲酸酯膜4 5合流，使黏合劑層47與附有脫 模紙之聚胺基甲酸酯膜45表面之聚胺基甲酸酯膜42對向 下，藉由壓延輥101予以貼合。如此形成皮革樣片80。然 後，所得的皮革樣片80，藉由捲取捲軸14以脫模紙5被 覆的狀態予以捲取。 於前述步驟中，於製程中積層中間物捲附於第10圖所 示之滾筒24a、24b時，頻頻發生無法順利進行搬送的問 題’且不易連續生產。另外，使好不容易所得的皮革樣片 在溫度4 0 °C、相對濕度6 0 %之條件下進行熟成處理3 5小 時。於熟成後’使所得的皮革樣片80切斷成所定的面積， 且剝離脫模紙，藉由與實施例1相同的方法進行評估層間 黏合性。結果’皮革樣片之剝離強度爲6.5kg/25mm，由濕 份硬化聚胺基甲酸酯2所形成的層與由聚胺基甲酸醋42所 成的層之界面有界面剝離情形。 -31 - 201016923 如上述實施例之結果可知，於本發明以聚胺基甲酸酯 不織布被覆第1濕份硬化聚胺基甲酸酯的表面後，再積層 第2濕份硬化聚胺基甲酸酯，形成皮革樣片之實施例1， 及以聚胺基甲酸酯不織布被覆第1濕份硬化聚胺基甲酸酯 的表面後，藉由來自水性聚胺基甲酸酯之黏合劑層黏合作 爲附脫模紙的聚胺基甲酸酯膜之預先形成的聚胺基甲酸酯 膜，以形成皮革樣片之實施例2中，生產時不會有第1濕 康 份硬化聚胺基甲酸酯2捲附於滾筒的情形，於製程中可順 〇 利地進行搬送，連續生產性優異。此外，以聚胺基甲酸酯 不織布被覆第1濕份硬化聚胺基甲酸酯的表面後，再藉由 噴霧塗布水性聚胺基甲酸酯樹脂，以形成第2聚胺基甲酸 酯層之實施例3中，由於藉由以聚胺基甲酸酯被覆，捲取 積層中間物時，亦可簡略生產步驟。另外，沒有以聚胺基 甲酸酯不織布3被覆第1濕份硬化聚胺基甲酸酯2的表面 之比較例1及2中，於生產時第1濕份硬化聚胺基甲酸酯 ❹ 的塗布層捲附於滾筒上，於製程中無法順利地進行搬送， 因此不易進行連續生產。 此外，實施例1〜3所得的皮革樣片，層間黏合性試驗 之剝離強度皆高，且在由第1濕份硬化聚胺基甲酸酯所形 成的層有內部剝離情形。另外，比較例所得的皮革樣片之 剝離強度低，第1濕份硬化聚胺基甲酸酯與第2濕份硬化 聚胺基甲酸酯的界面有剝離情形。此係於實施例i〜3中， -32- 201016923 聚胺基甲酸酯不織布對於第1聚胺基甲酸酯層及第2聚胺 基甲酸酯層具有增黏效果，即可達成主要的功能。 如上述說明，本發明之一局面係有關皮革樣片之製 法，其具備藉由在基布或脫模紙之表面上塗布經加熱熔融 的熱熔融型濕份硬化聚胺基甲酸酯，形成第1聚胺基甲酸 酯層之第1聚胺基甲酸酯層形成步驟，在前述第1聚胺基 甲酸酯層上貼合多孔性薄片之多孔性薄片貼合步驟，與在 前述多孔性薄片之外表面上形成第2聚胺基甲酸酯層之第 2聚胺基甲酸酯層形成步驟。 藉由該製法，由於使作爲第1聚胺基甲酸酯層所形成 的具有黏性之熱熔融型濕份硬化聚胺基甲酸酯的表面實質 上以不具黏性之多孔性薄片予以被覆，可抑制該黏性之不 良影響所導致的皮革樣片之生產性降低情形。而且，由於 多孔性薄片具有的空隙可發揮增黏效果，故可提高所形成 的第2聚胺基甲酸酯層與第1聚胺基甲酸酯層之黏合性。 φ 此外，藉由多孔性薄片時，由於可確保充分的水分通路， 故可充分地維持熱熔融型濕份硬化聚胺基甲酸酯之濕份硬 化性。其次，藉由使用無溶劑之熱熔融型濕份硬化聚胺基 甲酸酯，可減低有機溶劑之使用量。 另外，前述之製法，係於前述第2聚胺基甲酸酯層形 成步驟後，具備在第2聚胺基甲酸酯層之表面上貼合薄片 之薄片貼合步驟，於第1聚胺基甲酸酯層形成步驟中，在 基布之表面上形成第1聚胺基甲酸酯層時，前述薄片貼合 -33- 201016923 步驟之薄片爲脫模紙，在脫模紙之表面上形成第1聚胺基 甲酸紙層時，前述薄片爲基布較佳。藉由該構成時，由於 可在薄片貼合步驟中使用基布以取代在第1聚胺基甲酸酯 層形成步驟中使用基布，或可在薄片貼合步驟中使用脫模 紙取代在第1聚胺基甲酸酯層形成步驟中使用脫模紙，於 任何之製法中，可藉由剝離在第1聚胺基甲酸酯層形成步 驟或薄片貼合步驟中所使用的脫模紙，完成皮革樣片。 I 此外，於前述之製法中，前述多孔性薄片爲聚胺基甲 霸 酸酯不織布，前述多孔性薄片貼合步驟以藉由使前述聚胺 基甲酸酯不織布進行加熱壓押，予以平滑化，貼合於前述 第1聚胺基甲酸酯層之步驟較佳。藉由使該聚胺基甲酸酯 不織布進行加熱壓押，貼合於第1聚胺基甲酸酯層’使具 有很多空間的聚胺基甲酸酯不織布予以壓縮，形成具有適 度空隙之經平滑化的薄片。藉此，可提高由多孔性薄片所 形成的層之強度。而且，亦可提高前述第1聚胺基甲酸酯 〇 層及第2聚胺基甲酸酯層之黏合性。 前述多孔性薄片貼合步驟，包含在與使前述聚胺基甲 酸酯不織布貼合於第1聚胺基甲酸酯層的同時或貼合後， 使聚胺基甲酸酯不織布之面藉由加熱壓押’予以平滑化的 步驟時，由於聚胺基甲酸酯不織布可形成更爲平滑化的薄 片，就可更爲提高由多孔性薄片所形成的層之強度而言較 佳。 -34- 201016923 而且，前述多孔性薄片爲發泡性聚胺基甲酸酯薄片 時，由於容易預先調整空隙率，就容易調整強度或增黏效 果而言較佳。 於前述之製法中，在熔融或軟化狀態之前述第1聚胺 基甲酸酯層上貼合前述多孔性薄片，就可維持高的黏合力 且容易貼合多孔性薄片而言較佳。 前述第2聚胺基甲酸酯層形成步驟，爲在前述多孔性 ^ 薄片之外表面上塗布經加熱熔融的熱溶融型濕份硬化聚胺 警 基甲酸酯之步驟時，就可更爲減低有機溶劑之使用量而言 較佳。 此外，於前述之製法中，前述第2聚胺基甲酸酯層形 成步驟，爲使預先在薄片之表面上所形成的來自熱熔融型 濕份硬化聚胺基甲酸酯或水性聚胺基甲酸酯之聚胺基甲酸 酯膜黏合於前述多孔性薄片之外表面的步驟，在基布之表 面上形成第1聚胺基甲酸酯層時，前述薄片爲脫模紙，在 Ο 脫模紙之表面上形成第1聚胺基甲酸酯層時，前述薄片爲 基布，就可更爲減少有機溶劑之使用量而言較佳。 另外，於前述之製法中，前述第1聚胺基甲酸酯層或 第2聚胺基甲酸酯層爲發泡聚胺基甲酸酯層時，就可製得 富含彈性之柔軟的皮革樣片而言較佳。 而且，本發明之另一局面，係提供一種皮革樣片，其 係具備基布、在前述基布表面上積層的由熱熔融型濕份硬 化聚胺基甲酸酯所形成的第1聚胺基甲酸酯層 '在前述第 -35- 201016923 1聚胺基甲酸醋層上積層的多孔性薄片、與在前述多孔性 薄片上積層的第2聚胺基甲酸酯層。爲該構成時，藉由前 述多孔性薄片之空隙可發揮增黏效果，提高多孔性薄片與 第1聚胺基甲酸酯層及第2聚胺基甲酸酯層之黏合性。藉 此’可改善所得的皮革樣片之剝離強度及黏性狀態。另外， 可減低有機溶劑之使用量予以製造。 此外，前述多孔性薄片爲藉由進行加熱壓押予以平滑 化的聚胺基甲酸酯不織布時，就前述第1聚胺基甲酸酯層 參 及第2聚胺基甲酸酯層之黏合性、皮革樣片之平滑性及黏 性狀態優異而言較佳。 另外’前述第1聚胺基甲酸酯層爲發泡聚胺基甲酸酯 層時，就形成富含彈性之皮革樣片而言較佳。 而且’前述第2聚胺基甲酸酯層爲由熱熔融型濕份硬 化聚胺基甲酸酯或水性聚胺基甲酸酯所形成者時，可更爲 減低有機溶劑之使用量予以製造》 φ 〔產業上之利用價値〕 藉由本發明之皮革樣片之製法，由於實質上以不具黏 性之多孔性薄片被覆作爲第1聚胺基甲酸酯層所形成的具 有黏性之熱熔融型濕份硬化聚胺基甲酸酯的表面，可抑制 因該黏性之不良影響而導致皮革樣片之生產性降低的情 形。而且，由於使用無溶劑之熱熔融型濕份硬化聚胺基甲 酸酯，故可減低有機溶劑之使用量。此外，所得的皮革樣 •36- 201016923 片，藉由多孔性薄片之增黏效果’第1聚胺基甲酸酯層與 第2聚胺基甲酸酯層之黏合性高。 【圖式簡單說明】 第1圖係引用專利文獻1所記載的「第3圖」之圖面。 第2圖係說明第1實施形態之皮革樣片之製法的典型 步驟圖。 第3圖係藉由第1實施形態之步驟所得的皮革樣片之 截面典型圖。 第4圖係說明第2實施形態之皮革樣片之製法的典型 步驟圖。。 第5圖係藉由第1實施形態之步驟所得的皮革樣片之 截面典型圖。 第6圖係說明第3實施形態之皮革樣片之製法的典型 步驟圖。 第7圖係說明第4實施形態之聚胺基甲酸酯積層物之 φ 積層中間物的製法的典型步驟圖。 第8圖係說明在使第7圖中捲取的積層中間物之不織 布表面經加熱平滑化處理的不織布表面側上，藉由噴霧塗 布第2聚胺基甲酸酯層，且進行加熱壓押壓花處理之步驟 的典型步驟圖。 第9圖係在脫模紙上塗布第2熱熔融型濕份硬化聚胺 基甲酸酯，且貼合於第7圖中經捲取的積層中間物之不織 -37- 201016923 布表面經加熱平滑化處理的不織布表面側之步驟的典型步 驟圖。 第10圖係說明比較例2之皮革樣片之製法的典型步驟 圖。 【主要元件符號說明】 3〇 送出捲軸 31、32、33a、33b、34、35 滾筒 36 ❹ 3 7 送出捲軸 基材 38 捲取捲軸 3〇1 剝離紙（脫模紙） 3 02 工作線 3〇3、3 0 5 刮刀塗布機 3〇4 水蒸氣噴霧器 3 1 2 ' 3 1 4 ❿ 熱熔融型濕份硬化聚胺基甲 酸酯 基布 1 2 第1濕份硬化聚胺基甲酸酯 3 多孔性薄片 4 第2濕份硬化聚胺基甲酸酯 5 脫模紙 10 皮革樣片 11 送出捲軸 12 送出捲軸 -38- 201016923 13 14 20、22、23 ' 24a、24b、25 ' 27 2 1 > 26 100 ' 10 1 102 ' 104 50 44 © 45 42 43 20、22、23、24a、24b、25、26、27、 2 1 144 1 54 46R-70N manufactured by Lintec Co., Ltd. © [Example 1] A leather sample 10 was produced by using the manufacturing process shown in Fig. 2. Specifically, the reel 11 is fed out in advance, and the base fabric 1 is fed to the take-up reel 14 via the rollers 20, 22, 23, 24a, 24b, 25, and 27 at a speed of lm/min to form a line. Then, the heat-melted hot-melt type moisture-hardening polyurethane 2 accommodated in the resin crucible 102 is discharged in a molten state toward the base fabric 1 on the line. Then, the hot-melt type moisture-cured polyurethane 2 which has been passed down is applied onto the