JP2020186353A - Method of manufacturing porous body - Google Patents

Method of manufacturing porous body Download PDF

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JP2020186353A
JP2020186353A JP2019093763A JP2019093763A JP2020186353A JP 2020186353 A JP2020186353 A JP 2020186353A JP 2019093763 A JP2019093763 A JP 2019093763A JP 2019093763 A JP2019093763 A JP 2019093763A JP 2020186353 A JP2020186353 A JP 2020186353A
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urethane resin
porous body
silicone compound
resin composition
mass
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JP7331454B2 (en
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章恵 藤下
Akie Fujishita
章恵 藤下
前田　亮
Akira Maeda
亮 前田
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2019093763A priority Critical patent/JP7331454B2/en
Priority to TW109109118A priority patent/TW202106779A/en
Priority to KR1020200036744A priority patent/KR102298393B1/en
Priority to CN202010278642.3A priority patent/CN112029404B/en
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    • C08K5/00—Use of organic ingredients
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

To provide a method of manufacturing a porous body having fine uniform cells, and voluminous and soft feeling by a wet film-forming method.SOLUTION: The method of manufacturing a porous body includes subjecting a urethane resin composition containing a urethane resin (A), a solvent (B), and a film-forming auxiliary agent (C) to wet film-forming, where the film-forming auxiliary agent (C) is a silicone compound (cl) having an oxyethylene structure. Preferably, the silicone compound (cl) further has a hydroxyl group. The number average molecular weight of the silicone compound (cl) is preferably within a range of 500-5,000.SELECTED DRAWING: None

Description

本発明は、湿式製膜法による多孔体の製造方法に関する。 The present invention relates to a method for producing a porous body by a wet film forming method.

人工皮革・合成皮革の分野では、有機溶剤を含有するウレタン樹脂組成物を加工したシートが広く利用されている。前記ウレタン樹脂組成物の加工方法としては、乾式法及び湿式法があるが、これらの中でも、多孔体を形成する湿式法（湿式成膜法）は、良好な風合いや屈曲性等を付与するできるため、得られる皮革は高級品との位置づけにある（例えば、特許文献１を参照。）。 In the field of artificial leather and synthetic leather, a sheet processed with a urethane resin composition containing an organic solvent is widely used. There are a dry method and a wet method as a processing method of the urethane resin composition. Among these, the wet method for forming a porous body (wet film forming method) can impart good texture, flexibility and the like. Therefore, the obtained leather is positioned as a high-class product (see, for example, Patent Document 1).

一方、これらの性能を発現するには、セル形状の微細なコントロールが不可欠であるが、この制御は難しく、これを容易にする処方の構築が渇望されていた。 On the other hand, in order to exhibit these performances, fine control of cell shape is indispensable, but this control is difficult, and there has been a craving for the construction of a formulation that facilitates this control.

特開平４−３００３７０号公報Japanese Unexamined Patent Publication No. 4-300370

本発明が解決しようとする課題は、湿式成膜法により、細かく均一なセルを有し、かつ、ボリューム感がありソフトな風合いを有する多孔体を製造する方法を提供することにある。 An object to be solved by the present invention is to provide a method for producing a porous body having fine and uniform cells and having a voluminous feel and a soft texture by a wet film forming method.

本発明は、ウレタン樹脂（Ａ）、溶剤（Ｂ）、及び、成膜助剤（Ｃ）を含有するウレタン樹脂組成物を湿式成膜して多孔体を製造する方法であって、前記成膜助剤（Ｃ）が、オキシエチレン構造を有するシリコーン化合物（ｃ１）であることを特徴とする多孔体の製造方法を提供するものである。 The present invention is a method for producing a porous body by wet-forming a urethane resin composition containing a urethane resin (A), a solvent (B), and a film-forming auxiliary (C) to produce a porous body. It provides a method for producing a porous body, characterized in that the auxiliary agent (C) is a silicone compound (c1) having an oxyethylene structure.

本発明によれば、特定の成膜助剤を用いることで、湿式成膜法により、細かく均一なセルを有し、ボリューム感がありソフトな風合いを有する多孔体を製造することができる。よって、本発明は、研磨パッド、人工皮革・合成皮革の製造に特に好適に使用することができる。 According to the present invention, by using a specific film-forming auxiliary, it is possible to produce a porous body having fine and uniform cells, a voluminous feel, and a soft texture by a wet film-forming method. Therefore, the present invention can be particularly suitably used for the production of polishing pads, artificial leather and synthetic leather.

なお、本発明において前記「多孔体」とは、ウレタン樹脂組成物を湿式成膜法により凝固させれば自ずと得られる程度の多数の孔を有するものであり、例えば、面の厚さ方向に長い紡錘形または涙滴形の多孔構造を形成しているものをいう。 In the present invention, the "porous body" has a large number of pores that can be naturally obtained by solidifying the urethane resin composition by a wet film forming method, and is, for example, long in the thickness direction of the surface. A spindle-shaped or teardrop-shaped porous structure is formed.

