TW202243869A - Porous layer structure, and method for producing porous layer structure - Google Patents

Porous layer structure, and method for producing porous layer structure Download PDF

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TW202243869A
TW202243869A TW111102564A TW111102564A TW202243869A TW 202243869 A TW202243869 A TW 202243869A TW 111102564 A TW111102564 A TW 111102564A TW 111102564 A TW111102564 A TW 111102564A TW 202243869 A TW202243869 A TW 202243869A
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layer
water
base layer
layer structure
base
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TWI835056B (en
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綿貫祥汰
奥泉寛女
河村亮
佐佐木一弥
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日商大日精化工業股份有限公司
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    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Provided are: a porous layer structure in which satisfactory adhesion between a base material and a foamed layer produced by foaming a urethane prepolymer can be exhibited even when the range of density at which the formation of a foamed layer can be achieved is expanded to a lower range (i.e., a range in which a foamed layer can become softer), and can exhibit an excellent texture (softness); and a method for producing a porous layer structure. The porous layer structure comprises a base material 10, an under layer 20 provided on the base material 10 and formed from a blend solution containing a water-soluble resin, and a foamed layer 30 provided on the under layer 20 and produced by foaming a urethane prepolymer having an isocyanate group at an terminal thereof, in which the basis weight of the under layer 20 is 3 to 60 g/m2·dry, and the film rupture strength of the under layer 20 after being dried is 5 MPa or more.

Description

多孔層結構體及多孔層結構體之製造方法Porous layer structure and method for producing porous layer structure

本發明係關於一種多孔層結構體及多孔層結構體之製造方法。The present invention relates to a porous layer structure and a method for manufacturing the porous layer structure.

聚胺酯系樹脂製合成人造皮革之製造方法大致分為濕式法及乾式法。其中，使用濕式法所得之聚胺酯系樹脂製合成人造皮革之特徵在於，與乾式法相比，觸感更柔軟，具有高級感。 濕式法中所使用之聚胺酯系樹脂通常較多地使用N,N'-二甲基甲醯胺(DMF)或N-甲基-2-吡咯啶酮(NMP)作為有機溶劑，近年來，由於對於人體之有害性及環境問題，開始限制或禁止使用DMF等，迫切期望不使用DMF等有機溶劑之環保型合成人造皮革來作為代替品。 The manufacturing method of synthetic artificial leather made of polyurethane resin is roughly divided into wet method and dry method. Among them, the synthetic artificial leather made of polyurethane resin obtained by the wet method is characterized in that it has a softer touch and a high-quality feeling than the dry method. Polyurethane resins used in wet methods usually use N,N'-dimethylformamide (DMF) or N-methyl-2-pyrrolidone (NMP) as organic solvents. In recent years, Due to the harmfulness to the human body and environmental problems, the use of DMF and the like has been restricted or banned, and there is an urgent need for environmentally friendly synthetic artificial leather that does not use organic solvents such as DMF as a substitute.

作為不使用有機溶劑之環保型合成人造皮革，有使用反應型熱熔系接著劑(RHM)將基材與表皮層接著者，該反應型熱熔系接著劑為末端具有異氰酸基之胺基甲酸酯預聚物。 胺基甲酸酯預聚物末端具有異氰酸基之胺基甲酸酯預聚物與空氣中之水分(濕氣)反應而進行交聯反應，藉此表現出作為濕氣硬化型接著劑之功能。因此，包含末端具有異氰酸基之胺基甲酸酯預聚物之反應型熱熔系接著劑(RHM)為不使用有機溶劑之固形物成分100%之接著劑，目前作為環保型接著劑，需求不斷增加。 As an environmentally friendly synthetic artificial leather that does not use organic solvents, there are those that use reactive hot melt adhesives (RHM) to bond the substrate and the skin layer. The reactive hot melt adhesives are amines with isocyanate groups at the end. urethane prepolymer. Urethane prepolymers Urethane prepolymers with isocyanate groups at the end react with moisture (humidity) in the air to undergo cross-linking reactions, thereby exhibiting a moisture-curing adhesive function. Therefore, the reactive hot-melt adhesive (RHM) containing urethane prepolymers with isocyanate groups at the end is an adhesive with a solid content of 100% without using organic solvents, and is currently used as an environmentally friendly adhesive. , increasing demand.

又，關於合成人造皮革，為提高基材與接著層之接著性，有如下提案：於基材上塗佈或使基材中含浸包含水性聚胺酯樹脂(PUD)之調配液，使調配液乾燥後，於基材與接著層之間設置包含PUD之層(例如專利文獻1、2)。 根據專利文獻1、2，藉由設置包含PUD之層，可提高基材與接著層間之接著強度，但不止該PUD層之水分對發泡無任何貢獻，更無法兼具與藉由使用DMF之濕式法製成之合成人造皮革(發泡層密度：0.05 g/cm 3～0.4 g/cm 3左右)同等程度之質感(柔軟性)，後者通常被評價為柔軟。 此外，一般而言，當試圖藉由降低發泡層之發泡密度來提高柔軟度時，與基材之接著強度容易降低，結果還存在欠缺作為皮革之實用性之問題。 先前技術文獻 專利文獻 Also, for synthetic artificial leather, in order to improve the adhesiveness between the base material and the adhesive layer, there is a proposal to apply or impregnate the base material with a preparation solution containing a water-based polyurethane resin (PUD) on the base material, and then dry the preparation solution. , A layer containing PUD is provided between the base material and the adhesive layer (for example, Patent Documents 1 and 2). According to patent documents 1 and 2, by providing a layer containing PUD, the bonding strength between the base material and the bonding layer can be improved, but not only the moisture in the PUD layer does not contribute to foaming, but it cannot be combined with the effect of using DMF. Synthetic artificial leather (foam layer density: about 0.05 g/cm 3 ~0.4 g/cm 3 ) made by wet method has the same texture (softness), and the latter is usually evaluated as soft. In addition, in general, when an attempt is made to increase softness by reducing the foam density of the foam layer, the bonding strength to the base material tends to decrease, resulting in a problem of lack of practicality as leather. Prior Art Documents Patent Documents

專利文獻1：日本專利第4123418號公報 專利文獻2：日本專利特開2005-206970號公報 Patent Document 1: Japanese Patent No. 4123418 Patent Document 2: Japanese Patent Laid-Open No. 2005-206970

[發明所欲解決之問題][Problem to be solved by the invention]

本發明係為解決該問題點而成者，目的在於提供一種多孔層結構體及多孔層結構體之製造方法，該多孔層結構體即使將作為發泡層可實現之密度範圍擴展至更低之區域(作為發泡層更柔軟之區域)，亦能夠發揮基材與使胺基甲酸酯預聚物發泡而成之發泡層之良好密接性，且能夠發揮優異質感(柔軟性)。 [解決問題之技術手段] The present invention is made to solve this problem, and an object thereof is to provide a porous layer structure and a method for producing the porous layer structure, which can expand the range of density that can be realized as a foam layer to a lower level. The region (a region where the foam layer is softer) can also exhibit good adhesion between the base material and the foam layer formed by foaming the urethane prepolymer, and can exhibit excellent texture (softness). [Technical means to solve the problem]

本發明人等為解決上述問題而進行了銳意研究，結果發現，藉由在基材上形成利用包含水溶性樹脂之調配液所得之基底層，使得該基底層良好地表現出與基材之錨定作用，並且可利用調配液之水分使設置於基底層上之胺基甲酸酯預聚物無遺漏地充分發泡，因此可使發泡層之發泡形狀均勻且穩定，可解決該問題，從而想到本發明。即，本發明如下所述。The inventors of the present invention conducted earnest research to solve the above-mentioned problems, and as a result, found that by forming a base layer obtained by using a preparation solution containing a water-soluble resin on a base material, the base layer exhibits good anchoring with the base material. The urethane prepolymer placed on the base layer can be fully foamed without omission by using the moisture of the preparation liquid, so the foaming shape of the foam layer can be made uniform and stable, which can solve this problem , thus thinking of the present invention. That is, the present invention is as follows.

[1]一種多孔層結構體，其具備基材、設置於上述基材上之利用包含水溶性樹脂之調配液而形成之基底層、及設置於上述基底層上之使末端具有異氰酸基之胺基甲酸酯預聚物發泡而成之發泡層，且上述基底層之單位面積重量為3～60 g/m 2・dry，上述基底層之乾燥後之皮膜斷裂強度為5 MPa以上。 [2]如[1]中記載多孔層結構體，其中上述包含水溶性樹脂之調配液之黏度於25℃下為500～50,000 mPa・s。 [3]如[1]或[2]中記載之多孔層結構體，其中上述水溶性樹脂為選自由水性聚胺酯樹脂、水性聚乙二醇樹脂及水性聚乙烯醇樹脂所組成之群中之至少一種。 [4]如[3]中記載之多孔層結構體，其中上述水溶性樹脂為水性聚胺酯樹脂。 [5]如[3]中記載之多孔層結構體，其中上述水溶性樹脂為水性聚乙二醇樹脂，且上述水性聚乙二醇樹脂之數量平均分子量為50萬以上。 [6]如[1]至[5]中任一項記載之多孔層結構體，其中上述基底層與上述基材之厚度比為1：10～1：1,000。 [7]如[1]至[6]中任一項記載之多孔層結構體，其中上述發泡層之積層有上述基底層之面之相反面上具有表皮層。 [8]一種多孔層結構體之製造方法，其包括：基底層積層步驟，其係於基材上塗佈包含水溶性樹脂之調配液，於上述基材上形成濕潤狀態之基底層；及發泡層積層步驟，其係於上述濕潤狀態之基底層上配置末端具有異氰酸基之胺基甲酸酯預聚物，藉由上述基底層之水分使上述胺基甲酸酯預聚物發泡而形成發泡層；且上述基底層之單位面積重量為3～60 g/m 2・dry，上述基底層之乾燥後之皮膜斷裂強度為5 MPa以上。 [9]如[8]中記載之多孔層結構體之製造方法，其進而包括表皮層積層步驟，該表皮層積層步驟係於上述發泡層之積層有上述基底層之面之相反面上積層表皮層。 [10]如[8]或[9]中記載之多孔層結構體之製造方法，其於上述發泡層積層步驟之後，進而包括熟化步驟，該熟化步驟係實施促進上述發泡層之發泡之熟化處理。 [發明之效果] [1] A porous layer structure comprising a base material, a base layer formed on the base material from a preparation solution containing a water-soluble resin, and a base layer having an isocyanate group at the end provided on the base layer. The foam layer is formed by foaming the urethane prepolymer, and the weight per unit area of the base layer is 3-60 g/m2 · dry, and the film breaking strength of the base layer after drying is 5 MPa above. [2] The porous layer structure as described in [1], wherein the viscosity of the prepared solution containing the water-soluble resin is 500 to 50,000 mPa·s at 25°C. [3] The porous layer structure described in [1] or [2], wherein the water-soluble resin is at least one selected from the group consisting of water-based polyurethane resins, water-based polyethylene glycol resins, and water-based polyvinyl alcohol resins. A sort of. [4] The porous layer structure described in [3], wherein the water-soluble resin is a water-based polyurethane resin. [5] The porous layer structure described in [3], wherein the water-soluble resin is a water-based polyethylene glycol resin, and the number-average molecular weight of the water-based polyethylene glycol resin is 500,000 or more. [6] The porous layer structure according to any one of [1] to [5], wherein the thickness ratio of the base layer to the substrate is 1:10 to 1:1,000. [7] The porous layer structure according to any one of [1] to [6], wherein the foam layer has a skin layer on a surface opposite to the surface on which the base layer is laminated. [8] A method for producing a porous layer structure, comprising: a base layering step of coating a prepared liquid containing a water-soluble resin on a base material to form a base layer in a wet state on the base material; and Bubble layer lamination step, which is to arrange the urethane prepolymer having an isocyanate group at the end on the above-mentioned base layer in a wet state, and make the above-mentioned urethane prepolymer foam by the moisture of the above-mentioned base layer The foam layer is formed by foaming; and the weight per unit area of the above base layer is 3-60 g/m 2 ·dry, and the film breaking strength of the above base layer after drying is above 5 MPa. [9] The method for producing a porous layer structure as described in [8], which further includes a skin lamination step of laminating on the surface of the foam layer opposite to the surface on which the base layer is laminated. epidermis. [10] The method for producing a porous layer structure as described in [8] or [9], which further includes an aging step of promoting foaming of the above-mentioned foam layer after the above-mentioned foam lamination step. The ripening treatment. [Effect of Invention]

根據本發明，可提供一種多孔層結構體及多孔層結構體之製造方法，該多孔層結構體即使將作為發泡層可實現之密度範圍擴展至更低之區域(作為發泡層更柔軟之區域)，亦能夠發揮基材與使胺基甲酸酯預聚物發泡而成之發泡層之良好密接性，且能夠發揮優異質感(柔軟性)。According to the present invention, it is possible to provide a porous layer structure and a method for producing the porous layer structure, which can expand the density range achievable as a foam layer to a lower region (softer as a foam layer) region), it can also exhibit good adhesion between the base material and the foamed layer formed by foaming the urethane prepolymer, and can exhibit excellent texture (softness).

以下，對本發明之實施方式(本實施方式)詳細地進行說明，但本發明並不限定於該實施方式。Hereinafter, although the embodiment (this embodiment) of this invention is demonstrated in detail, this invention is not limited to this embodiment.

[多孔層結構體] 如圖1所示，本實施方式之多孔層結構體具備基材10、設置於基材10上之利用包含水溶性樹脂之調配液而形成之基底層20、及設置於基底層20上之使末端具有異氰酸基之胺基甲酸酯預聚物發泡而成之發泡層30。 [Porous layer structure] As shown in FIG. 1 , the porous layer structure of the present embodiment includes a base material 10, a base layer 20 formed on the base material 10 using a preparation solution containing a water-soluble resin, and a base layer 20 formed on the base layer 20. The foam layer 30 is formed by foaming a urethane prepolymer having an isocyanate group at the end.

(基材) 作為基材10，可使用先前公知之合成人造皮革之基材，例如可例舉：包含斜紋織物、平紋織物等之梭織物、使該梭織物之棉布料機械地起毛所得之起毛布、嫘縈布、尼龍布、聚酯布、Kevlar布、不織布(聚酯、尼龍、各種乳膠)、各種膜、及片等。 (Substrate) As the substrate 10, a conventionally known synthetic artificial leather substrate can be used, for example, a woven fabric including a twill weave, a plain weave, etc., a raised cloth obtained by mechanically raising the cotton cloth of the woven fabric, and rayon. Cloth, nylon cloth, polyester cloth, Kevlar cloth, non-woven cloth (polyester, nylon, various latex), various films, and sheets, etc.