surface of the base fabric 1 by a reversible roll coater 21 having a heating roll having a surface temperature of 110 °C. At this time, the coating thickness was adjusted to 2 0 0 /z m. Then, the surface of the coating layer of the hot-melt type moisture-cured polyurethane 2 in a molten or softened state is sent out from the take-up reel 12 to the polyurethane non-woven fabric 3», and the polyurethane non-woven fabric 3 By laminating the surface of the coating layer of the first moisture-curing polyurethane 2 by heating the calender roll 1 while heating and smoothing the polyurethane 3 on the surface - 24 - 201016923 And a micro hole or a communication hole is formed inside. Further, at this time, the surface temperature of the calender roll 100 was 155 ° C. Next, the laminated intermediate formed by the heat-smoothed polyurethane woven fabric 3 is bonded to the hot-melt type moisture-cured polyurethane 4 via the rollers 23, 24a, 24b, and 25 The resin spreader 104 is conveyed directly below. Then, the hot-melt type moisture-hardening polyurethane 4 accommodated in the resin spreader 1〇4 is flowed down on the laminated intermediate in a molten state by a heating roll having a surface temperature of 11 〇°C. The reversible roll coater 26 is applied to form a second polyurethane layer. At this time, the coating thickness was adjusted to 40 #m. Thereafter, the release paper 5 is fed from the transfer reel 13 and bonded to the coated hot-melt type moisture-cured polyurethane 4 by a calender roll 1〇1. Thus, a leather piece 1 having the layer structure shown in Fig. 3 was formed. Next, the obtained leather piece 10 is taken up by the take-up roll 14 in a state of being covered with the release paper 5. G In the above-mentioned process, there is no phenomenon that the laminated intermediate is wound around the rolls 24a, 24b, etc., and it is excellent in continuous productivity. Then, the leather piece 10 was aged for 35 hours under the conditions of a temperature of 40 ° C and a relative humidity of 60% in a wound state. After the aging, the obtained leather swatch 10 was cut into a predetermined area, and the release paper 5 was peeled off, and the interlayer adhesion was evaluated by the following method. (Interlayer adhesion) -25- 201016923 On the surface of the second polyurethane layer 4 of the peeled leather sample 10 of the release paper, the cloth is melted and melted [Trademark: Merco Tape, Sun Chemical Co., Ltd.) The pressure was measured at 130 ° C for 5 seconds, and the peel strength was measured using a Tensilon (manufactured by Shimadzu Corporation) based on JIS K6854-2 at a front end speed of 20 0 mm/min. Moreover, the position of the portion which was peeled off at this time was confirmed. As a result, the peeling strength of the leather piece 10 was 10 / 6 kg / 25 mm, and there was an internal peeling in the layer 1 of the base fabric. [Example 2] 皮革 The leather sample piece 50 was produced using the manufacturing process as shown in Fig. 4. Specifically, the reel U is fed out in advance, and the base fabric 1 is fed to the take-up reel 14 via the rollers 20, 22, 23, 24a, 24b, 25, 26, and 27 at a speed of lm/min to form a line. Then, the heat-melted hot-melt type moisture-hardening polyurethane 2 accommodated in the resin spreader 102 is flowed in a molten state toward the base fabric 1 on the line. Then, the hot-melt type moisture-cured polyurethane 2 which passed down was applied onto the surface of the base fabric 1 by a reversible roll coater 21 having a Q-heat roll having a surface temperature of 110 °C. At this time, the coating thickness was adjusted to 30/zm. Then, the polyurethane 3 non-woven fabric 3 of the reel 12 is fed out to the surface of the coating layer of the hot-melt type moisture-cured polyurethane 2 in a molten or softened state, and is bonded by heating calender rolls 100. On the surface of the coating layer of the first moisture-curing polyurethane 2, the polyurethane non-woven fabric 3 is simultaneously smoothed by heating to form fine pores or continuous pores on the surface and inside. Further, at this time, the surface temperature of the heating calender roll 100 was 155 °C. -26- 201016923 Next, the laminated intermediate formed by the heat-smoothed polyurethane 3 is bonded to the aqueous polyurethane adhesive 44 via the rollers 23, 24a, 24b, and 25 The resin hopper 144 is conveyed directly below. Then, the aqueous polyurethane adhesive 44 contained in the resin crucible 144 is discharged onto the surface of the polyurethane non-woven fabric 3, and is applied to the polyamine in a