本発明は、ウレタン樹脂（Ａ）、溶剤（Ｂ）、及び、特定の成膜助剤（Ｃ）を含有するウレタン樹脂組成物を湿式成膜して多孔体を製造する方法である。 The present invention is a method for producing a porous body by wet-forming a urethane resin composition containing a urethane resin (A), a solvent (B), and a specific film-forming auxiliary (C).

本発明においては、成膜助剤（Ｃ）として、オキシエチレン構造を有するシリコーン化合物（ｃ１）を用いることが必須である。前記ポリオール（ｃ１）は、親水性が高く、ウレタン樹脂が凝固する際に水を呼び込みやすいため、セルを制御しやすく、良好な風合いを有する多孔体を得ることができる。 In the present invention, it is essential to use the silicone compound (c1) having an oxyethylene structure as the film forming aid (C). Since the polyol (c1) has high hydrophilicity and easily attracts water when the urethane resin solidifies, it is easy to control the cell and a porous body having a good texture can be obtained.

前記シリコーン化合物（ｃ１）は、シロキサン結合で構成される主鎖を有し、前記主鎖の末端又は側鎖にオキシエチレン構造を有するオイル状のシリコーン化合物である。 The silicone compound (c1) is an oil-like silicone compound having a main chain composed of siloxane bonds and having an oxyethylene structure at the end or side chain of the main chain.

前記シリコーン化合物（ｃ１）としては、親水性がより向上し、より一層優れたセル形成、及び、風合いが得られる点から、反応性基を有することが好ましい。前記反応性基としては、例えば、水酸基、エポキシ基等が挙げられる。これらの中でも、より一層優れたセル形成、及び、風合いが得られる点から、水酸基を有することが好ましい。 The silicone compound (c1) preferably has a reactive group from the viewpoint of further improving hydrophilicity, forming even more excellent cells, and obtaining a texture. Examples of the reactive group include a hydroxyl group and an epoxy group. Among these, it is preferable to have a hydroxyl group from the viewpoint of obtaining even more excellent cell formation and texture.

前記シリコーン化合物（ｃ１）の数平均分子量としては、より一層優れたセル形成、及び、風合いが得られる点から、５００〜５，０００の範囲であることが好ましく、１，０００〜４，０００の範囲がより好ましい。なお、前記シリコーン化合物（ｃ１）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。 The number average molecular weight of the silicone compound (c1) is preferably in the range of 500 to 5,000, preferably in the range of 1,000 to 4,000, from the viewpoint of obtaining even more excellent cell formation and texture. The range is more preferred. The number average molecular weight of the silicone compound (c1) is a value measured under the following conditions by a gel permeation chromatography (GPC) method.

前記シリコーン化合物（ｃ１）としては、例えば、「ＫＦ３５５Ａ」、「ＫＦ６４４」、「ＫＦ６２０４」、「Ｘ−２２−４５９２」、「Ｘ−２２−４２７２」、「ＫＦ６１２３」、「Ｘ−２２−４７４１」、「ＫＦ１００２」（以上、信越化学工業株式会社製）、「ＢＹ１６−２０１」、「ＳＦ−８４２７」、「ＳＦ−８４２８」、「ＦＺ−２１６２」、「ＳＨ３７７３Ｍ」（以上、東レ・ダウコーニング株式会社製）等を市販品として入手することができる。 Examples of the silicone compound (c1) include "KF355A", "KF644", "KF6204", "X-22-4592", "X-22-2472", "KF6123", and "X-22-4471". , "KF1002" (above, manufactured by Shin-Etsu Chemical Co., Ltd.), "BY16-201", "SF-8427", "SF-8428", "FZ-2162", "SH3773M" (above, Toray Dow Corning shares) (Made by the company) etc. can be obtained as a commercial product.

前記シリコーン化合物（ｃ１）の含有量としては、より一層優れたセル形成、及び、風合いが得られる点から、前記ウレタン樹脂（Ａ）１００質量部に対して、０．１〜３０質量部の範囲であることが好ましく、０．５〜２０質量部の範囲がより好ましい。 The content of the silicone compound (c1) is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of obtaining even more excellent cell formation and texture. Is preferable, and the range of 0.5 to 20 parts by mass is more preferable.

本発明で用いるウレタン樹脂（Ａ）としては、例えば、ポリオール（ａ１）とポリイソシアネート（ａ２）との反応物を用いることができる。 As the urethane resin (A) used in the present invention, for example, a reaction product of the polyol (a1) and the polyisocyanate (a2) can be used.

前記ポリオール（ａ１）としては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。 As the polyol (a1), for example, a polyester polyol, a polyether polyol, a polycarbonate polyol, or the like can be used. These polyols may be used alone or in combination of two or more.

前記ポリオール（ａ１）の数平均分子量としては、多孔体の機械的特性、及び、柔軟性の点から、５００〜１０，０００の範囲であることが好ましく、７００〜８，０００の範囲がより好ましい。なお、前記ポリオール（ａ１）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The number average molecular weight of the polyol (a1) is preferably in the range of 500 to 10,000, more preferably in the range of 700 to 8,000, from the viewpoint of mechanical properties and flexibility of the porous body. .. The number average molecular weight of the polyol (a1) indicates a value measured by a gel permeation chromatography (GPC) method.