基材10之厚度並無特別限定，只要可供利用包含水溶性樹脂之調配液形成基底層20即可，就保持多孔層結構體之機械強度之觀點而言，較佳為0.01～2.0 mm，更佳為0.02～1.5 mm。The thickness of the base material 10 is not particularly limited, as long as the base layer 20 can be formed using a preparation solution containing a water-soluble resin. From the viewpoint of maintaining the mechanical strength of the porous layer structure, it is preferably 0.01 to 2.0 mm. More preferably, it is 0.02 to 1.5 mm.

(基底層) 基底層20係將包含水溶性樹脂之調配液塗佈於基材10上，於基材10上以特定塗佈量(單位面積重量)設置為大致均勻之厚度。如圖1及圖2所示，基底層20可為一部分含浸於基材10中之狀態。 基底層20以下文所述之單位面積重量大致均勻且無遺漏地設置於整個基材10上，藉此與設置於基底層20上之發泡層30之接觸變得均勻，使得向發泡層30供給之水分量於平面(界面)方向上固定。 藉由使自基底層20供給之每單位面積之水分量之分佈固定，使得利用濕氣硬化型胺基甲酸酯預聚物所形成之發泡層20之發泡形狀均勻且穩定(即，可確實地防止產生過度發泡之部位或產生發泡形狀、尺寸之不均)，藉此可發揮優異質感(柔軟性)，並且使基材與發泡層間之接著性提高。 (basal layer) The base layer 20 is coated on the substrate 10 with a formulated solution containing a water-soluble resin, and is set to a substantially uniform thickness on the substrate 10 with a specific coating amount (weight per unit area). As shown in FIGS. 1 and 2 , the base layer 20 may be partially impregnated in the base material 10 . The base layer 20 is substantially uniformly and completely arranged on the entire base material 10 with the weight per unit area described below, whereby the contact with the foamed layer 30 disposed on the base layer 20 becomes uniform, so that the foamed layer 30 30 The amount of moisture supplied is fixed in the plane (interface) direction. By fixing the distribution of the amount of moisture per unit area supplied from the base layer 20, the foamed shape of the foamed layer 20 formed using the moisture-curable urethane prepolymer is uniform and stable (ie, It can reliably prevent excessive foaming or unevenness in foam shape and size), thereby exhibiting excellent texture (softness) and improving the adhesion between the base material and the foam layer.

基底層20之單位面積重量為3～60 g/m 2・dry。 當基底層20之單位面積重量未達3 g/m 2・dry時，設置於基底層20上之發泡層30之發泡容易變得不充分，而且基材10與發泡層30之密接性變得不良。又，當基底層20之單位面積重量超過60 g/m 2・dry時，發泡層30過度發泡，難以使發泡形狀及尺寸均勻且穩定，基底層20之皮膜物性容易對合成人造皮革之觸感造成不良影響，由於該等原因故而無法發揮優異質感(柔軟性)。 就使設置於基底層20上之發泡層30均勻且充分地發泡而使發泡形狀均勻且穩定之觀點而言，基底層20之單位面積重量較佳為5～50 g/m 2・dry，更佳為6～45 g/m 2・dry，進而較佳為7～40 g/m 2・dry。 The weight per unit area of the base layer 20 is 3-60 g/m 2 ·dry. When the weight per unit area of the base layer 20 is less than 3 g/m2 · dry, the foaming of the foam layer 30 disposed on the base layer 20 tends to be insufficient, and the adhesion between the base material 10 and the foam layer 30 is likely to be insufficient. Sex becomes bad. Also, when the weight per unit area of the base layer 20 exceeds 60 g/m 2 ·dry, the foam layer 30 will foam excessively, making it difficult to make the foam shape and size uniform and stable, and the physical properties of the base layer 20 will easily affect the synthetic artificial leather. The tactile feeling is adversely affected, and excellent texture (softness) cannot be exhibited due to these reasons. From the viewpoint of uniformly and sufficiently foaming the foamed layer 30 provided on the base layer 20 to make the foamed shape uniform and stable, the weight per unit area of the base layer 20 is preferably 5 to 50 g/m 2 . dry, more preferably 6 to 45 g/m 2 ·dry, still more preferably 7 to 40 g/m 2 ·dry.

基底層20之皮膜斷裂強度係乾燥後之皮膜斷裂強度，且為5 MPa以上。 當基底層20之乾燥後之皮膜斷裂強度未達5 MPa時，基底層20與基材10及發泡層30之剝離強度不足，基材10與發泡層30之密接性變得不良。 就使基底層20與基材10及發泡層30之剝離強度良好之觀點而言，基底層20之乾燥後之皮膜斷裂強度較佳為8 MPa以上，更佳為10 MPa以上，進而較佳為12 MPa以上。基底層20之乾燥後之皮膜斷裂強度之上限並無特別限定。 再者，基底層20之乾燥後之皮膜斷裂強度可藉由使用自動立體測圖儀之方法進行測定。作為具體之基底層20之皮膜斷裂強度之測定，可藉由實施例之「皮膜斷裂強度試驗」中記載之方法進行測定。 The breaking strength of the film of the base layer 20 refers to the breaking strength of the film after drying, and is more than 5 MPa. When the film breaking strength after drying of the base layer 20 is less than 5 MPa, the peel strength between the base layer 20, the base material 10 and the foam layer 30 is insufficient, and the adhesion between the base material 10 and the foam layer 30 becomes poor. From the viewpoint of making the peel strength between the base layer 20 and the substrate 10 and the foam layer 30 good, the film breaking strength after drying of the base layer 20 is preferably 8 MPa or more, more preferably 10 MPa or more, and even more preferably It is above 12 MPa. The upper limit of the film breaking strength after drying of the base layer 20 is not particularly limited. Furthermore, the film breaking strength of the base layer 20 after drying can be measured by using an automatic stereograph. As a specific measurement of the film breaking strength of the base layer 20, it can be measured by the method described in the "film breaking strength test" of the embodiment.

就發揮多孔層結構體之優異質感(柔軟性)之觀點而言，基底層20與基材10之厚度比較佳為1：10～1：1,000，更佳為1：30～1：750，進而較佳為1：70～1：500。 再者，基底層20與基材10之厚度比係基底層20之厚度t與基材10之厚度T的比率，但於如圖1所示含浸於基材10中之情形時，基底層20之厚度t還包含含浸於基材10中之部位之厚度，基材10之厚度T為減去含浸有基底層20之部位之厚度所得者。 From the viewpoint of exerting the excellent texture (softness) of the porous layer structure, the thickness ratio between the base layer 20 and the substrate 10 is preferably 1:10 to 1:1,000, more preferably 1:30 to 1:750, and further Preferably it is 1:70 to 1:500. Furthermore, the thickness ratio of the base layer 20 to the base material 10 is the ratio of the thickness t of the base layer 20 to the thickness T of the base material 10, but when impregnated in the base material 10 as shown in FIG. 1 , the base layer 20 The thickness t also includes the thickness of the part impregnated in the substrate 10, and the thickness T of the substrate 10 is obtained by subtracting the thickness of the part impregnated with the base layer 20.

上述基底層20之厚度t可根據利用SEM所得之截面圖像(參照圖2)藉由10點平均進行測量而算出。 另一方面，於基底層20無法藉由利用SEM所得之截面圖像加以確認之情形時，於離型紙(大日本印刷股份有限公司製造之「DNTP-FL」)上，以與基底層20之乾燥時之單位面積重量相等之方式塗佈測量對象之包含水溶性樹脂之調配液，作為乾燥步驟，依序經過於60℃下進行4分鐘、於100℃下進行3分鐘、於120℃下進行3分鐘之各步驟後，將離型紙上所形成之基底層之厚度視為測量對象之基底層20之厚度t。 作為將離型紙上所形成之基底層之厚度視為測量對象之基底層20之厚度t的根據，將包含水性聚胺酯樹脂(大日精化工業股份有限公司製造之「RESAMINE D-6065NP」)作為水溶性樹脂之調配液之乾燥時之單位面積重量、調配液黏度及上述離型紙上所形成之基底層20之厚度之具體關係示於表1中。如表1所示，可知基底層20之單位面積重量與黏度之變化無較大關聯，與離型紙上所形成之基底層之厚度相關。 The thickness t of the above-mentioned base layer 20 can be calculated by measuring the average of 10 points from the cross-sectional image (see FIG. 2 ) obtained by SEM. On the other hand, when the base layer 20 cannot be confirmed by the cross-sectional image obtained by SEM, on a release paper ("DNTP-FL" manufactured by Dainippon Printing Co., Ltd.), the base layer 20 is separated from the base layer 20. Coat the prepared solution containing water-soluble resin to be measured so that the weight per unit area during drying is equal. As a drying step, proceed at 60°C for 4 minutes, at 100°C for 3 minutes, and at 120°C. After each step for 3 minutes, the thickness of the base layer formed on the release paper was regarded as the thickness t of the base layer 20 of the measurement object. As the basis for considering the thickness of the base layer formed on the release paper as the thickness t of the base layer 20 to be measured, water-based polyurethane resin ("RESAMINE D-6065NP" manufactured by Dainichi Seika Co., Ltd.) was used as a water-soluble Table 1 shows the relationship between the weight per unit area, the viscosity of the formulated solution, and the thickness of the base layer 20 formed on the above-mentioned release paper when the formulated solution of the permanent resin is dried. As shown in Table 1, it can be seen that the weight per unit area of the base layer 20 has no significant relationship with the change of viscosity, but is related to the thickness of the base layer formed on the release paper.

[表1] 表1 乾燥時之單位面積重量(g/m 2・dry) 調配液黏度 (mPa・s/25℃) 基底層厚度 (μm) 5 500 4 3,000 4 10,000 5 50,000 5 25 500 21 3,000 22 10,000 23 50,000 25 50 500 42 3,000 45 10,000 48 50,000 50 [Table 1] Table 1 Weight per unit area when dry (g/m 2・dry) Prepared solution viscosity (mPa・s/25℃) Base layer thickness (μm) 5 500 4 3,000 4 10,000 5 50,000 5 25 500 twenty one 3,000 twenty two 10,000 twenty three 50,000 25 50 500 42 3,000 45 10,000 48 50,000 50

＜包含水溶性樹脂之調配液＞ 形成本發明之基底層20之包含水溶性樹脂之調配液係使水溶性樹脂分散於水中而成之調配液。作為水溶性樹脂，例如可例舉：水性聚胺酯樹脂、水性聚乙二醇樹脂、水性聚乙烯醇樹脂及水性丙烯酸樹脂等，較佳為選自由水性聚胺酯樹脂、水性聚乙二醇樹脂及水性聚乙烯醇樹脂所組成之群中之至少一種。其中，作為水溶性樹脂，較佳為水性聚胺酯樹脂。水性聚胺酯樹脂係藉由使多異氰酸酯化合物與多元醇成分反應而製造。只要可形成基底層20，則並無特別限定，但為提高於水中之分散性，可例舉於聚胺酯樹脂之分子內導入有親水性基者等。該親水性基可為陰離子、陽離子及非離子中之任一種，例如可例舉：(α)於分子內具有1個以上之活性氫基且具有羧基、磺酸基及其鹽之陰離子性化合物；(β)於分子內具有1個以上之活性氫基且含有包含環氧乙烷之重複單元之基、或包含環氧乙烷之重複單元與其他環氧烷之重複單元之基的非離子性化合物等。 再者，水溶性樹脂相對於整個調配液之含量(塗料固形物成分)並無特別限定，但若過少，則於添加增黏劑之情形時不易表現出效果，因此一般而言，可設為5～60質量%，較佳為10～50質量%，更佳為15～40質量%。 ＜Preparation solution containing water-soluble resin＞ The preparation solution containing the water-soluble resin that forms the base layer 20 of the present invention is a preparation solution obtained by dispersing the water-soluble resin in water. As the water-soluble resin, for example, water-based polyurethane resin, water-based polyethylene glycol resin, water-based polyvinyl alcohol resin and water-based acrylic resin, etc., are preferably selected from water-based polyurethane resin, water-based polyethylene glycol resin and water-based polyethylene glycol resin. At least one of the group consisting of vinyl alcohol resins. Among them, water-based polyurethane resin is preferred as the water-soluble resin. Water-based polyurethane resins are produced by reacting polyisocyanate compounds and polyol components. It will not be specifically limited as long as the base layer 20 can be formed, but in order to improve the dispersibility in water, the thing in which the hydrophilic group was introduced into the molecule|numerator of a polyurethane resin etc. is mentioned, for example. The hydrophilic group may be any of anionic, cationic, and nonionic, for example, (α) anionic compounds having one or more active hydrogen groups in the molecule, carboxyl groups, sulfonic acid groups, and salts thereof ;(β) Nonionic nonionic having one or more active hydrogen groups in the molecule and containing repeating units of ethylene oxide, or repeating units of ethylene oxide and repeating units of other alkylene oxides sexual compounds, etc. Furthermore, the content of the water-soluble resin relative to the entire preparation solution (coating solids content) is not particularly limited, but if it is too small, it is difficult to show the effect when adding a tackifier. Therefore, generally speaking, it can be set as 5-60 mass %, Preferably it is 10-50 mass %, More preferably, it is 15-40 mass %.

《水性聚胺酯樹脂》 構成本發明之水性聚胺酯樹脂之聚胺酯樹脂主要包含多元醇成分與異氰酸酯成分。 "Waterborne Polyurethane Resin" The polyurethane resin constituting the water-based polyurethane resin of the present invention mainly includes a polyol component and an isocyanate component.

〈多元醇成分〉 成為本發明中之多元醇成分之多元醇並無特別限定，可例舉：聚碳酸酯多元醇、聚醚多元醇、聚酯多元醇、聚內酯多元醇、聚烯烴多元醇、及聚甲基丙烯酸酯二醇等。 <Polyol component> The polyol used as the polyol component in the present invention is not particularly limited, and examples include: polycarbonate polyol, polyether polyol, polyester polyol, polylactone polyol, polyolefin polyol, and polymethylmethacrylate polyol. Acrylate diol, etc.

多元醇之數量平均分子量只要為500以上即可，並無特別限制，較佳為500～4,000左右，進而較佳為1,000～3,000左右。該等多元醇可單獨使用，或將2種以上組合使用，就長期耐久性之觀點而言，較佳為包含聚碳酸酯二醇。 再者，數量平均分子量為聚苯乙烯換算之數量平均分子量，通常可藉由凝膠滲透層析法(GPC)測定而求得。 The number average molecular weight of the polyol is not particularly limited as long as it is 500 or more, but it is preferably about 500 to 4,000, and more preferably about 1,000 to 3,000. These polyols may be used alone or in combination of two or more, but polycarbonate diol is preferably contained from the viewpoint of long-term durability. In addition, the number average molecular weight is the number average molecular weight of polystyrene conversion, and can usually obtain|require it by gel permeation chromatography (GPC) measurement.