uniform thickness by a knife coater 154. The urethane is not on the surface of the fabric 3. At this time, the coating thickness was adjusted to 50/zm. Thereafter, drying is carried out by a drying oven 46 to form an adhesive layer 47 from the aqueous polyurethane adhesive 44. Then, it is merged with the release paper-attached polyurethane film 45 fed from the feed roller 43 to form the polyamine of the adhesive layer 47 and the surface of the polyurethane film 45 to which the release paper is attached. The urethane film 42 is applied downward by the calender roll 101. The leather piece 50 having the layer constitution as shown in Fig. 5 is thus formed. Then, the obtained leather piece 50 is taken up by the take-up reel 14 in a state of being covered with the release paper 5. In the above-mentioned step, the phenomenon that the laminated intermediate is wound around the drum or the like is not caused in the process, and it is excellent in continuous productivity. Next, in the wound state, the leather piece 50 was subjected to a aging treatment under the conditions of a temperature of 40 ° C and a relative humidity of 60% for 35 hours. After the aging, the obtained leather swatch 50 was cut into a predetermined area, and the release paper 5 was peeled off, and the interlayer adhesion was evaluated by the same method as in Example i. As a result, the peel strength of the leather piece 50 was 13.3 kg / 2 5 mm, and there was an internal peeling in the first layer of the base fabric. [Example 3] -27- 201016923 A polyurethane laminate was produced using the manufacturing process as shown in Figs. 7 and 8. Specifically, as shown in Fig. 7, the reel 11 is fed out, and the base fabric 1 is fed to the take-up reel 74 at a speed of lm/min through the drum 20 to form a line. Then, the heat-melted hot-melt type moisture-hardening polyurethane 2 accommodated in the resin crucible 102 is discharged in a molten state toward the base fabric 1 on the line. Then, the hot-melt type moisture-cured polyurethane 2 which has been passed down is applied onto the surface of the base fabric 1 by a reversible roll coater 21 having a heating roll having a surface temperature of 11 °C. At this time, the coating thickness was adjusted to 200/zm. Then, the surface of the coating layer of the hot-melt type moisture-cured polyurethane 2 in a molten or softened state is sent out from the take-up reel 12 to the polyurethane nonwoven fabric 3, and the calender roll 100 is attached thereto by heating. On the surface of the coating layer of the moisture-cured polyurethane 2, a build-up intermediate 140 is formed. Then, the laminated intermediate 140 is taken up by the take-up reel 74. Next, the wound laminated intermediate 140 was subjected to a ripening treatment for 35 hours under the conditions of a temperature of 40 t and a relative humidity of 60%. The surface of the polyurethane non-woven fabric 3 of the laminated intermediate 140 after the aging is heated and smoothed by a calender roll at a temperature of 155 ° C to form the first polyurethane layer and the polyamine group. The total thickness of the acid ester nonwoven layer was 125 μm. Fine pores or communication pores are formed in the inside and on the surface of the heat-smoothed polyurethane nonwoven fabric 3. Then, as shown in Fig. 8, on the surface of the polyurethane non-woven fabric 3 on the surface layer of the laminated intermediate 140, spray coating was applied by a spray coater 200 to have a solid content of 15 g/m2. The polyurethane resin is used as a second polyurethane layer from -28 to 201016923, and is dried in a drying furnace 46. Further, by heating the calender roll 101 and heating the embossing by a flat plate, the mold is pressed and processed. A polyurethane laminate having both fine wrinkles and smoothness. The interlayer adhesion was evaluated by the same method as in Example 1 using the obtained polyurethane laminate. As a result, the peel strength of the polyurethane laminate was 12.5 kg / 25 mm, and there was internal peeling in the first layer of the base fabric. [Comparative Example 1] A step of replacing the urethane nonwoven fabric 3 having the affixed with the urethane 3 as shown in Fig. 2 except for the process of using the step of attaching the urethane non-woven fabric 3 as shown in Fig. 1 The process is to make leather samples, and the examples! Leather swatches were produced identically. Specifically, as shown in Fig. 1, the release paper 301 is fed from the take-up reel 30 to the take-up reel 38 at a speed of lm/min to form a line. Then, the release paper 301 attached to the delivery reel 30 is carried on the rollers 31 and 32 and conveyed. Then, a hot-melt type moisture-cured polyurethane 312 is melted by a knife coater 303 on the surface of the release paper 301 to form a film layer. At this time, the coating thickness was adjusted to 40/zm. Then, water vapor is blown by the water vapor atomizer 304 on the film layer formed of the hot-melt type moisture-cured polyurethane 312. Next, it is carried on the rollers 33a, 33b, fed into the drum 34, and coated with the hot-melt type moisture-cured polyurethane 314 in a molten state by a knife coater 305. Then, the base fabric 37 is supplied from the take-up reel 36, and The base fabric 37 was bonded to the adhesive layer of the hot-melt type moisture-cured polyurethane with a roll 35 to produce a leather sample. -29- 201016923 In the above-mentioned step, when the intermediate material is wound up in the drums 33a and 33b shown in Fig. 1 during the process, the problem that the conveyance cannot be smoothly performed frequently occurs, and it is difficult to continuously produce. Further, the leather piece which was easily obtained was subjected to a ripening treatment at a temperature of 40 ° C and a relative humidity of 60% for 35 hours. After the aging, the obtained leather plaque was cut into a predetermined area, and the release paper was peeled off, and the interlayer adhesion was evaluated by the same method as in Example 1. As a result, the peel strength of the leather piece was 6.5 kg/25 mm, and the interface formed by the moisture-based hardening polyurethane 3 1 2 and the layer formed by the moisture-hardening polyurethane 314 was Interface peeling situation. [Comparative Example 2] A step of replacing the urethane-nonwoven fabric 3 having the affixed with the urethane 3 as shown in Fig. 4 except that the step of blowing water vapor by the steam atomizer 304 as shown in Fig. 10 was used. A leather sample piece was produced in the same manner as in Example 2 except that the leather sample piece 80 was produced. Specifically, the take-up reel 14 feeds the reel 11 in advance at a speed of 1 m/min, and the base fabric 1' is fed through the rollers 20, 23, 24a, 24b, 25, 26, and 27 to form a line. Then, the heat-melted hot-melt type moisture-hardening polyurethane 2 accommodated in the resin crucible 102 is discharged in a molten state toward the base fabric 1 on the line. Then, the hot-melt type moisture-cured polyurethane 2 which has been passed down is applied onto the surface of the base fabric 1 by a reversible roll coater 21 having a heating roll having a surface temperature of no. At this time, the coating thickness was adjusted to 30; / m. Then, water vapor of -30-201016923 was blown on the film layer formed of the hot-melt type moisture-cured polyurethane 2 by a water vapor atomizer 3〇4. Then, the rollers 23, 24a, 24b, and 25 are conveyed directly under the resin crucible 144 containing the aqueous polyurethane adhesive 44. Then, the aqueous polyurethane adhesive 44 contained in the resin spreader 144 is passed over the surface of the film formed of the hot-melt type moisture-cured polyurethane 2, by a knife coater 154. Apply in a uniform thickness. At this time, the coating thickness was adjusted to 50 / / m. Thereafter, drying is carried out by a drying oven 46 to form an adhesive layer 47 from the aqueous polyurethane adhesive 44. Then, it is merged with the release paper-attached polyurethane film 45 fed from the feed roller 43 to bond the adhesive layer 47 to the surface of the release film-attached polyurethane film 45. The urethane film 42 is applied downward by the calender roll 101. The leather piece 80 is thus formed. Then, the obtained leather piece 80 is taken up by the take-up reel 14 in a state of being covered with the release paper 5. In the above-mentioned step, when the laminated intermediates are attached to the rolls 24a and 24b shown in Fig. 10 during the process, the problem that the conveyance cannot be smoothly performed frequently occurs, and continuous production is not easy. Further, the leather piece which was easily obtained was subjected to a ripening treatment at a temperature of 40 ° C and a relative humidity of 60% for 35 hours. After the aging, the obtained leather plaque 80 was cut into a predetermined area, and the release paper was peeled off, and the interlayer adhesion was evaluated by the same method as in Example 1. As a result, the peel strength of the leather sample was 6.5 kg / 25 mm, and the interface formed by the moisture-hardened polyurethane 2 and the layer formed