〈異氰酸酯成分〉 成為本發明中之異氰酸酯成分之異氰酸酯並無特別限定，較佳為脂肪族二異氰酸酯、脂環族二異氰酸酯、及芳香族二異氰酸酯等二官能多異氰酸酯。 作為多異氰酸酯之具體例，有甲苯二異氰酸酯、4-甲氧基-1,3-苯二異氰酸酯、4-異丙基-1,3-苯二異氰酸酯、4-氯-1,3-苯二異氰酸酯、4-丁氧基-1,3-苯二異氰酸酯、2,4-二異氰酸酯-二苯醚、1,3,5-三甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、伸四甲苯基二異氰酸酯、1,5-萘二異氰酸酯、聯苯胺二異氰酸酯、鄰硝基聯苯胺二異氰酸酯、4,4'-二異氰酸基聯苄、1,4-四亞甲基二異氰酸酯、1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己烷二異氰酸酯、二甲苯二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、1,5-四氫萘二異氰酸酯、異佛爾酮二異氰酸酯、及二環己基甲烷4,4'-二異氰酸酯等。 再者，於多孔層結構體用於需要柔軟性、機械物性及耐變色性之用途中之情形時，較佳為主要使用脂肪族二異氰酸酯或脂環族二異氰酸酯。 <Isocyanate component> The isocyanate used as the isocyanate component in the present invention is not particularly limited, but difunctional polyisocyanates such as aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate are preferable. Specific examples of polyisocyanate include toluene diisocyanate, 4-methoxy-1,3-benzenediisocyanate, 4-isopropyl-1,3-benzenediisocyanate, 4-chloro-1,3-benzenediisocyanate, Isocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate-diphenyl ether, 1,3,5-trimethylbenzene diisocyanate, 4,4'-diphenylmethane diisocyanate, Tetracresyl diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanatobibenzyl, 1,4-tetramethylene diisocyanate Isocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, xylene diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate, etc. Furthermore, when the porous layer structure is used for applications requiring flexibility, mechanical properties, and discoloration resistance, it is preferable to mainly use aliphatic diisocyanate or alicyclic diisocyanate.

多異氰酸酯成分之異氰酸基當量相對於全部成分之羥基當量的比較佳為0.8～1.9，更佳為0.9～1.5。若NCO/OH處於上述範圍內，則柔軟性及耐久性更加良好。The ratio of the isocyanate group equivalent of the polyisocyanate component to the hydroxyl group equivalent of all components is preferably from 0.8 to 1.9, more preferably from 0.9 to 1.5. When NCO/OH exists in the said range, flexibility and durability will become more favorable.

〈添加劑〉 本發明之包含水溶性樹脂之調配液亦可視需要含有添加劑。作為添加劑，例如可例舉：增黏劑、交聯劑、抗氧化劑(受阻酚系、亞磷酸酯系、硫醚系等)、光穩定劑(受阻胺系等)、紫外線吸收劑(二苯甲酮系、苯并***系等)、氣體變色穩定劑(肼系等)、及金屬減活劑等。 <additive> The formulation solution containing the water-soluble resin of the present invention may also contain additives if necessary. Examples of additives include tackifiers, crosslinking agents, antioxidants (hindered phenols, phosphites, sulfides, etc.), photostabilizers (hindered amines, etc.), ultraviolet absorbers (diphenyl Ketone-based, benzotriazole-based, etc.), gas discoloration stabilizers (hydrazine-based, etc.), and metal deactivators, etc.

〈交聯劑〉 作為交聯劑，例如較佳為包含選自由異氰酸酯系交聯劑、碳二醯亞胺系交聯劑、㗁唑啉系交聯劑及環氧系交聯劑所組成之群中之至少一種，更佳為包含選自由異氰酸酯系、碳二醯亞胺系及㗁唑啉系交聯劑所組成之群中之至少一種。 若交聯劑之使用量過多，則存在引起基底層20之脆化、因未反應之交聯劑引起之塑化等不良情況之情形，因此交聯劑之使用量相對於水溶性樹脂(水分散體)100質量份，以交聯劑固形物成分換算值計，較佳為10質量份以下，進而較佳為0.5～8.0質量份。 〈Crosslinking agent〉 As the cross-linking agent, for example, preferably at least one selected from the group consisting of isocyanate-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents and epoxy-based cross-linking agents , more preferably at least one selected from the group consisting of isocyanate-based, carbodiimide-based and oxazoline-based crosslinking agents. If the amount of the crosslinking agent used is too much, then there is a situation that causes embrittlement of the base layer 20, plasticization caused by unreacted crosslinking agent, etc. Dispersion) 100 parts by mass, based on the converted value of the solid content of the crosslinking agent, preferably 10 parts by mass or less, more preferably 0.5 to 8.0 parts by mass.

《包含水溶性樹脂之調配液之黏度》 包含水溶性樹脂之調配液於25℃下之黏度可藉由添加增黏劑等之方式等進行適當調整。具體而言，較佳為500～50,000 mPa・s，更佳為550～45,000 mPa・s，進而較佳為600～40,000 mPa・s。 藉由使包含水溶性樹脂之調配液於25℃下之黏度為上述下限值以上，於基材10上塗佈調配液時，可於抑制調配液含浸於基材10中之同時形成基底層20之塗膜。又，藉由使包含水溶性樹脂之調配液於25℃下之黏度為上述上限值以下，於基材10上塗佈調配液時，可防止基底層20之塗膜成為斑狀。即，藉由使包含水溶性樹脂之調配液於25℃下之黏度為上述範圍，使得塗佈性良好，可於基材10上均勻且無遺漏地形成基底層20之塗膜。 "Viscosity of formulations containing water-soluble resins" The viscosity of the formulated solution containing the water-soluble resin at 25°C can be appropriately adjusted by adding a tackifier and the like. Specifically, it is preferably from 500 to 50,000 mPa·s, more preferably from 550 to 45,000 mPa·s, and still more preferably from 600 to 40,000 mPa·s. By setting the viscosity of the prepared liquid containing the water-soluble resin at 25° C. to be equal to or higher than the above-mentioned lower limit value, when the prepared liquid is coated on the base material 10 , it is possible to form a base layer while suppressing the impregnation of the prepared liquid into the base material 10 . 20 coating film. In addition, by making the viscosity of the prepared liquid containing the water-soluble resin at 25° C. below the above-mentioned upper limit, when the prepared liquid is coated on the substrate 10, the coating film of the base layer 20 can be prevented from becoming uneven. That is, by making the viscosity of the prepared solution containing the water-soluble resin in the above-mentioned range at 25° C., the applicability is improved, and the coating film of the base layer 20 can be uniformly and completely formed on the base material 10 .

《水性聚乙二醇樹脂》 本發明之水性聚乙二醇樹脂為成為下述數量平均分子量之水性聚乙二醇樹脂之乙二醇之聚合物。 《Waterborne Polyethylene Glycol Resin》 The water-based polyethylene glycol resin of the present invention is a polymer of ethylene glycol that becomes the water-based polyethylene glycol resin of the following number average molecular weight.

〈作為水溶性樹脂之水性聚乙二醇樹脂之數量平均分子量〉 就良好地形成基底層20之觀點、獲得最佳發泡密度之觀點而言，作為水溶性樹脂之水性聚乙二醇樹脂之數量平均分子量較佳為50萬以上，更佳為60萬以上。又，即使數量平均分子量過高，亦存在基底層20之形成容易性或發泡密度降低的情況，因此較佳為700萬以下，更佳為600萬以下，進而較佳為200萬以下。 再者，數量平均分子量為聚苯乙烯換算之數量平均分子量，通常可藉由凝膠滲透層析法(GPC)測定而求得。 <Number average molecular weight of water-based polyethylene glycol resin as water-soluble resin> From the standpoint of forming the base layer 20 well and obtaining the best foam density, the number average molecular weight of the water-based polyethylene glycol resin as the water-soluble resin is preferably 500,000 or more, more preferably 600,000 or more. Also, even if the number average molecular weight is too high, the ease of formation of the base layer 20 and the foaming density may decrease, so it is preferably 7 million or less, more preferably 6 million or less, and still more preferably 2 million or less. In addition, the number average molecular weight is the number average molecular weight of polystyrene conversion, and can usually obtain|require it by gel permeation chromatography (GPC) measurement.

《包含水溶性樹脂(水性聚胺酯樹脂)之調配液之製造方法》 關於本發明中之包含水性聚胺酯樹脂作為水溶性樹脂之調配液之製造方法，例如可例舉以下(1)及(2)之方法等： (1)經由：反應步驟，其使多元醇、具有陰離子性親水性基之化合物(α)或作為親水性環氧烷成分之化合物(β)與異氰酸酯反應；以及乳化及高分子量化步驟，其於反應後添加界面活性劑等，並添加離子交換水與二胺等之混合液，一面乳化，一面進行高分子化之方法；且將乳化及高分子量化步驟中之添加界面活性劑等之時之攪拌設為100～300 rpm左右之緩慢攪拌，將添加離子交換水與二胺等之混合液時之攪拌設為4,000～6,000 rpm左右之強烈攪拌 (2)於具有槽內循環用攪拌葉與剪力賦予用攪拌葉之攪拌槽中，至少使多元醇、異氰酸酯及作為親水性環氧烷成分之化合物進行反應及乳化。 藉由該製造方法，可以前文所述之較高之不揮發性成分濃度有效率地製造具有前文所述之體積平均粒徑之水性聚胺酯樹脂。又，可製成所需之黏度。 "Manufacturing method of preparation liquid containing water-soluble resin (water-based polyurethane resin)" Regarding the manufacturing method of the preparation solution comprising water-based polyurethane resin as water-soluble resin in the present invention, for example, the following methods (1) and (2) can be exemplified: (1) via: a reaction step of reacting a polyol, a compound (α) having an anionic hydrophilic group, or a compound (β) as a hydrophilic alkylene oxide component with isocyanate; and an emulsification and high molecular weight step of After the reaction, add a surfactant, etc., and add a mixture of ion-exchanged water and diamine, etc., while emulsifying and polymerizing; and add surfactants, etc. in the emulsification and high molecular weight steps The stirring is set to a slow stirring of about 100-300 rpm, and the stirring is set to a strong stirring of about 4,000-6,000 rpm when adding a mixture of ion-exchanged water and diamine, etc. (2) In a stirring tank having a stirring blade for circulation in the tank and a stirring blade for imparting shear force, at least a polyol, an isocyanate, and a compound as a hydrophilic alkylene oxide component are reacted and emulsified. By this production method, the water-based polyurethane resin having the above-mentioned volume average particle diameter can be efficiently produced at the above-mentioned relatively high concentration of non-volatile components. Also, it can be made into desired viscosity.

《包含水溶性樹脂(水性聚乙二醇樹脂、水性聚乙二醇樹脂、水性聚乙烯醇樹脂)之調配液之製造方法》 關於本發明中之包含水性聚乙二醇樹脂、水性聚乙二醇樹脂及水性聚乙烯醇樹脂作為水溶性樹脂之調配液之製造方法，例如可藉由適當選擇水性聚乙二醇樹脂、水性聚乙二醇樹脂及水性聚乙烯醇樹脂作為調配液之主劑，適量調配增黏液及水等並進行攪拌，而獲得所需黏度之調配液。 "Manufacturing method of preparation liquid containing water-soluble resin (water-based polyethylene glycol resin, water-based polyethylene glycol resin, water-based polyvinyl alcohol resin)" Regarding the preparation method of the preparation solution comprising water-based polyethylene glycol resin, water-based polyethylene glycol resin and water-based polyvinyl alcohol resin as water-soluble resins in the present invention, for example, water-based polyethylene glycol resin, water-based Polyethylene glycol resin and water-based polyvinyl alcohol resin are used as the main ingredients of the preparation solution, and an appropriate amount of viscosifying liquid and water are prepared and stirred to obtain a preparation solution of the desired viscosity.

(發泡層) 發泡層30設置於基底層20上，係使末端具有異氰酸基之胺基甲酸酯預聚物發泡而成之層。即，發泡層30為包含末端具有異氰酸基之胺基甲酸酯預聚物之發泡物之層。 (foam layer) The foam layer 30 is provided on the base layer 20 and is a layer formed by foaming a urethane prepolymer having an isocyanate group at the end. That is, the foam layer 30 is a layer containing a foam of a urethane prepolymer having an isocyanate group at its terminal.

就兼具多孔層結構體之優異質感(柔軟性)及剝離強度之觀點而言，發泡層30之密度較佳為0.03～0.30 g/cm 3，更佳為0.05～0.25 g/cm 3，進而較佳為0.07～0.20 g/cm 3。再者，發泡層30之密度可藉由實施例中記載之方法進行測定。 From the viewpoint of both the excellent texture (softness) and peel strength of the porous layer structure, the density of the foam layer 30 is preferably 0.03-0.30 g/cm 3 , more preferably 0.05-0.25 g/cm 3 , More preferably, it is 0.07 to 0.20 g/cm 3 . Furthermore, the density of the foam layer 30 can be measured by the method described in the examples.

發泡層30之厚度根據所塗佈之聚胺基甲酸酯預聚物之厚度或所製作之皮革種類而改變，因此並無特別限定。例如，就兼具多孔層結構體之優異質感(柔軟性)及剝離強度之觀點而言，為0.05～1.0 mm左右即可，較佳為0.1～1.0 mm左右。The thickness of the foam layer 30 varies depending on the thickness of the polyurethane prepolymer to be applied or the type of leather to be produced, and thus is not particularly limited. For example, from the viewpoint of achieving both excellent texture (softness) and peel strength of the porous layer structure, it is only about 0.05 to 1.0 mm, preferably about 0.1 to 1.0 mm.

發泡層30介隔基底層20而積層於基材10上，藉此基材10、基底層20及發泡層30之密接性提高，可在該等不剝離的情況下發揮優異耐久性。又，由於發泡層30於不產生過度發泡部分或發泡之形狀及尺寸不均的情況下以較低密度進行發泡，因此多孔層結構體於維持優異之剝離強度及耐久性之同時具有良好質感(柔軟性)。The foam layer 30 is laminated on the base material 10 through the base layer 20, thereby improving the adhesion between the base material 10, the base layer 20, and the foam layer 30, and exhibiting excellent durability without peeling off. In addition, since the foamed layer 30 is foamed at a relatively low density without excessively foamed parts or uneven shape and size of the foam, the porous layer structure maintains excellent peel strength and durability. Has good texture (softness).