of the polyurethane condensate 42 had an interface peeling. -31 - 201016923 As a result of the above examples, it is understood that after coating the surface of the first moisture-curing polyurethane with a polyurethane non-woven fabric, the second moisture-hardening polyamine group is laminated. The acid ester, Example 1 for forming a leather plaque, and the surface of the first moisture-cured polyurethane coated with a polyurethane non-woven fabric, and the adhesive layer from the aqueous polyurethane Adhesively bonded to a preformed polyurethane film of a release paper polyurethane film to form a leather sample, in the second embodiment, there is no first wet hardening polyamine group. In the case where the toluene 2 rolls are attached to the drum, they can be smoothly conveyed in the process, and the continuous productivity is excellent. Further, after coating the surface of the first moisture-cured polyurethane with a polyurethane non-woven fabric, the aqueous polyurethane resin is spray-coated to form a second polyurethane. In the third embodiment of the layer, since the laminated intermediate is taken up by coating with the polyurethane, the production step can be simplified. Further, in Comparative Examples 1 and 2 in which the surface of the first moisture-curing polyurethane 2 was not coated with the polyurethane non-woven fabric 3, the first moisture-cured polyurethane bismuth phthalate was produced at the time of production. The coating layer is attached to the drum and cannot be smoothly conveyed during the process, so continuous production is difficult. Further, the leather samples obtained in Examples 1 to 3 had high peel strength in the interlayer adhesion test and internal peeling in the layer formed of the first moisture-cured polyurethane. Further, the leather sample obtained in the comparative example had a low peeling strength, and the interface between the first moisture-cured polyurethane and the second moisture-cured polyurethane had a peeling property. In the examples i to 3, the -32-201016923 polyurethane woven fabric has a viscosity-increasing effect on the first polyurethane layer and the second polyurethane layer, and the main effect can be achieved. The function. As described above, one aspect of the present invention relates to a method for producing a leather sample comprising forming a heat-melted moisture-curing polyurethane on a surface of a base fabric or a release paper by heat-melting a first polyurethane coating layer forming step of the polyurethane layer, a porous sheet bonding step of laminating a porous sheet on the first polyurethane layer, and the porous layer A second polyurethane layer forming step of forming a second polyurethane layer on the outer surface of the sheet. According to this production method, the surface of the viscous hot-melt type moisture-curing polyurethane formed as the first polyurethane layer is substantially covered with a non-tacky porous sheet. It can suppress the decrease in the productivity of the leather sample caused by the adverse effect of the viscosity. Further, since the voids of the porous sheet exhibit a viscosity-increasing effect, the adhesion between the formed second polyurethane layer and the first polyurethane layer can be improved. Further, in the case of the porous sheet, since sufficient moisture passage can be secured, the moisture-hardening property of the hot-melt type moisture-cured polyurethane can be sufficiently maintained. Secondly, the use amount of the organic solvent can be reduced by using a solvent-free hot-melt type moisture-curing polyurethane. Further, in the above-described method, after the second polyurethane layer forming step, a sheet bonding step of laminating a sheet on the surface of the second polyurethane layer is provided in the first polyamine In the step of forming a urethane layer, when the first polyurethane layer is formed on the surface of the base fabric, the sheet of the sheet-bonding-33-201016923 step is a release paper on the surface of the release paper. When the first polyurethane paper layer is formed, the sheet is preferably a base fabric. With this configuration, the base fabric can be used in the sheet bonding step instead of using the base fabric in the first polyurethane layer forming step, or the release paper can be used in the sheet bonding step. The release paper is used in the first polyurethane layer forming step, and in any of the methods, the release film used in the first polyurethane layer forming step or the sheet bonding step can be peeled off. Paper, complete leather