用以將發泡層30自基材10剝離之剝離力較佳為1.0 kgf/inch以上，更佳為1.2 kgf/inch以上，進而較佳為1.5 kgf/inch以上。藉由用以將發泡層30自基材10剝離之剝離力為上述下限值以上，例如可獲得超過作為發泡合成人造皮革而言無實用上之問題之水準的與基材10之密接性(剝離強度)。用以將發泡層30自基材10剝離之剝離力之上限並無特別限定。 再者，關於用以將發泡層30自基材10剝離之剝離力之測定，可藉由實施例之「剝離強度試驗」中記載之方法進行測定。 The peeling force for peeling the foam layer 30 from the substrate 10 is preferably at least 1.0 kgf/inch, more preferably at least 1.2 kgf/inch, and still more preferably at least 1.5 kgf/inch. When the peeling force for peeling the foam layer 30 from the base material 10 is equal to or greater than the above-mentioned lower limit value, for example, close contact with the base material 10 can be obtained beyond a level that is practically problematic as a foamed synthetic artificial leather. properties (peel strength). The upper limit of the peeling force for peeling the foam layer 30 from the substrate 10 is not particularly limited. In addition, about the measurement of the peeling force for peeling the foam layer 30 from the base material 10, it can measure by the method described in the "peeling strength test" of an Example.

又，本實施方式之胺基甲酸酯預聚物實質上不含揮發成分。即，可在不使用有機溶劑之情況下製造多孔層結構體，因此不存在有害性問題及環境問題。 此處，於本發明中，所謂「實質上不含揮發成分」意指未意圖性地包含有機溶劑等揮發成分，更具體而言係指不存在有機溶劑。 Moreover, the urethane prepolymer of this embodiment does not contain a volatile component substantially. That is, since the porous layer structure can be produced without using an organic solvent, there are no harmfulness problems or environmental problems. Here, in the present invention, "substantially not containing volatile components" means that volatile components such as organic solvents are not intentionally contained, and more specifically, organic solvents do not exist.

＜胺基甲酸酯預聚物＞ 胺基甲酸酯預聚物包含多元醇成分、異氰酸酯成分、及其他適當成分。即，本實施方式之末端具有異氰酸基之胺基甲酸酯預聚物係由多元醇成分與多異氰酸酯成分獲得之胺基甲酸酯預聚物。尤其是，該胺基甲酸酯預聚物係濕氣硬化型胺基甲酸酯預聚物，可於藉由基底層20之水分進行濕氣硬化時發泡，藉此獲得本發明之多孔層結構體。 ＜Urethane Prepolymer＞ The urethane prepolymer contains a polyol component, an isocyanate component, and other appropriate components. That is, the urethane prepolymer which has an isocyanate group at the terminal of this embodiment is a urethane prepolymer obtained from a polyol component and a polyisocyanate component. In particular, the urethane prepolymer is a moisture-curable urethane prepolymer that can foam when moisture-cured by moisture in the base layer 20, thereby obtaining the porous structure of the present invention. layer structure.

〈多元醇成分〉 成為胺基甲酸酯預聚物之多元醇成分之多元醇並無特別限定，可例舉：聚碳酸酯多元醇、聚醚多元醇、聚酯多元醇、聚內酯多元醇、聚烯烴多元醇、及聚甲基丙烯酸酯二醇等。 <Polyol component> The polyol used as the polyol component of the urethane prepolymer is not particularly limited, and examples include: polycarbonate polyol, polyether polyol, polyester polyol, polylactone polyol, polyolefin polyol Alcohol, and polymethacrylate diol, etc.

作為多元醇成分，可含有聚碳酸酯多元醇成分，以提高耐水解性，獲得更良好之耐久性。於含有聚碳酸酯多元醇成分之情形時，於全部多元醇成分中，較佳為含有50質量%以上，更佳為含有70～90質量%。As a polyol component, polycarbonate polyol component can be included to improve hydrolysis resistance and obtain better durability. When containing a polycarbonate polyol component, it is preferable to contain 50 mass % or more of all polyol components, and it is more preferable to contain 70-90 mass %.

多元醇之數量平均分子量只要為500以上即可，並無特別限制，較佳為500～4,000左右，進而較佳為1,000～3,000左右。該等多元醇可單獨使用或將2種以上組合使用，就長期耐久性之觀點而言，較佳為包含聚碳酸酯二醇。 再者，數量平均分子量為聚苯乙烯換算之數量平均分子量，通常可藉由凝膠滲透層析法(GPC)測定而求出。 The number average molecular weight of the polyol is not particularly limited as long as it is 500 or more, but it is preferably about 500 to 4,000, and more preferably about 1,000 to 3,000. These polyols may be used alone or in combination of two or more, and polycarbonate diol is preferably included from the viewpoint of long-term durability. In addition, the number average molecular weight is a number average molecular weight in terms of polystyrene, and can usually be calculated|required by the gel permeation chromatography (GPC) measurement.

〈異氰酸酯成分〉 用作本實施方式之胺基甲酸酯預聚物之合成成分之異氰酸酯並無特別限定，較佳為脂肪族二異氰酸酯、脂環族二異氰酸酯、及芳香族二異氰酸酯等二官能多異氰酸酯。 作為成為異氰酸酯成分之多異氰酸酯之具體例，有：甲苯二異氰酸酯、4-甲氧基-1,3-苯二異氰酸酯、4-異丙基-1,3-苯二異氰酸酯、4-氯-1,3-苯二異氰酸酯、4-丁氧基-1,3-苯二異氰酸酯、2,4-二異氰酸酯-二苯醚、1,3,5-三甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、伸四甲苯基二異氰酸酯、1,5-萘二異氰酸酯、聯苯胺二異氰酸酯、鄰硝基聯苯胺二異氰酸酯、4,4'-二異氰酸基聯苄、1,4-四亞甲基二異氰酸酯、1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己烷二異氰酸酯、二甲苯二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、1,5-四氫萘二異氰酸酯、異佛爾酮二異氰酸酯、及二環己基甲烷4,4'-二異氰酸酯等。其中，較佳為至少包含4,4'-二苯基甲烷二異氰酸酯(MDI)。 <Isocyanate component> The isocyanate used as the synthesis component of the urethane prepolymer of this embodiment is not particularly limited, but difunctional polyisocyanates such as aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate are preferable. Specific examples of the polyisocyanate used as the isocyanate component include: toluene diisocyanate, 4-methoxy-1,3-benzenediisocyanate, 4-isopropyl-1,3-benzenediisocyanate, 4-chloro-1 ,3-Benzene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate-diphenyl ether, 1,3,5-trimethylbenzene diisocyanate, 4,4'-diphenyl Methyl methane diisocyanate, tetracresyl diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanatobibenzyl, 1,4- Tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, Xylene diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate, etc. . Among them, it is preferable to contain at least 4,4'-diphenylmethane diisocyanate (MDI).

於如車輛用途或淡色系用途等需要耐光性之情形時，較佳為將4,4'-二苯基甲烷二異氰酸酯與脂肪族二異氰酸酯或脂環族二異氰酸酯併用。When light resistance is required, such as vehicle use or light-colored use, it is preferable to use 4,4'-diphenylmethane diisocyanate together with aliphatic diisocyanate or alicyclic diisocyanate.

關於製成本實施方式之胺基甲酸酯預聚物時之多元醇與多異氰酸酯之比率，多異氰酸酯成分之異氰酸基當量相對於整個多元醇成分之羥基當量的比較佳為1.33～5.0，更佳為1.5～3.0。若NCO/OH處於上述範圍內，則柔軟性及與基材10之剝離強度均更加良好。Regarding the ratio of polyol to polyisocyanate when producing the urethane prepolymer of this embodiment, the ratio of the isocyanate group equivalent of the polyisocyanate component to the hydroxyl equivalent of the entire polyol component is preferably 1.33 to 5.0. More preferably, it is 1.5-3.0. When NCO/OH is in the said range, both flexibility and the peeling strength with the base material 10 will become more favorable.

本實施方式之胺基甲酸酯預聚物之製造方法並無特別限定。例如可以NCO/OH達到1.33～5.0之方式將多異氰酸酯混合至前文所述之多元醇中，於80～120℃下反應60～120分鐘左右而加以製造。The manufacturing method of the urethane prepolymer of this embodiment is not specifically limited. For example, it can be produced by mixing polyisocyanate into the above-mentioned polyol so that NCO/OH becomes 1.33-5.0, and reacting at 80-120° C. for about 60-120 minutes.

再者，於胺基甲酸酯預聚物中，可視需要適當調配多官能基多異氰酸酯、熱塑性聚合物、及黏著賦予樹脂等。In addition, in the urethane prepolymer, a multifunctional polyisocyanate, a thermoplastic polymer, and an adhesion-imparting resin may be appropriately formulated as needed.

(表皮層) 本實施方式之多孔層結構體亦可如圖3所示，於發泡層30之積層有基底層20之面之相反面上具有表皮層40。 表皮層40並無特別限定，例如可例舉藉由溶劑系聚胺基甲酸酯、水系聚胺基甲酸酯、及TPU(Thermoplastic polyurethanes，熱塑性聚胺酯彈性體橡膠)等表皮層形成用塗料所形成者。 (epidermal layer) The porous layer structure of this embodiment may also have a skin layer 40 on the surface of the foam layer 30 opposite to the surface on which the base layer 20 is laminated, as shown in FIG. 3 . The skin layer 40 is not particularly limited, and for example, it may be made of a paint for forming a skin layer such as solvent-based polyurethane, water-based polyurethane, and TPU (Thermoplastic polyurethanes, thermoplastic polyurethane elastomer rubber). former.

如上所述，本實施方式之多孔層結構體可適宜用作合成人造皮革及人工皮革，適用於鞋、衣服、包、傢俱、車輛內裝材(例如儀錶面板、門、控制台、及座椅)、隔熱材料、吸音材料、及衝擊吸收材料等。As described above, the porous layer structure of this embodiment can be suitably used as synthetic artificial leather and artificial leather, and is suitable for shoes, clothes, bags, furniture, and vehicle interior materials (such as instrument panels, doors, consoles, and seats). ), heat insulation materials, sound-absorbing materials, and impact-absorbing materials.

[多孔層結構體之製造方法] 本實施方式之多孔層結構體之製造方法包括：基底層積層步驟，其係於基材10上塗佈包含水溶性樹脂之調配液，於基材10上形成基底層20；及發泡層積層步驟，其係於基底層20上配置末端具有異氰酸基之胺基甲酸酯預聚物，藉由基底層20之水分使胺基甲酸酯預聚物發泡而形成發泡層30。 以下，對各步驟進行說明。 [Manufacturing method of porous layer structure] The manufacturing method of the porous layer structure of the present embodiment includes: a base lamination layer step, which is to apply a preparation solution containing a water-soluble resin on the base material 10 to form the base layer 20 on the base material 10; and a foaming lamination layer step, which is to arrange the urethane prepolymer having an isocyanate group on the base layer 20, and the urethane prepolymer is foamed by the moisture of the base layer 20 to form the foam layer 30 . Each step will be described below.

(基底層積層步驟) 首先，於所準備之基材10之一面上，塗佈收容於塗佈機之包含水溶性樹脂之調配液，於基材10上形成濕潤狀態之基底層20。再者，利用包含水溶性樹脂之調配液所得之基底層20之單位面積重量取決於調配液之塗佈量及黏度，以基底層20之單位面積重量達到3～60 g/m 2・dry之方式塗佈調配液。 (Base Lamination Step) First, on one surface of the prepared substrate 10 , the prepared solution containing a water-soluble resin contained in a coater is applied to form the base layer 20 in a wet state on the substrate 10 . Furthermore, the weight per unit area of the base layer 20 obtained by using the prepared liquid containing water-soluble resin depends on the coating amount and viscosity of the prepared liquid, and the weight per unit area of the base layer 20 reaches 3-60 g/m2 · dry. way to apply the formulation.

(發泡層積層步驟) 繼而，於濕潤狀態之基底層20上配置末端具有異氰酸基之胺基甲酸酯預聚物。作為配置胺基甲酸酯預聚物之方法，例如可例舉於基底層20上塗佈收容於熔化器等塗佈機中之胺基甲酸酯預聚物之方法。 再者，為使發泡層30水發泡，重要的是於基底層20乾燥前以與基底層20接觸之方式配置胺基甲酸酯預聚物。藉此，配置於基底層20上之胺基甲酸酯預聚物藉由基底層20之水分而發泡，從而形成發泡層30。 (Foam lamination step) Next, a urethane prepolymer having an isocyanate group at the end is disposed on the base layer 20 in a wet state. As a method of arranging the urethane prepolymer, for example, a method of coating the urethane prepolymer accommodated in a coater such as a melter on the base layer 20 may be mentioned. Furthermore, in order to foam the foaming layer 30 with water, it is important to place the urethane prepolymer in contact with the base layer 20 before the base layer 20 is dried. Thus, the urethane prepolymer disposed on the base layer 20 is foamed by the moisture in the base layer 20 , thereby forming the foamed layer 30 .

胺基甲酸酯預聚物塗膜之厚度(剛塗佈後、即發泡前之厚度)取決於胺基甲酸酯預聚物之黏度及組成，較佳為50～500 μm，更佳為60～400 μm，更佳為70～300 μm。The thickness of the urethane prepolymer coating film (thickness immediately after coating, that is, before foaming) depends on the viscosity and composition of the urethane prepolymer, preferably 50-500 μm, more preferably It is 60-400 μm, more preferably 70-300 μm.

(表皮層積層步驟) 本實施方式之多孔層結構體之製造方法亦可進而包括表皮層積層步驟，其係於發泡層30之積層有基底層20之面之相反面上積層表皮層40。再者，為使表皮層40以密接於發泡層30之方式積層，於發泡層30之發泡結束前、即基底層20乾燥前，以與發泡層30接觸之方式配置表皮層40。 (Lamination of epidermis step) The manufacturing method of the porous layer structure of this embodiment may further include a skin layering step, which is to layer the skin layer 40 on the surface of the foam layer 30 opposite to the surface on which the base layer 20 is layered. Furthermore, in order to laminate the skin layer 40 in close contact with the foam layer 30, the skin layer 40 is arranged in contact with the foam layer 30 before the foaming of the foam layer 30 is completed, that is, before the base layer 20 is dried. .

於包括表皮層積層步驟之情形時，較佳為將末端具有異氰酸基之胺基甲酸酯預聚物塗佈於表皮層40之一面上，以配置胺基甲酸酯預聚物塗膜。繼而，利用層壓等使設置於表皮層40上之胺基甲酸酯預聚物塗膜與設置於基材10上之基底層20貼合，藉此可於基底層20上配置末端具有異氰酸基之胺基甲酸酯預聚物。此時，為使發泡層30良好地發泡，重要的是於基底層20乾燥前、即基底層20處於濕潤狀態時，以與基底層20接觸之方式配置發泡層30。In the case of including the step of skin layering, it is preferable to apply a urethane prepolymer having an isocyanate group on one side of the skin layer 40 to configure the urethane prepolymer coating. membrane. Next, the urethane prepolymer coating film provided on the skin layer 40 is bonded to the base layer 20 provided on the base material 10 by lamination or the like, thereby disposing on the base layer 20 a terminal having a different Cyanate-based urethane prepolymer. At this time, in order to foam the foam layer 30 well, it is important to place the foam layer 30 in contact with the base layer 20 before the base layer 20 dries, that is, when the base layer 20 is in a wet state.

(熟化步驟) 本實施方式之多孔層結構體之製造方法亦可於發泡層積層步驟之後進而包括熟化步驟，其係實施促進發泡層30之發泡之熟化處理。於熟化步驟中，使發泡層積層步驟後之多孔層結構體於15～80℃、40～95%RH之狀態下保持48～120小時，而實施熟化處理。藉由該熟化處理促進發泡，從而製作本實施方式之多孔層結構體。 (curing step) The manufacturing method of the porous layer structure of this embodiment may further include an aging step after the foam lamination step, which is to perform an aging treatment to promote the foaming of the foam layer 30 . In the aging step, the porous layer structure after the foaming lamination step is kept at 15-80° C. and 40-95% RH for 48-120 hours to perform aging treatment. Foaming is promoted by this aging treatment, and the porous layer structure of this embodiment is produced.

(水蒸氣接觸步驟) 又，於本製造方法中，於發泡層積層步驟與熟化步驟之間亦可包括水蒸氣接觸步驟，其係使發泡層積層步驟後之多孔層結構體與水蒸氣接觸。於水蒸氣接觸步驟中，將環境設為30～60℃(較佳為35～55℃)、80%RH以上(較佳為85%RH以上)，該環境下之時間亦取決於溫度條件及濕度條件，較佳為設為20秒以上(較佳為25～60秒)。 藉由水蒸氣接觸步驟，可使多孔層結構體之含水率提高，因此容易於之後之熟化處理步驟中獲得良好之發泡倍率。即，可良好地控制發泡程度。 (water vapor contact step) In addition, in this production method, a water vapor contact step may be included between the foam lamination step and the aging step, which is to contact the porous layer structure after the foam lamination step with water vapor. In the water vapor contact step, the environment is set to 30-60°C (preferably 35-55°C), 80%RH or more (preferably 85%RH or more), and the time in this environment also depends on temperature conditions and The humidity condition is preferably set at 20 seconds or longer (preferably 25 to 60 seconds). The moisture content of the porous layer structure can be increased by the steam contact step, so it is easy to obtain a good expansion ratio in the subsequent aging treatment step. That is, the degree of foaming can be well controlled.

藉由如上所述之步驟，基底層20均勻且無遺漏地設置於基材10上，配置於基底層20上之胺基甲酸酯預聚物與基底層20之接觸均勻，藉此，自基底層20供給之水分量固定，可形成發泡形狀均勻且穩定之發泡層20。藉由形成發泡形狀均勻且穩定之發泡層20，可在維持較高密接性之同時，獲得發揮優異質感(柔軟性)之多孔層結構體。Through the above-mentioned steps, the base layer 20 is uniformly and completely arranged on the base material 10, and the contact between the urethane prepolymer disposed on the base layer 20 and the base layer 20 is uniform, thereby, from The amount of moisture supplied to the base layer 20 is constant, and a foam layer 20 with a uniform and stable foam shape can be formed. By forming the foam layer 20 with a uniform and stable foam shape, a porous layer structure exhibiting excellent texture (softness) can be obtained while maintaining high adhesion.

再者，多孔層結構體可以本來之狀態直接用作合成人造皮革，亦可適當進行例如表面處理劑之塗佈或與其他基材之貼合等處理。 [實施例] Furthermore, the porous layer structure can be used as a synthetic artificial leather in its original state, or it can be properly treated such as coating of a surface treatment agent or lamination with other substrates. [Example]

其次，藉由實施例及比較例，對本發明加以詳細說明。然而，本發明並不限定於實施例等。Next, the present invention will be described in detail with examples and comparative examples. However, the present invention is not limited to Examples and the like.

(基底層用調配液之製備(其1：水性聚胺酯樹脂)) 作為施加基底層之調配液之主劑，選擇RESAMINE D-6065NP、RESAMINE DN-0445、RESAMINE D-1063(水性聚胺酯樹脂、大日精化工業股份有限公司製造)，逐次少量地調配三仙膠(DSP Gokyo Food ＆ Chemical股份有限公司製造)2%水溶液(增黏液A)或D-87(大日精化工業股份有限公司製造、增黏液B)使其增黏，直至各個實施例/比較例達到表2、3中記載之黏度，獲得基底層用調配液(B-1)。 關於使用有交聯劑之調配液(實施例5、6)，向所得之基底層用調配液(B-1)中，進而分別各以表2中記載之量調配RESAMINE D-52(碳二醯亞胺系交聯劑(固形物成分40%)、大日精化工業股份有限公司製造)或RESAMINE D-65(異氰酸酯系交聯劑(固形物成分70%)、大日精化工業股份有限公司製造)，製成基底層用調配液(B-2)。再者，實施例5中之碳二醯亞胺系交聯劑之質量份係相對於水性聚胺酯樹脂之固形物成分為50%之水分散體100質量份的質量份。又，實施例6中之異氰酸酯系交聯劑之質量份係相對於水性聚胺酯樹脂之固形物成分為43%之水分散體100質量份的質量份。 各基底層用調配液(B-1、B-2)之固形物成分濃度(質量%)如表2、3所示。 (Preparation of preparation solution for base layer (part 1: water-based polyurethane resin)) As the main agent of the preparation solution for applying the base layer, RESAMINE D-6065NP, RESAMINE DN-0445, and RESAMINE D-1063 (water-based polyurethane resin, manufactured by Dainichi Seika Co., Ltd.) were selected, and Sanxian gum (DSP Gokyo Food & Chemical Co., Ltd.) 2% aqueous solution (thickening liquid A) or D-87 (Dainichi Seika Co., Ltd., thickening liquid B) to make it thicker until each embodiment/comparative example reaches Table 2 , Viscosity described in 3, to obtain the formulation solution (B-1) for the base layer. Regarding the preparation solution (Examples 5 and 6) using a cross-linking agent, RESAMINE D-52 (carbon two Imide-based cross-linking agent (solid content 40%), manufactured by Dainichi Seika Co., Ltd.) or RESAMINE D-65 (isocyanate-based cross-linking agent (solid content 70%), Dainichi Seika Co., Ltd. production) to prepare the preparation solution (B-2) for the base layer. Furthermore, the parts by mass of the carbodiimide-based crosslinking agent in Example 5 is 100 parts by mass of the aqueous dispersion with a solid content of 50% relative to the aqueous polyurethane resin. Moreover, the mass parts of the isocyanate type crosslinking agent in Example 6 is the mass part of 100 mass parts of aqueous dispersions with solid content of 43% with respect to the aqueous polyurethane resin. Tables 2 and 3 show the solid content concentrations (mass %) of the prepared liquids (B-1, B-2) for each base layer.

(基底層用調配液之製備(其2：水性聚乙二醇樹脂)) 作為施加基底層之調配液之主劑，選擇L-11(數量平均分子量：約11萬)、E-45(數量平均分子量：60萬～100萬)、E-75(數量平均分子量：約200萬)、E-300(數量平均分子量：約700萬)(水性聚乙二醇(PEG)、明成化學工業股份有限公司製造)，作為黏度調整劑，逐次少量地調配水，直至達到表4中記載之黏度，獲得基底層用調配液(B-3)。 關於使用有交聯劑之調配液(實施例18、19)，向所得之基底層用調配液(B-3)中，進而分別各以表4中記載之量調配RESAMINE D-65(異氰酸酯系交聯劑(固形物成分70%)、大日精化工業股份有限公司製造)，製成基底層用調配液(B-4)。再者，實施例18、19中之異氰酸酯系交聯劑之質量份係相對於水性聚乙二醇之固形物成分為6%之水分散體100質量份的質量份。 各基底層用調配液(B-3、B-4)之固形物成分濃度(質量%)如表4所示。 (Preparation of preparation solution for base layer (part 2: water-based polyethylene glycol resin)) As the main ingredient of the preparation solution for applying the base layer, L-11 (number average molecular weight: about 110,000), E-45 (number average molecular weight: 600,000 to 1 million), E-75 (number average molecular weight: about 200 10,000), E-300 (number average molecular weight: about 7 million) (water-based polyethylene glycol (PEG), manufactured by Mingcheng Chemical Industry Co., Ltd.), as a viscosity modifier, gradually deploy water in small amounts until reaching the viscosity in Table 4. According to the recorded viscosity, the preparation solution (B-3) for the base layer was obtained. Regarding the preparation solution (Examples 18 and 19) using a crosslinking agent, RESAMINE D-65 (isocyanate-based A cross-linking agent (solid content 70%), manufactured by Dainichi Seika Co., Ltd.) was used to make a preparation solution (B-4) for the base layer. Furthermore, the mass parts of the isocyanate-based crosslinking agent in Examples 18 and 19 are 100 mass parts of an aqueous dispersion with a solid content of 6% of aqueous polyethylene glycol. Table 4 shows the solid content concentration (mass %) of each base layer formulation solution (B-3, B-4).

(基底層用調配液之製備(其3：水性聚乙烯醇樹脂)) 作為施加基底層之調配液之主劑，選擇PVA105(水性聚乙烯醇(PVA)、可樂麗股份有限公司製造)，作為黏度調整劑，逐次少量地調配水，直至達到表5中記載之黏度，獲得基底層用調配液(B-5)。 關於使用有交聯劑之調配液(實施例23、24)，向所得之基底層用調配液(B-5)中，進而分別各以表5中記載之量調配RESAMINE D-65(異氰酸酯系交聯劑(固形物成分70%)、大日精化工業股份有限公司製造)，製成基底層用調配液(B-6)。再者，實施例23、24中之異氰酸酯系交聯劑之質量份係相對於水性聚乙烯醇樹脂之固形物成分為20%之水分散體100質量份的質量份。 各基底層用調配液(B-5、B-6)之固形物成分濃度(質量%)如表5所示。 (Preparation of preparation solution for base layer (part 3: water-based polyvinyl alcohol resin)) As the main ingredient of the preparation solution for applying the base layer, PVA105 (water-based polyvinyl alcohol (PVA), manufactured by Kuraray Co., Ltd.) was selected as a viscosity modifier, and water was gradually prepared in small amounts until the viscosity recorded in Table 5 was reached. The preparation solution (B-5) for base layer was obtained. Regarding the preparation solution (Examples 23 and 24) using a crosslinking agent, RESAMINE D-65 (isocyanate-based A cross-linking agent (solid content 70%), manufactured by Dainichi Seika Co., Ltd.) was used to make a preparation solution (B-6) for the base layer. Furthermore, the mass parts of the isocyanate-based crosslinking agent in Examples 23 and 24 are 100 mass parts of a water dispersion having a solid content of 20% relative to the water-based polyvinyl alcohol resin. Table 5 shows the solid content concentration (mass %) of each base layer formulation solution (B-5, B-6).

(基底層用調配液之製備(其4：水性聚胺酯樹脂)) 選擇用作實施例6之增黏劑之D-87(水性聚胺酯樹脂、大日精化工業股份有限公司製造)來作為施加基底層之調配液之主劑，作為黏度調整劑，逐次少量地調配水，直至達到表6中記載之黏度，獲得基底層用調配液(B-7)。 關於使用有交聯劑之調配液(實施例31、32)，向所得之基底層用調配液(B-7)中，進而分別各以表4中記載之量調配RESAMINE D-65(異氰酸酯系交聯劑(固形物成分70%)、大日精化工業股份有限公司製造)，製成基底層用調配液(B-8)。再者，實施例31、32中之異氰酸酯系交聯劑之質量份係相對於水性聚胺酯樹脂之固形物成分為20%之水分散體100質量份的質量份。 各基底層用調配液(B-7、B-8)之固形物成分濃度(質量%)如表6所示。 (Preparation of preparation solution for base layer (part 4: water-based polyurethane resin)) D-87 (water-based polyurethane resin, manufactured by Dainichi Seika Co., Ltd.) used as the tackifier of Example 6 was selected as the main agent of the preparation solution for applying the base layer, and as a viscosity modifier, a small amount of water was prepared successively. , until reaching the viscosity recorded in Table 6, to obtain the formulation solution (B-7) for the base layer. Regarding the preparation solution (Examples 31 and 32) using a crosslinking agent, RESAMINE D-65 (isocyanate-based A cross-linking agent (solid content 70%), manufactured by Dainichi Seika Co., Ltd.) was used to prepare the preparation solution for the base layer (B-8). Furthermore, the mass parts of the isocyanate-based crosslinking agent in Examples 31 and 32 is 100 mass parts of the aqueous dispersion whose solid content is 20% with respect to the aqueous polyurethane resin. Table 6 shows the solid content concentration (mass %) of each base layer formulation solution (B-7, B-8).

(基底層用調配液之製備(其5：水性丙烯酸樹脂)) 作為施加基底層之調配液之主劑，選擇XK-12、XK-36(水性丙烯酸樹脂、Covestro Japan股份有限公司製造)，逐次少量地調配A-7100(丙烯酸系增黏劑、東亞合成股份有限公司製造、增黏液C)使其增黏，直至達到表7中記載之黏度，獲得基底層用調配液(B-9)。 各基底層用調配液(B-9)之固形物成分濃度(質量%)如表7所示。 (Preparation of preparation solution for base layer (part 5: water-based acrylic resin)) Select XK-12 and XK-36 (water-based acrylic resin, manufactured by Covestro Japan Co., Ltd.) as the main ingredients of the preparation solution for applying the base layer, and gradually prepare A-7100 (acrylic tackifier, Toa Gosei Co., Ltd.) The viscosity-increasing liquid C) manufactured by the company was increased until it reached the viscosity recorded in Table 7 to obtain the preparation liquid (B-9) for the base layer. Table 7 shows the solid content concentration (mass %) of each base layer preparation solution (B-9).