samples. Further, in the above-described production method, the porous sheet is a polyurethane-based nonwoven fabric, and the porous sheet bonding step is smoothed by heating and pressing the polyurethane nonwoven fabric. Preferably, the step of bonding to the first polyurethane layer is preferred. By heat-pressing the polyurethane non-woven fabric, it is bonded to the first polyurethane layer to compress a polyurethane having a large space to form a moderate void. Smoothed sheet. Thereby, the strength of the layer formed of the porous sheet can be increased. Further, the adhesion between the first polyurethane layer and the second polyurethane layer can be improved. The porous sheet bonding step is carried out by laminating the polyurethane lining layer with or without bonding the polyurethane lining layer to the first polyurethane layer. In the step of smoothing by heating and pressing, since the polyurethane non-woven fabric can form a smoother sheet, it is preferable to further increase the strength of the layer formed of the porous sheet. Further, when the porous sheet is a foamable polyurethane sheet, it is easy to adjust the strength or the viscosity-increasing effect because it is easy to adjust the void ratio in advance. In the above-mentioned production method, it is preferred that the porous sheet is bonded to the first polyurethane layer in a molten or softened state to maintain a high adhesive strength and to easily bond the porous sheet. The second polyurethane layer forming step is a step of applying a heat-melted hot-melt type moisture-cured polyamine-based carbamate on the outer surface of the porous sheet. It is preferred to reduce the amount of the organic solvent used. Further, in the above-described production method, the second polyurethane layer forming step is a step of forming a hot-melt type moisture-cured polyurethane or an aqueous polyamine group which is formed on the surface of the sheet in advance. The step of bonding a formic acid polyurethane film to the outer surface of the porous sheet, when the first polyurethane layer is formed on the surface of the base fabric, the sheet is a release paper, and the sheet is a release paper. When the first polyurethane layer is formed on the surface of the release paper, the sheet is a base fabric, and the amount of the organic solvent used can be further reduced. Further, in the above production method, when the first polyurethane layer or the second polyurethane layer is a foamed polyurethane layer, an elastic softness can be obtained. Leather swatches are preferred. Further, in another aspect of the present invention, there is provided a leather plaque comprising a base fabric and a first polyamine group formed of a hot-melt type moisture-cured polyurethane on a surface of the base fabric. The formic acid ester layer is a porous sheet laminated on the polyurethane layer of the above-mentioned -35-201016923 1 and a second polyurethane layer laminated on the porous sheet. In this configuration, the voids of the porous sheet can exhibit a viscosity-increasing effect, and the adhesion between the porous sheet and the first polyurethane layer and the second polyurethane layer can be improved. By this, the peel strength and the viscous state of the obtained leather plaque can be improved. In addition, it can be manufactured by reducing the amount of the organic solvent used. Further, when the porous sheet is a polyurethane woven fabric which is smoothed by heating and pressing, bonding of the first polyurethane layer to the second polyurethane layer It is preferable that the smoothness and the viscous state of the leather and the leather sheet are excellent. Further, when the first polyurethane layer is a foamed polyurethane layer, it is preferable to form an elastic-rich leather sample. Further, when the second polyurethane layer is formed of a hot-melt type moisture-cured polyurethane or an aqueous polyurethane, it can be produced by further reducing the amount of the organic solvent used. φ [Industrial use price 値] By the method for producing a leather sample of the present invention, a viscous hot-melt type which is formed by coating a porous sheet which is not viscous as a first polyurethane layer The surface of the moisture-cured polyurethane can suppress the decrease in the productivity of the leather sample due to the adverse effect of the viscosity. Further, since the solvent-free hot-melt type moisture-curing polyurethane is used, the amount of the organic solvent used can be reduced. Further, the obtained leather sample 36-201016923 sheet has a high adhesion effect by the porous sheet, and the adhesion between the first polyurethane layer and the second polyurethane layer is high. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 refers to the drawing of "Fig. 3" described in Patent Document 1. Fig. 2 is a view showing a typical procedure of a method for producing a leather sample piece according to the first embodiment. Fig. 3 is a typical cross-sectional view of a leather piece obtained by the procedure of the first embodiment. Fig. 4 is a view showing a typical procedure of a method for producing a leather sample piece according to the second embodiment. . Fig. 5 is a typical cross-sectional view of a leather piece obtained by the procedure of the first embodiment. Fig. 6 is a view showing a typical procedure of a method for producing a leather piece of the third embodiment. Fig. 7 is a view showing a typical procedure for producing a φ laminated intermediate of the polyurethane laminate of the fourth embodiment. Fig. 8 is a view showing the surface of the non-woven fabric on which the surface of the non-woven fabric of the laminated intermediate material taken up in Fig. 7 is subjected to heat-smoothing treatment, by spraying the second polyurethane layer, and performing heat pressing. A typical step diagram of the steps of embossing. Figure 9 is a diagram of coating a second hot-melt type moisture-cured polyurethane on a release paper, and laminating the laminated intermediate in the drawing of Figure 7 to a non-woven fabric - 37 - 201016923 A typical step diagram of the step of smoothing the non-woven surface side. Fig. 10 is a view showing a typical procedure for the production of the leather sample of Comparative Example 2. [Main component symbol description] 3〇Receiving reels 31, 32, 33a, 33b, 34, 35 Roller 36 ❹ 3 7 Feeding reel base material 38 Reeling reel 3〇1 Release paper (release paper) 3 02 Working line 3〇 3, 3 0 5 blade coater 3〇4 steam sprayer 3 1 2 ' 3 1 4 ❿ hot melt type moisture hardening polyurethane fabric 1 2 first moisture hardening polyurethane 3 Porous sheet 4 Second moisture-hardening polyurethane 5 Release paper 10 Leather sample 11 Delivery reel 12 Delivery reel -38- 201016923 13 14 20, 22, 23 ' 24a, 24b, 25 ' 27 2 1 &gt ; 26 100 ' 10 1 102 ' 104 50 44 © 45 42 43 20, 22, 23, 24a, 24b, 25, 26, 27, 2 1 144 1 54 46

60 140 74 200 送出捲軸 捲取捲軸 、28滾筒 可逆式輥塗布器 壓延機 樹脂塡料機 皮革樣片 水性聚胺基甲酸酯黏合劑 附有脫模紙之聚胺基甲酸酯 聚胺基甲酸酯膜 送出捲軸 28搬送滾筒 可逆式輥塗布器 樹脂塡料機 壓延輥 乾燥爐 黏合劑層 皮革樣片 積層中間物 捲取捲軸 噴霧塗裝機 皮革樣片 -39- 8060 140 74 200 Feeding Reel Take-up Reel, 28 Roller Reversible Roll Applicator Calender Resin Dipper Leather Sample Waterborne Polyurethane Adhesive Polyurethane Polyurethane with Release Paper Acid film delivery reel 28 transport roller reversible roller coater resin skimmer calender roll drying oven adhesive layer leather sample laminated intermediate winding reel spray coating machine leather sample -39- 80

Claims (1)

201016923 七、申請專利範圍： 1. 一種皮革樣片之製法，其特徵爲具備藉由在基布或脫模紙 表面上塗布經加熱熔融的熱熔融型濕份硬化聚胺基甲酸 酯以形成第1聚胺基甲酸酯層的第1聚胺基甲酸酯層形成 步驟，在前述第1聚胺基甲酸酯層上貼合多孔性薄片之多 孔性薄片貼合步驟，及在前述多孔性薄片之外表面上形成 第2聚胺基甲酸酯層的第2聚胺基甲酸酯層形成步驟。 2. 如申請專利範圍第1項之皮革樣片之製法，其中另外具備 φ 在前述第2聚胺基甲酸酯層形成步驟後，於第2聚胺基甲酸 酯層之表面上貼合薄片的薄片貼合步驟，在基布之表面上形 成第1聚胺基甲酸酯層時，前述薄片爲脫模紙，在脫模紙之 表面上形成第1聚胺基甲酸酯層時，前述薄片爲基布。 3. 如申請專利範圍第1或2項之皮革樣片之製法，其中前述 多孔性薄片爲聚胺基甲酸酯不織布，前述多孔性薄片貼合 步驟係使前述聚胺基甲酸酯不織布藉由加熱押壓處理、予 以平滑化，貼合於前述第1聚胺基甲酸酯層的步驟。 4. 如申請專利範圍第3項之皮革樣片之製法，其中前述多 毚 W 孔性薄片貼合步驟，包含在使前述聚胺基甲酸酯不織布 貼合於第1聚胺基甲酸酯層的同時或貼合後，使聚胺基 甲酸酯不織布之面藉由加熱押壓處理、予以平滑化。 5. 如申請專利範圍第1或2項之皮革樣片之製法，其中前 述多孔性薄片爲發泡性聚胺基甲酸酯薄片。 6. 如申請專利範圍第1或2項之皮革樣片之製法，其中在 熔融或軟化狀態之前述第1聚胺基甲酸酯層上貼合前述 多孔性薄片。 -40- 201016923 7. 如申請專利範圍第1或2項之皮革樣片之製法，其中前 述第2聚胺基甲酸酯層形成步驟爲在前述多孔性薄片之 外表面上，塗布經加熱熔融的熱熔融型濕份硬化聚胺基 甲酸酯之步驟。 8. 如申請專利範圍第1項之皮革樣片之製法，其中前述第2 聚胺基甲酸酯層形成步驟係使預先在薄片表面上所形成 的熱熔融型濕份硬化聚胺基甲酸酯或來自水性聚胺基甲 酸酯之聚胺基甲酸酯膜’黏合於前述多孔性薄片的外表 ©面的步驟，在基布之表面上形成第1聚胺基甲酸酯層時， 前述薄片爲脫模紙，在脫模紙之表面上形成第1聚胺基 甲酸酯層時，前述薄片爲基布。 9.如申請專利範圍第1或2項之皮革樣片之製法，其中前 述第1聚胺基甲酸酯層或第2聚胺基甲酸酯層爲發泡聚 胺基甲酸酯層。 10.—種皮革樣片，其特徵爲具備基布、在前述基布表面上 積層的由熱熔融型濕份硬化聚胺基甲酸酯所形成的第1 聚胺基甲酸酯層、在前述第1聚胺基甲酸酯層上積層的 Φ 多孔性薄片、與在前述多孔性薄片上積層的第2聚胺基 甲酸酯層。 11.如申請專利範圍第10項之皮革樣片，其中前述多孔性薄片 爲藉由加熱壓押處理予以平滑化的聚胺基甲酸酯不織布。 12.如申請專利範圍第10或11項之皮革樣片，其中前述第 1聚胺基甲酸酯層爲發泡聚胺基甲酸酯層。 13.如申請專利範圍第10或11項之皮革樣片，其中前述第 2聚胺基甲酸酯層爲由熱熔融型濕份硬化聚胺基甲酸酯 或水性聚胺基甲酸酯所形成者。 -41 -201016923 VII. Patent application scope: 1. A method for preparing a leather sample, which is characterized in that it has a hot-melt type moisture-hardening polyurethane coated by heating and melting on a surface of a base cloth or a release paper to form a first a first polyurethane coating layer forming step of the polyurethane layer, a porous sheet bonding step of bonding the porous sheet to the first polyurethane layer, and the porous layer A second polyurethane layer forming step of forming a second polyurethane layer on the outer surface of the sheet. 