(表皮之製作) 將合成人造皮革用之作為溶劑型聚胺酯樹脂之RESAMINE NE-8875-30M(大日精化工業股份有限公司)、作為合成人造皮革用著色劑之Seika Seven BS-780(大日精化工業股份有限公司)、作為稀釋溶劑之甲基乙基酮及二甲基甲醯胺混合，藉由棒式塗佈機將250 μm/wet之塗佈量均勻地塗佈於離型紙上後，於120℃下使其乾燥5分鐘，獲得具備膜厚40～50 μm之表皮層40之附有表皮之膜。 (Creating of skin) RESAMINE NE-8875-30M (Dainichi Seika Co., Ltd.) as a solvent-based polyurethane resin for synthetic artificial leather, Seika Seven BS-780 (Dainichi Seika Co., Ltd.) as a colorant for synthetic artificial leather , Methyl ethyl ketone and dimethyl formamide as a diluting solvent are mixed, and the coating amount of 250 μm/wet is evenly coated on the release paper by a rod coater, and then used at 120°C This was dried for 5 minutes to obtain a skinned film having a skin layer 40 with a film thickness of 40 to 50 μm.

(合成人造皮革之製作) [實施例1～34、比較例2～4] 於上述附有表皮之膜之表皮層40上，塗佈加熱至100℃之RESAMINE F-916(胺基甲酸酯預聚物、濕氣硬化型接著劑、大日精化工業股份有限公司製造)，以形成塗佈膜厚150 μm之胺基甲酸酯預聚物塗膜。 又，於作為聚酯之圓型編織物之厚度1.0 mm之聚酯底布(基材10)上，以形成為各個實施例/比較例中記載之重量(g/m 2・dry)之方式，塗佈包含濕潤狀態之基底層用調配液(B-1)～(B-9)之層(基底層20)。 然後，將表皮層40上所形成之胺基甲酸酯預聚物之塗膜配置為與形成於基材10上之基底層20接觸，於層壓輥溫度40℃下直接進行加壓壓接，藉此使胺基甲酸酯預聚物發泡，形成發泡層30。 作為熟化步驟，於溫度35℃、相對濕度65%之環境下進行5天熟化後，自離型紙上剝離，獲得合成人造皮革。 (Production of synthetic artificial leather) [Examples 1-34, Comparative Examples 2-4] On the skin layer 40 of the above-mentioned film with skin, RESAMINE F-916 (urethane Prepolymer, moisture-curing adhesive, manufactured by Dainichi Seika Co., Ltd.) to form a urethane prepolymer coating film with a coating film thickness of 150 μm. Also, on a polyester base fabric (substrate 10) having a thickness of 1.0 mm as a polyester circular knit, the weight (g/m 2 ·dry) described in each example/comparative example is formed , apply a layer (base layer 20 ) containing the prepared liquids (B-1) to (B-9) for the base layer in a wet state. Then, the coating film of the urethane prepolymer formed on the skin layer 40 is placed in contact with the base layer 20 formed on the base material 10, and pressure bonding is performed directly at a temperature of 40° C. , whereby the urethane prepolymer is foamed to form the foamed layer 30 . As an aging step, after aging for 5 days in an environment with a temperature of 35° C. and a relative humidity of 65%, it was peeled off from the release paper to obtain synthetic artificial leather.

[比較例1] 於上述附有表皮之膜之表皮層40上，塗佈加熱至100℃之RESAMINE F-916(胺基甲酸酯預聚物、濕氣硬化型接著劑、大日精化工業股份有限公司製造)，以形成塗佈膜厚150 μm之胺基甲酸酯預聚物塗膜。 又，使作為聚酯之圓型編織物之厚度1.0 mm之聚酯底布(基材10)中含浸相對於聚酯底布之重量為50%量之水。 然後，將表皮層40上所形成之胺基甲酸酯預聚物之塗膜配置為與含浸有水之基材10接觸，於層壓輥溫度40℃下直接進行加壓壓接，藉此使胺基甲酸酯預聚物發泡，形成發泡層30。 作為熟化步驟，於溫度35℃、相對濕度65%之環境下進行5天熟化後，自離型紙上剝離，獲得合成人造皮革。 [Comparative example 1] On the skin layer 40 of the above-mentioned skinned film, apply RESAMINE F-916 (urethane prepolymer, moisture-curing adhesive, manufactured by Dainichi Seika Co., Ltd.) heated to 100°C , to form a urethane prepolymer coating film with a film thickness of 150 μm. Also, a polyester base fabric (substrate 10) having a thickness of 1.0 mm, which is a polyester circular knit, was impregnated with water in an amount of 50% relative to the weight of the polyester base fabric. Then, the coating film of the urethane prepolymer formed on the skin layer 40 is placed in contact with the substrate 10 impregnated with water, and pressure-bonded directly at a lamination roll temperature of 40° C., thereby The urethane prepolymer is foamed to form the foamed layer 30 . As an aging step, after aging for 5 days in an environment with a temperature of 35° C. and a relative humidity of 65%, it was peeled off from the release paper to obtain synthetic artificial leather.

(基底層用調配液之塗佈性) 於作為聚酯之圓型編織物之厚度1.0 mm之聚酯底布(基材10)上，以形成為各個實施例/比較例中記載之重量(g/m 2・dry)之方式，塗佈包含濕潤狀態之基底層用調配液(B-1)～(B-9)之層(基底層20)，對此時之塗佈性進行評估。將能夠於基材10上均勻且無遺漏地形成基底層20之塗膜者判定為「良好」，將無法均勻且無遺漏地形成基底層20之塗膜者判定為「差」。 (Applicability of prepared liquid for base layer) On a polyester base fabric (substrate 10) having a thickness of 1.0 mm as a polyester circular knit fabric, the weight described in each example/comparative example ( g/m 2 ·dry) to coat a layer (base layer 20) containing the preparation solutions for base layer (B-1) to (B-9) in a wet state, and evaluate the coatability at that time. Those who could form the coating film of the base layer 20 uniformly and without omission on the substrate 10 were judged as "good", and those who could not form the coating film of the base layer 20 uniformly and without omission were judged as "poor".

(皮膜斷裂強度試驗) 針對所得之各合成人造皮革中所使用之基底層20，藉由以下之方法對皮膜斷裂強度進行測定。 以形成為各個實施例/比較例中記載之重量(g/m 2・dry)之方式，於離型紙(大日本印刷股份有限公司製造之「DNTP-FL」)上塗佈各基底層用調配液(B-1)～(B-9)，並使其乾燥，將所得之膜使用啞鈴型裁切刀(dumbbell)沖裁成寬1.5 cm、長5.0 cm，製作試樣。 然後，於距離試樣之兩端分別為1.5 cm之部分貼附Cellotape(米其邦(Nichiban)公司製造之「CT-12S」)，固定於島津製作所製造之自動立體測圖儀AGS-J之抓持具上，以200 mm/min之速度進行拉伸，將試樣斷裂之拉伸強度除以試樣之截面面積，將所得之值作為皮膜斷裂強度。 (Film Breaking Strength Test) With respect to the base layer 20 used in each of the obtained synthetic artificial leathers, the breaking strength of the skin film was measured by the following method. The formulation for each base layer was coated on a release paper ("DNTP-FL" manufactured by Dainippon Printing Co., Ltd.) so that the weight (g/m 2 ·dry) described in each example/comparative example Liquids (B-1) to (B-9) were dried, and the resulting film was punched out with a dumbbell-shaped cutter (dumbbell) into a width of 1.5 cm and a length of 5.0 cm to prepare a sample. Then, Cellotape ("CT-12S" manufactured by Nichiban Co., Ltd.) was attached to the part 1.5 cm away from both ends of the sample, and fixed on the automatic stereograph AGS-J manufactured by Shimadzu Corporation. On the gripper, stretch at a speed of 200 mm/min, divide the tensile strength at break of the sample by the cross-sectional area of the sample, and use the obtained value as the breaking strength of the film.

(剝離強度試驗) 於所得之各合成人造皮革上熱壓接合寬17 mm之聚胺酯系HM膠帶後，製作25 mm寬之短條狀測定試樣，利用AGS-J(島津製作所)以200 mm/min之速度對拉伸接著強度進行測定。 一般而言，藉由為1.5 kgf/inch以上，判斷獲得了超過作為發泡合成人造皮革而言無實用上之問題之水準的與基材10之密接性(剝離強度)。 (Peel strength test) After thermocompression-bonding polyurethane-based HM tape with a width of 17 mm on each of the obtained synthetic artificial leathers, a short strip-shaped measurement sample with a width of 25 mm was prepared, and pulled at a speed of 200 mm/min by AGS-J (Shimadzu Corporation) Elongation is measured next to strength. Generally, when it is 1.5 kgf/inch or more, it judges that the adhesiveness (peel strength) with the base material 10 which exceeded the level which has no practical problem as a foamed synthetic artificial leather was obtained.

(發泡程度評估：發泡層之密度) 將所得之各合成人造皮革切成10 cm×10 cm見方，對重量進行測定。另外，測定10 cm×10 cm之形成有包含基底層用調配液(B-1)～(B-6)之基底層20之基材10、自附有表皮之膜上剝離了離型紙之表皮層40的重量，根據下述式算出發泡層30之密度。 (1)合成人造皮革之重量測定、計算： 由合成人造皮革整體之重量(1)、基材10之重量(2)、表皮層40之重量(3)、基底層20之重量(4)，根據下述式求得發泡層30之重量。 發泡層30之重量(5)＝(1)－(2)－(3)－(4) (2)合成人造皮革之厚度測定、計算： 由合成人造皮革整體之厚度(6)、基材10之厚度(7)、表皮層40之厚度(9)、基底層20之厚度(10)，根據下述式求得發泡層30之厚度。 發泡層30之厚度(11)＝(6)－(7)－(9)－(10) (3)發泡層30之密度計算：根據下述式求得發泡層30之密度。 發泡層30之密度＝(5)÷((11)×10×10)(g/cm 3) 再者，可判斷，藉由使發泡層30之密度為0.03 g/cm 3～0.30 g/cm 3，能夠兼具良好柔軟性與較大剝離強度。 (Evaluation of degree of foaming: density of foamed layer) Each of the obtained synthetic artificial leathers was cut into a square of 10 cm x 10 cm, and the weight was measured. In addition, the base material 10 formed with the base layer 20 including the base layer preparation solutions (B-1) to (B-6) and the skin with the release paper peeled from the film with the skin were measured 10 cm × 10 cm The weight of the layer 40 is calculated from the density of the foam layer 30 according to the following formula. (1) Determination and calculation of the weight of synthetic artificial leather: From the overall weight of synthetic artificial leather (1), the weight of substrate 10 (2), the weight of skin layer 40 (3), and the weight of base layer 20 (4), The weight of the foam layer 30 is calculated|required according to the following formula. The weight of the foam layer 30 (5)=(1)-(2)-(3)-(4) (2) Measurement and calculation of the thickness of the synthetic artificial leather: From the overall thickness (6) of the synthetic artificial leather, the base material The thickness (7) of 10, the thickness (9) of the skin layer 40, and the thickness (10) of the base layer 20 can obtain the thickness of the foam layer 30 according to the following formula. Thickness of foam layer 30 (11)=(6)-(7)-(9)-(10) (3) Calculation of density of foam layer 30: Calculate the density of foam layer 30 according to the following formula. Density of the foam layer 30 = (5)÷((11)×10×10)(g/cm 3 ) Furthermore, it can be judged that by making the density of the foam layer 30 0.03 g/cm 3 to 0.30 g /cm 3 , which can have both good flexibility and high peel strength.

(質感(柔軟性)評估) 關於所得之各合成人造皮革之柔軟性，以標準合成人造皮革為標準，藉由手觸感觸進行比較，評估指標如下。再者，若評估為A～C，則合格。 A：與標準合成人造皮革相比更柔軟 B：與標準合成人造皮革同等程度地柔軟 C：與標準合成人造皮革相比稍硬 D：與標準合成人造皮革相比硬得多 (Texture (softness) evaluation) With regard to the softness of the synthetic artificial leather obtained, the standard synthetic artificial leather was used as the standard, and the evaluation index was as follows for comparison by hand touch. In addition, if the evaluation is A to C, it is a pass. A: Softer than standard synthetic faux leather B: Same level of softness as standard synthetic faux leather C: Slightly stiffer than standard synthetic faux leather D: Much stiffer than standard synthetic faux leather

《標準合成人造皮革之製作》 於上述離型紙上所形成之具備膜厚45 μm之表皮層40之附有表皮的膜上，塗佈以RESAMINE UD-8351NT(聚胺酯樹脂接著劑、大日精化工業股份有限公司製造)100質量份、C-50交聯劑(異氰酸酯系交聯劑、大日精化工業股份有限公司製造)10質量份之組成進行調整所得之接著劑，以形成厚度100 μm之接著劑層。 之後，進行80℃/2分鐘之預乾燥，將所得之接著劑層配置為與作為聚酯之圓型編織物之厚度1.0 mm之聚酯底布(基材10)接觸，於層壓輥溫度40℃下進行加壓壓接。之後，於50℃/48小時之條件下進行熟化，獲得用於質感(柔軟性)評估之標準合成人造皮革(使用有MEK之普通乾式皮革)。 "The Production of Standard Synthetic Artificial Leather" Apply 100 parts by mass of RESAMINE UD-8351NT (polyurethane resin adhesive, manufactured by Dainichi Seika Co., Ltd.) , C-50 cross-linking agent (isocyanate-based cross-linking agent, manufactured by Dainichi Seika Co., Ltd.) 10 parts by mass of the adhesive to form an adhesive layer with a thickness of 100 μm. Afterwards, pre-dry at 80°C/2 minutes, and place the obtained adhesive layer in contact with a polyester base fabric (substrate 10) with a thickness of 1.0 mm, which is a polyester circular braid. Pressure bonding was performed at 40°C. Afterwards, it was aged at 50° C./48 hours to obtain a standard synthetic artificial leather (ordinary dry leather with MEK) for texture (softness) evaluation.

[關於合格與否判定] 於各表中，將剝離強度為1.5 kgf/inch以上且質感(柔軟性)評估為A～C者判定為「合格」，將不符合該標準者判定為「不合格」。 [About pass or fail judgment] In each table, those with a peel strength of 1.5 kgf/inch or more and texture (softness) evaluations of A to C were judged as "pass", and those that did not meet the criteria were judged as "failure".

[表2] 表2    實施例 1 2 3 4 5 6 7 8 9 10 發泡層 濕氣硬化型接著劑 F-916 基底層 水性聚胺酯樹脂 D-6065NP DN-0445 D-1063 D-6065NP 增黏劑 水＋三仙膠 D-87 水＋三仙膠 黏度(mPa・s/25℃) 3,000 3,000 3,000 3,000 3,000 3,000 600 40,000 400 60,000 異氰酸酯系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - - 6 ＜4.2＞ - - - - 碳二醯亞胺系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - 4 ＜1.6＞ - - - - - 單位面積重量(g/m 2・dry) 5 10 50 10 10 10 10 15 10 15 塗料固形物成分(%) 20 20 35 20 20 20 20 20 20 20 塗佈膜厚 [使用棒式塗佈機時之標準塗佈膜厚] 棒式塗佈機No.10[23 μ・wet] 50 μ・wet 150 μ・wet 50 μ・wet 50 μ・wet 50 μ・wet 50 μ・wet 50 μ・wet 50 μ・wet 50 μ・wet 基底層(乾燥)厚度(μm) 4 9 45 9 10 9 9 15 8 15 基材 基底層與基材之厚度比 1：250 1：125 1：20 1：125 1：125 1：125 1：140 1：65 1：140 1：55 底布含水處理 無 無 無 無 無 無 無 無 無 無 評估 基底層用調配液塗佈性 良好 良好 良好 良好 良好 良好 良好 良好 差 塗佈調配液後瞬間含浸至基材 差 調配液塗膜為斑狀，難以均勻塗佈 基底層皮膜斷裂強度 ＞30 MPa ＞30 MPa ＞30 MPa 5.5 MPa 12.6 MPa 18.3 MPa ＞30 MPa ＞30 MPa ＞30 MPa ＞30 MPa 剝離強度(kgf/inch) 2.1 2.8 3.3 1.6 2.0 2.3 1.9 4.5 0.6 1.1 發泡層之密度(g/cm 3) 0.09 0.13 0.13 0.13 0.15 0.13 0.11 0.11 0.07 0.36 發泡層厚度(μm) 1000 700 700 700 600 700 800 800 1200 250 質感 A A B A A B A B A C 合格與否判定 合格 合格 合格 合格 合格 合格 合格 合格 不合格 不合格 [Table 2] Table 2 Example 1 2 3 4 5 6 7 8 9 10 foam layer moisture curing adhesive F-916 basal layer Waterborne Polyurethane Resin D-6065NP DN-0445 D-1063 D-6065NP Tackifier Water + Sanxianjiao D-87 Water + Sanxianjiao Viscosity (mPa・s/25℃) 3,000 3,000 3,000 3,000 3,000 3,000 600 40,000 400 60,000 Isocyanate-based crosslinking agent (parts by mass) <Active ingredient = solid content conversion value> - - - - - 6 <4.2> - - - - Carbodiimide-based crosslinking agent (parts by mass) <active ingredient = solid content conversion value> - - - - 4 <1.6> - - - - - Weight per unit area (g/m 2・dry) 5 10 50 10 10 10 10 15 10 15 Coating solids composition (%) 20 20 35 20 20 20 20 20 20 20 Coating film thickness [Standard coating film thickness when using a bar coater] Rod Coater No.10[23 μ・wet] 50μ・wet 150μ・wet 50μ・wet 50μ・wet 50μ・wet 50μ・wet 50μ・wet 50μ・wet 50μ・wet Base layer (dry) thickness (μm) 4 9 45 9 10 9 9 15 8 15 Substrate Thickness ratio of base layer to base material 1:250 1:125 1:20 1:125 1:125 1:125 1:140 1:65 1:140 1:55 Base fabric water treatment none none none none none none none none none none Evaluate Coatability of prepared liquid for base layer good good good good good good good good Instant impregnation to the substrate after poor coating The coating film of the poorly formulated solution is patchy, and it is difficult to coat evenly basal membrane breaking strength ＞30MPa ＞30MPa ＞30 MPa 5.5 MPa 12.6 MPa 18.3 MPa ＞30 MPa ＞30 MPa ＞30 MPa ＞30 MPa Peel strength (kgf/inch) 2.1 2.8 3.3 1.6 2.0 2.3 1.9 4.5 0.6 1.1 Density of foam layer (g/cm 3 ) 0.09 0.13 0.13 0.13 0.15 0.13 0.11 0.11 0.07 0.36 Foam layer thickness (μm) 1000 700 700 700 600 700 800 800 1200 250 texture A A B A A B A B A C Qualified or not judged qualified qualified qualified qualified qualified qualified qualified qualified unqualified unqualified

[表3] 表3    比較例 1 2 3 4 發泡層 濕氣硬化型接著劑 F-916 基底層 水性聚胺酯樹脂 - D-6065NP D-1063 增黏劑 - 水＋三仙膠 黏度(mPa・s/25℃) - 3,000 3,000 3,000 異氰酸酯系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - 碳二醯亞胺系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - 單位面積重量(g/m 2・dry) - 2 70 10 塗料固形物成分(%) - 20 35 20 塗佈膜厚 [使用棒式塗佈機時之標準塗佈膜厚] - 棒式塗佈機No.8 [18 μ・wet] 200 μ・wet 50μ・wef 基底層(乾燥)厚度(μm) - 2 64 9 基材 基底層與基材之厚度比 - 1：550 1：15 1：125 底布含水處理 有(50%) 無 無 無 評估 基底層用調配液塗佈性 - 良好 良好 良好 基底層皮膜斷裂強度 - ＞30 MPa ＞30 MPa ＜5.0 MPa 剝離強度(kgf/inch) 0.9 0.8 3.8 0.6 發泡層之密度(g/cm 3) 0.09 0.16 0.08 0.13 發泡層厚度(μm) 1000 550 1100 700 質感 B B D D 合格與否判定 不合格 不合格 不合格 不合格 [table 3] table 3 comparative example 1 2 3 4 foam layer moisture curing adhesive F-916 basal layer Waterborne Polyurethane Resin - D-6065NP D-1063 Tackifier - Water + Sanxianjiao Viscosity (mPa・s/25℃) - 3,000 3,000 3,000 Isocyanate-based crosslinking agent (parts by mass) <Active ingredient = solid content conversion value> - - - - Carbodiimide-based crosslinking agent (parts by mass) <active ingredient = solid content conversion value> - - - - Weight per unit area (g/m 2・dry) - 2 70 10 Coating solids composition (%) - 20 35 20 Coating film thickness [Standard coating film thickness when using a bar coater] - Rod Coater No.8 [18 μ・wet] 200μ・wet 50μ・wef Base layer (dry) thickness (μm) - 2 64 9 Substrate Thickness ratio of base layer to base material - 1:550 1:15 1:125 Base fabric water treatment Yes (50%) none none none Evaluate Coatability of prepared liquid for base layer - good good good basal membrane breaking strength - ＞30MPa ＞30 MPa ＜5.0MPa Peel strength (kgf/inch) 0.9 0.8 3.8 0.6 Density of foam layer (g/cm 3 ) 0.09 0.16 0.08 0.13 Foam layer thickness (μm) 1000 550 1100 700 texture B B D. D. Qualified or not judged unqualified unqualified unqualified unqualified

再者，關於表2、3中之基底層用調配液之塗佈膜厚，除標明為棒式塗佈機以外，均係藉由模嘴塗佈所得，該模嘴塗佈係與模槽隔開一定間隔地塗佈基底層用調配液，因此將模槽與基材之間隔作為剛塗佈後之濕潤狀態之塗佈膜厚的參考值。 並且，作為表2、3中之基底層用調配液之塗佈膜厚，標明為棒式塗佈機者係表示利用所記載之號數之棒式塗佈機進行塗佈，將自該棒式塗佈機之製造商資料(第一理化股份有限公司)引用之濕潤狀態之標準膜厚作為濕潤狀態之塗佈膜厚的參考值一併記載於括號內。 Furthermore, regarding the coating film thickness of the preparation solution for the base layer in Tables 2 and 3, except for those marked as bar coaters, they are all obtained by coating with a die. The preparation solution for the base layer is applied at regular intervals, so the interval between the cavity and the substrate is used as a reference value for the coating film thickness in the wet state immediately after coating. In addition, as the coating film thickness of the prepared solution for the base layer in Tables 2 and 3, those indicated as rod coaters mean that the rod coaters of the numbers described are used for coating. The standard film thickness in the wet state quoted in the manufacturer's information of the type coating machine (Daiichi Chemical Co., Ltd.) is recorded in parentheses as the reference value of the coating film thickness in the wet state.

關於表2、3中之基底層(乾燥)厚度，實施例3、8、10、比較例3係根據利用SEM所得之截面圖像藉由10點平均進行測量而算出。 另一方面，實施例1、2、4～7、9、比較例2、4由於無法藉由利用SEM所得之截面圖像確認到基底層20，因此於離型紙(大日本印刷股份有限公司製造之「DNTP-FL」)上，以與基底層20之乾燥時之單位面積重量相等之方式，塗佈測量對象之包含水性聚胺酯樹脂之調配液，作為乾燥步驟，依序經過於60℃下進行4分鐘、於100℃下進行3分鐘、於120℃下進行3分鐘之各步驟後，將離型紙上所形成基底層之厚度作為測量對象之基底層20之厚度。 Regarding the base layer (dry) thicknesses in Tables 2 and 3, Examples 3, 8, 10, and Comparative Example 3 were calculated based on 10-point average measurements based on cross-sectional images obtained by SEM. On the other hand, in Examples 1, 2, 4 to 7, 9, and Comparative Examples 2 and 4, the base layer 20 could not be confirmed by using the cross-sectional images obtained by SEM, so they were used on release paper (manufactured by Dainippon Printing Co., Ltd. On the "DNTP-FL"), the preparation liquid containing water-based polyurethane resin to be measured is coated in such a way that the weight per unit area is equal to that of the base layer 20 when it is dried. As a drying step, it is carried out at 60°C in sequence. After the steps of 4 minutes, 3 minutes at 100°C, and 3 minutes at 120°C, the thickness of the base layer formed on the release paper was taken as the thickness of the base layer 20 to be measured.

根據表2、3，可知本實施例即使將發泡密度降低至未達0.3 g/cm 3，表現出與先前之皮革、例如藉由使用DMF之濕式法製作之合成人造皮革相同程度之優異質感(柔軟性)，亦可發揮良好密接性。 又，本實施例相較於如比較例1所示使基材中含浸水之情形，可獲得較高之剝離強度。推測其原因在於，比較例1中，由於使用脫水機進行脫水等，每單位面積之水分量之分佈容易產生不均，可成為發泡層之濕氣硬化型接著劑局部地過度發泡或過度地含浸於底布中。 According to Tables 2 and 3, it can be seen that even if the foaming density is lowered to less than 0.3 g/cm 3 , this example shows the same level of excellence as the previous leather, such as the synthetic artificial leather produced by the wet method using DMF. Good texture (softness) and good adhesion. In addition, compared with the case of impregnating the base material with water as shown in Comparative Example 1, this example can obtain higher peel strength. The reason for this is presumed to be that in Comparative Example 1, due to the use of a dehydrator for dehydration, etc., the distribution of the amount of moisture per unit area tends to be uneven, and the moisture-curing adhesive that can become a foam layer is partially foamed or excessively foamed. impregnated into the base cloth.

[表4] 表4    實施例 11 12 13 14 15 16 17 18 19 發泡層 濕氣硬化型接著劑 F-916 基底層 水溶性樹脂 E-45 L-11 E-75 E-300 E-45 PEG 黏度調整劑 水 黏度(mPa・s/25℃) 3,000 400 60,000 4,000 3,000 3,000 4,000 3,000 3,000 異氰酸酯系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - - - - 2 5 碳二醯亞胺系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - - - - - - 單位面積重量(g/m 2・dry) 17 10 15 20 15 10 20 17 17 塗料固形物成分(%) 6 1 10 20 5 1 20 6 6 塗佈膜厚 [使用棒式塗佈機時之標準塗佈膜厚] 300 1000 150 100 300 1000 100 300 300 基底層(乾燥)厚度(μm) 15 9 15 18 14 9 18 15 15 基材 基底層與基材之厚度比 1：55 1：92 1：55 1：46 1：59 1：92 1：46 1：55 1：55 底布含水處理 無 無 無 無 無 無 無 無 無 評估 基底層用調配液塗佈性 良好 差 塗佈調配液後瞬間含浸至基材 差 調配液塗膜為斑狀，難以均勻塗佈 差 塗佈調配液後瞬間含浸至基材 良好 良好 差 塗佈調配液後瞬間含浸至基材 良好 良好 基底層皮膜斷裂強度 10.7 MPa 10.2 MPa 10.8 MPa 10.5 MPa 10.9 MPa 11.1 MPa 11.0 MPa 15.3 MPa 20.7 MPa 剝離強度(kgf/inch) 2.4 0.8 1.2 1.0 2.3 2.1 1.0 2.6 3.0 發泡層之密度(g/cm 3) 0.11 0.11 0.30 0.09 0.11 0.09 0.09 0.11 0.12 發泡層厚度(μm) 800 800 300 1000 800 1000 1000 800 750 質感 A C C B A A B A B 合格與否判定 合格 不合格 不合格 不合格 合格 合格 不合格 合格 合格 [Table 4] Table 4 Example 11 12 13 14 15 16 17 18 19 foam layer moisture curing adhesive F-916 basal layer water soluble resin E-45 L-11 E-75 E-300 E-45 PEG Viscosity modifier water Viscosity (mPa・s/25℃) 3,000 400 60,000 4,000 3,000 3,000 4,000 3,000 3,000 Isocyanate-based crosslinking agent (parts by mass) <Active ingredient = solid content conversion value> - - - - - - - 2 5 Carbodiimide-based crosslinking agent (parts by mass) <active ingredient = solid content conversion value> - - - - - - - - - Weight per unit area (g/m 2・dry) 17 10 15 20 15 10 20 17 17 Coating solids composition (%) 6 1 10 20 5 1 20 6 6 Coating film thickness [Standard coating film thickness when using a bar coater] 300 1000 150 100 300 1000 100 300 300 Base layer (dry) thickness (μm) 15 9 15 18 14 9 18 15 15 Substrate Thickness ratio of base layer to base material 1:55 1:92 1:55 1:46 1:59 1:92 1:46 1:55 1:55 Base fabric water treatment none none none none none none none none none Evaluate Coatability of prepared liquid for base layer good Instant impregnation to the substrate after poor coating The coating film of the poorly formulated solution is patchy, and it is difficult to coat evenly Instant impregnation to the substrate after poor coating good good Instant impregnation to the substrate after poor coating good good basal membrane breaking strength 10.7 MPa 10.2 MPa 10.8 MPa 10.5MPa 10.9 MPa 11.1MPa 11.0 MPa 15.3MPa 20.7 MPa Peel strength (kgf/inch) 2.4 0.8 1.2 1.0 2.3 2.1 1.0 2.6 3.0 Density of foam layer (g/cm 3 ) 0.11 0.11 0.30 0.09 0.11 0.09 0.09 0.11 0.12 Foam layer thickness (μm) 800 800 300 1000 800 1000 1000 800 750 texture A C C B A A B A B Qualified or not judged qualified unqualified unqualified unqualified qualified qualified unqualified qualified qualified