2. The method for producing a leather sample according to claim 1, wherein φ is further provided on the surface of the second polyurethane layer after the step of forming the second polyurethane layer In the sheet bonding step, when the first polyurethane layer is formed on the surface of the base fabric, the sheet is a release paper, and when the first polyurethane layer is formed on the surface of the release paper, The aforementioned sheet is a base fabric. 3. The method for producing a leather sample according to claim 1 or 2, wherein the porous sheet is a polyurethane non-woven fabric, and the porous sheet bonding step is such that the polyurethane is non-woven. The step of heating and pressing, smoothing, and bonding to the first polyurethane layer. 4. The method for producing a leather sample according to the third aspect of the invention, wherein the multi-twist W sheet bonding step comprises bonding the polyurethane nonwoven fabric to the first polyurethane layer. At the same time or after bonding, the surface of the polyurethane non-woven fabric is smoothed by heating and pressing. 5. The method of claim 1, wherein the porous sheet is a foamable polyurethane sheet. 6. The method of producing a leather piece according to claim 1 or 2, wherein the porous sheet is bonded to the first polyurethane layer in a molten or softened state. The method for producing a leather sample according to claim 1 or 2, wherein the second polyurethane layer forming step is coating heat-melted on the outer surface of the porous sheet. The step of hot-melt type moisture-hardening polyurethane. 8. The method of claim 1, wherein the second polyurethane layer forming step is a hot-melt type moisture-hardening polyurethane formed on the surface of the sheet in advance. Or the step of adhering the polyurethane film of aqueous polyurethane to the outer surface of the porous sheet, when the first polyurethane layer is formed on the surface of the base fabric, The sheet is a release paper, and when the first polyurethane layer is formed on the surface of the release paper, the sheet is a base fabric. 9. The method of claim 1, wherein the first polyurethane layer or the second polyurethane layer is a foamed polyurethane layer. 10. A leather swatch characterized by comprising a base fabric, a first polyurethane layer formed of a hot-melt type moisture-curing polyurethane laminated on a surface of the base fabric, A Φ porous sheet laminated on the first polyurethane layer and a second polyurethane layer laminated on the porous sheet. 11. The leather plaque of claim 10, wherein the porous sheet is a polyurethane woven fabric which is smoothed by a heat pressing treatment. 12. The leather plaque of claim 10 or 11, wherein the first polyurethane layer is a foamed polyurethane layer. 13. The leather swatch of claim 10 or 11, wherein the second polyurethane layer is formed by a hot melt type moisture hardening polyurethane or an aqueous polyurethane. By. -41 -
TW098128752A 2008-08-28 2009-08-27 Leather sheet and process for manufacturing the same TW201016923A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI508864B (en) * 2012-08-08 2015-11-21

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* Cited by examiner, † Cited by third party
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DE102012202866A1 (en) 2012-02-24 2013-08-29 Adidas Ag Material for shoe upper
JP5583743B2 (en) * 2012-12-13 2014-09-03 高圧クロス株式会社 Synthetic leather and its manufacturing method
JP6725387B2 (en) * 2016-09-28 2020-07-15 積水化学工業株式会社 Resin liquid coating machine, composite sheet manufacturing method
JP6542436B2 (en) * 2018-06-18 2019-07-10 株式会社イノアックコーポレーション Skin material and method of manufacturing the same
CN110644244A (en) * 2019-09-03 2020-01-03 清远市齐力合成革有限公司 Production method of environment-friendly soft wrinkle mirror synthetic leather
CN114481643A (en) * 2020-10-26 2022-05-13 广东奥柏兴新材料有限公司 Solvent-free breathable moisture-permeable shoe lining leather and manufacturing method thereof

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* Cited by examiner, † Cited by third party
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JPS591822B2 (en) * 1979-10-22 1984-01-14 アキレス株式会社 Synthetic leather with excellent hydrolysis resistance and light resistance
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* Cited by examiner, † Cited by third party
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