[表5] 表5    實施例 20 21 22 23 24 25 26 發泡層 濕氣硬化型接著劑 F-916 基底層 水溶性樹脂 PVA105 PVA 黏度調整劑 水 黏度(mPa・s/25℃) 3,000 500 20,000 3,000 3,000 300 60,000 異氰酸酯系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - 2 5 - - 碳二醯亞胺系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - - - - 單位面積重量(g/m 2・dry) 20 17 32 20 20 23 50 塗料固形物成分(%) 20 6 32 20 20 15 50 塗佈膜厚 [使用棒式塗佈機時之標準塗佈膜厚] 100 300 100 100 100 150 100 基底層(乾燥)厚度(μm) 18 14 30 18 18 20 50 基材 基底層與基材之厚度比 1：46 1：59 1：28 1：46 1：46 1：41 1：17 底布含水處理 無 無 無 無 無 無 無 評估 基底層用調配液塗佈性 良好 良好 良好 良好 良好 差 塗佈調配液後瞬間含浸至基材 差 調配液塗膜為斑狀，難以均勻塗佈 基底層皮膜斷裂強度 12.1 MPa 11.4 MPa 12.5 MPa 21.4 MPa 29.3 MPa 10.8 MPa 13.1 MPa 剝離強度(kgf/inch) 2.8 2.4 3.3 3.1 3.6 0.8 1.2 發泡層之密度(g/cm 3) 0.10 0.09 0.11 0.11 0.13 0.08 0.26 發泡層厚度(μm) 900 1000 800 850 700 1100 350 質感 A A A A B C C 合格與否判定 合格 合格 合格 合格 合格 不合格 不合格 [table 5] table 5 Example 20 twenty one twenty two twenty three twenty four 25 26 foam layer moisture curing adhesive F-916 basal layer water soluble resin PVA105 PVA Viscosity modifier water Viscosity (mPa・s/25℃) 3,000 500 20,000 3,000 3,000 300 60,000 Isocyanate-based crosslinking agent (parts by mass) <Active ingredient = solid content conversion value> - - - 2 5 - - Carbodiimide-based crosslinking agent (parts by mass) <active ingredient = solid content conversion value> - - - - - - - Weight per unit area (g/m 2・dry) 20 17 32 20 20 twenty three 50 Coating solids composition (%) 20 6 32 20 20 15 50 Coating film thickness [Standard coating film thickness when using a bar coater] 100 300 100 100 100 150 100 Base layer (dry) thickness (μm) 18 14 30 18 18 20 50 Substrate Thickness ratio of base layer to base material 1:46 1:59 1:28 1:46 1:46 1:41 1:17 Base fabric water treatment none none none none none none none Evaluate Coatability of prepared liquid for base layer good good good good good Instant impregnation to the substrate after poor coating The coating film of the poorly formulated solution is patchy, and it is difficult to coat evenly basal membrane breaking strength 12.1 MPa 11.4MPa 12.5 MPa 21.4 MPa 29.3 MPa 10.8 MPa 13.1MPa Peel strength (kgf/inch) 2.8 2.4 3.3 3.1 3.6 0.8 1.2 Density of foam layer (g/cm 3 ) 0.10 0.09 0.11 0.11 0.13 0.08 0.26 Foam layer thickness (μm) 900 1000 800 850 700 1100 350 texture A A A A B C C Qualified or not judged qualified qualified qualified qualified qualified unqualified unqualified

[表6] 表6    實施例 27 28 29 30 31 32 發泡層 濕氣硬化型接著劑 F-916 基底層 水溶性樹脂 D-87 水性聚胺酯樹脂 黏度調整劑 水 黏度(mPa・s/25℃) 1,000 500 50,000 300 3,000 3,000 異氰酸酯系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - 2 5 碳二醯亞胺系交聯劑(質量份) ＜有效成分＝固形物成分換算值＞ - - - - - - 單位面積重量(g/m 2・dry) 30 48 50 21 30 30 塗料固形物成分(%) 20 16 50 14 20 20 塗佈膜厚 [使用棒式塗佈機時之標準塗佈膜厚] 150 150 100 150 150 150 基底層(乾燥)厚度(μm) 27 46 50 18 27 27 基材 基底層與基材之厚度比 1：31 1：18 1：17 1：46 1：31 1：31 底布含水處理 無 無 無 無 無 無 評估 基底層用調配液塗佈性 良好 良好 良好 差 塗佈調配液後瞬間含浸至基材 良好 良好 基底層皮膜斷裂強度 6.2 MPa 5.8 MPa 6.5 MPa 5.8 MPa 7.7 MPa 10.4 MPa 剝離強度(kgf/inch) 1.8 1.6 2.0 0.9 2.1 2.3 發泡層之密度(g/cm 3) 0.13 0.13 0.15 0.08 0.13 0.15 發泡層厚度(μm) 700 700 600 1100 700 600 質感 A A A C A B 合格與否判定 合格 合格 合格 不合格 合格 合格 [Table 6] Table 6 Example 27 28 29 30 31 32 foam layer moisture curing adhesive F-916 basal layer water soluble resin D-87 Waterborne Polyurethane Resin Viscosity modifier water Viscosity (mPa・s/25℃) 1,000 500 50,000 300 3,000 3,000 Isocyanate-based crosslinking agent (parts by mass) <Active ingredient = solid content conversion value> - - - - 2 5 Carbodiimide-based crosslinking agent (parts by mass) <active ingredient = solid content conversion value> - - - - - - Weight per unit area (g/m 2・dry) 30 48 50 twenty one 30 30 Coating solids composition (%) 20 16 50 14 20 20 Coating film thickness [Standard coating film thickness when using a bar coater] 150 150 100 150 150 150 Base layer (dry) thickness (μm) 27 46 50 18 27 27 Substrate Thickness ratio of base layer to base material 1:31 1:18 1:17 1:46 1:31 1:31 Base fabric water treatment none none none none none none Evaluate Coatability of prepared liquid for base layer good good good Instant impregnation to the substrate after poor coating good good basal membrane breaking strength 6.2 MPa 5.8 MPa 6.5MPa 5.8 MPa 7.7 MPa 10.4 MPa Peel strength (kgf/inch) 1.8 1.6 2.0 0.9 2.1 2.3 Density of foam layer (g/cm 3 ) 0.13 0.13 0.15 0.08 0.13 0.15 Foam layer thickness (μm) 700 700 600 1100 700 600 texture A A A C A B Qualified or not judged qualified qualified qualified unqualified qualified qualified

[表7] 表7    實施例 33 34 發泡層 濕氣硬化型接著劑 F-916 基底層 水溶性樹脂 XK-12 XK-36 水性丙烯酸樹脂 黏度調整劑 A-7100 黏度(mPa・s/25℃) 4,000 4,000 異氰酸酯系交聯劑 (質量份) ＜有效成分＝固形物成分換算值＞ - - 碳二醯亞胺系交聯劑 (質量份) ＜有效成分＝固形物成分換算值＞ - - 單位面積重量(g/m 2・dry) 20 20 塗料固形物成分(%) 20 20 塗佈膜厚 [使用棒式塗佈機時之標準塗佈膜厚] 100 100 基底層(乾燥)厚度(μm) 18 18 基材 基底層與基材之厚度比 1：46 1：46 底布含水處理 無 無 評估 基底層用調配液塗佈性 差 塗佈調配液後接著時含浸至基材 差 塗佈調配液後接著時含浸至基材 基底層皮膜斷裂強度 ＞30 MPa ＞30 MPa 剝離強度(kgf/inch) 2.7 1.8 發泡層之密度(g/cm 3) 0.14 0.13 發泡層厚度(μm) 650 700 質感 C C 合格與否判定 不合格 不合格 [Table 7] Table 7 Example 33 34 foam layer moisture curing adhesive F-916 basal layer water soluble resin XK-12 XK-36 Waterborne Acrylic Resin Viscosity modifier A-7100 Viscosity (mPa・s/25℃) 4,000 4,000 Isocyanate-based crosslinking agent (parts by mass) <Active ingredient = solid content conversion value> - - Carbodiimide-based crosslinking agent (parts by mass) <active ingredient = solid content conversion value> - - Weight per unit area (g/m 2・dry) 20 20 Coating solids composition (%) 20 20 Coating film thickness [Standard coating film thickness when using a bar coater] 100 100 Base layer (dry) thickness (μm) 18 18 Substrate Thickness ratio of base layer to base material 1:46 1:46 Base fabric water treatment none none Evaluate Coatability of prepared liquid for base layer Impregnated to the substrate after poor coating formulation Impregnated to the substrate after poor coating formulation basal membrane breaking strength ＞30MPa ＞30 MPa Peel strength (kgf/inch) 2.7 1.8 Density of foam layer (g/cm 3 ) 0.14 0.13 Foam layer thickness (μm) 650 700 texture C C Qualified or not judged unqualified unqualified

10:基材 20:基底層 30:發泡層 40:表皮層 10: Substrate 20: Base layer 30: foam layer 40: epidermis

圖1係表示本實施方式之多孔層結構體之示意性剖視圖(其1)。 圖2係本實施方式之多孔層結構體之利用掃描電子顯微鏡(SEM)所得之剖面照片。 圖3係表示本實施方式之多孔層結構體之示意性剖視圖(其2)。 FIG. 1 is a schematic cross-sectional view (Part 1) showing a porous layer structure of the present embodiment. Fig. 2 is a cross-sectional photograph of the porous layer structure of the present embodiment obtained with a scanning electron microscope (SEM). Fig. 3 is a schematic cross-sectional view (Part 2) showing the porous layer structure of the present embodiment.

10:基材 10: Substrate

20:基底層 20: Base layer

30:發泡層 30: foam layer

Claims (10)

一種多孔層結構體，其具備： 基材、 設置於上述基材上之利用包含水溶性樹脂之調配液而形成之基底層、及 設置於上述基底層上之使末端具有異氰酸基之胺基甲酸酯預聚物發泡而成之發泡層，且 上述基底層之單位面積重量為3～60 g/m 2・dry， 上述基底層之乾燥後之皮膜斷裂強度為5 MPa以上。 A porous layer structure comprising: a base material, a base layer formed on the base material using a preparation solution containing a water-soluble resin, and an amine having an isocyanate group at a terminal provided on the base layer The foam layer is formed by foaming urethane prepolymer, and the weight per unit area of the above base layer is 3-60 g/m 2 ·dry, and the film breaking strength of the above base layer after drying is above 5 MPa. 如請求項1之多孔層結構體，其中上述包含水溶性樹脂之調配液之黏度於25℃下為500～50,000 mPa・s。The porous layer structure according to claim 1, wherein the viscosity of the above-mentioned formulation solution containing the water-soluble resin is 500-50,000 mPa·s at 25°C. 如請求項1或2之多孔層結構體，其中上述水溶性樹脂為選自由水性聚胺酯樹脂、水性聚乙二醇樹脂及水性聚乙烯醇樹脂所組成之群中之至少一種。The porous layer structure according to claim 1 or 2, wherein the water-soluble resin is at least one selected from the group consisting of water-based polyurethane resin, water-based polyethylene glycol resin, and water-based polyvinyl alcohol resin. 如請求項3之多孔層結構體，其中上述水溶性樹脂為水性聚胺酯樹脂。The porous layer structure according to claim 3, wherein the water-soluble resin is a water-based polyurethane resin. 如請求項3之多孔層結構體，其中上述水溶性樹脂為水性聚乙二醇樹脂，且上述水性聚乙二醇樹脂之數量平均分子量為50萬以上。The porous layer structure according to claim 3, wherein the water-soluble resin is a water-based polyethylene glycol resin, and the number-average molecular weight of the water-based polyethylene glycol resin is more than 500,000. 如請求項1至5中任一項之多孔層結構體，其中上述基底層與上述基材之厚度比為1：10～1：1,000。The porous layer structure according to any one of claims 1 to 5, wherein the thickness ratio of the base layer to the substrate is 1:10 to 1:1,000. 如請求項1至6中任一項之多孔層結構體，其中上述發泡層之積層有上述基底層之面之相反面上具有表皮層。The porous layer structure according to any one of claims 1 to 6, wherein the foamed layer has a skin layer on a surface opposite to the surface on which the base layer is laminated. 一種多孔層結構體之製造方法，其包括： 基底層積層步驟，其係於基材上塗佈包含水溶性樹脂之調配液，於上述基材上形成濕潤狀態之基底層；及 發泡層積層步驟，其係於上述濕潤狀態之基底層上配置末端具有異氰酸基之胺基甲酸酯預聚物，藉由上述基底層之水分使上述胺基甲酸酯預聚物發泡而形成發泡層；且 上述基底層之單位面積重量為3～60 g/m 2・dry， 上述基底層之乾燥後之皮膜斷裂強度為5 MPa以上。 A method for manufacturing a porous layer structure, comprising: a base layer build-up step, which is to apply a preparation solution containing a water-soluble resin on a substrate to form a base layer in a wet state on the above-mentioned base material; and a foamed build-up layer step, which is to arrange the urethane prepolymer having an isocyanate group on the base layer in the above wet state, and form the above urethane prepolymer by foaming the above base layer with moisture Foam layer; and the base layer has a weight per unit area of 3-60 g/m 2 ·dry, and the dry film breaking strength of the base layer is above 5 MPa. 如請求項8之多孔層結構體之製造方法，其進而包括表皮層積層步驟，該表皮層積層步驟係於上述發泡層之積層有上述基底層之面之相反面上積層表皮層。The manufacturing method of the porous layer structure according to claim 8, which further includes a skin layering step, wherein the skin layering step is to layer a skin layer on the surface of the foam layer opposite to the surface on which the base layer is layered. 如請求項8或9之多孔層結構體之製造方法，其於上述發泡層積層步驟之後進而包括熟化步驟，該熟化步驟係實施促進上述發泡層之發泡之熟化處理。The manufacturing method of the porous layer structure according to claim 8 or 9, which further includes a curing step after the above-mentioned foam lamination step, and the curing step is to perform a curing treatment to promote the foaming of the above-mentioned foam layer.
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