前記ポリオール（ａ１）には、必要に応じて、数平均分子量が５００未満の鎖伸長剤（ａ１−１）を併用してもよい。前記鎖伸長剤（ａ１−１）としては、例えば、水酸基を有する鎖伸長剤、アミノ基を有する鎖伸長剤等を用いることができる。これらの鎖伸長剤（ａ１−１）は単独で用いても２種以上を併用してもよい。 A chain extender (a1-1) having a number average molecular weight of less than 500 may be used in combination with the polyol (a1), if necessary. As the chain extender (a1-1), for example, a chain extender having a hydroxyl group, a chain extender having an amino group, or the like can be used. These chain extenders (a1-1) may be used alone or in combination of two or more.

前記水酸基を有する鎖伸長剤としては、例えば、エチレングリコール、ジエチレンリコール、トリエチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ヘキサメチレングリコール、サッカロース、メチレングリコール、グリセリン、ソルビトール等の脂肪族ポリオール化合物；ビスフェノールＡ、４，４’−ジヒドロキシジフェニル、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルスルホン、水素添加ビスフェノールＡ、ハイドロキノン等の芳香族ポリオール化合物；水などを用いることができる。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。 Examples of the chain extender having a hydroxyl group include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol. Aliphatic polyol compounds such as saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc. Aromatic polyol compound; water and the like can be used. These chain extenders may be used alone or in combination of two or more.

前記アミノ基を有する鎖伸長剤としては、例えば、エチレンジアミン、１，２−プロパンジアミン、１，６−ヘキサメチレンジアミン、ピペラジン、２−メチルピペラジン、２，５−ジメチルピペラジン、イソホロンジアミン、４，４’−ジシクロヘキシルメタンジアミン、３，３’−ジメチル−４，４’−ジシクロヘキシルメタンジアミン、１，２−シクロヘキサンジアミン、１，４−シクロヘキサンジアミン、アミノエチルエタノールアミン、ヒドラジン、ジエチレントリアミン、トリエチレンテトラミン等を用いることができる。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。 Examples of the chain extender having an amino group include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazin, 2,5-dimethylpiperazine, isophoronediamine, 4,4. '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, etc. Can be used. These chain extenders may be used alone or in combination of two or more.

前記ポリイソシアネート（ａ２）としては、例えば、４，４’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネート、クルードジフェニルメタンジイソシアネート、フェニレンジイソシアネート、トリエンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ポリイソシアネート；シクロヘキサンジイソシアネート、水添キシリレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート等の脂環式ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。 Examples of the polyisocyanate (a2) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylenediisocyanate, trienediisocyanate, naphthalenediocyanate, xylylene diisocyanate, tetra. Aromatic polyisocyanates such as methylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic polyisocyanates such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate should be used. Can be done. These polyisocyanates may be used alone or in combination of two or more.

前記ウレタン樹脂（Ａ）の製造方法としては、例えば、前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）と必要に応じて前記鎖伸長剤（ａ１−１）とを仕込み、反応させることによって製造する方法が挙げられる。これらの反応は、５０〜１００℃の温度で概ね３〜１０時間行うことが好ましい。また、前記反応は、後述する溶剤（Ｂ）中で行ってもよい。 As a method for producing the urethane resin (A), for example, the polyol (a1), the polyisocyanate (a2), and if necessary, the chain extender (a1-1) are charged and reacted. The method can be mentioned. These reactions are preferably carried out at a temperature of 50 to 100 ° C. for approximately 3 to 10 hours. Further, the reaction may be carried out in the solvent (B) described later.

前記ポリオール（ａ１）が有する水酸基並びに前記鎖伸長剤（ａ１−１）が有する水酸基及びアミノ基の合計と、前記ポリイソシアネート（ａ２）が有するイソシアネート基とのモル比［（イソシアネート基）／（水酸基及びアミノ基）］としては、０．８〜１．２の範囲であることが好ましく、０．９〜１．１の範囲であることがより好ましい。 The molar ratio of the total of the hydroxyl group of the polyol (a1) and the hydroxyl group and amino group of the chain extender (a1-1) to the isocyanate group of the polyisocyanate (a2) [(isocyanate group) / (hydroxyl group) And amino group)] is preferably in the range of 0.8 to 1.2, and more preferably in the range of 0.9 to 1.1.

以上の方法により得られるウレタン樹脂（Ａ）の重量平均分子量としては、多孔体の機械的強度及び柔軟性の点から、５，０００〜１，０００，０００の範囲であることが好ましく、１０，０００〜５００，０００の範囲がより好ましい。なお、前記ウレタン樹脂（Ａ）の重量平均分子量は、前記ポリオール（ａ１）の数平均分子量と同様に測定して得られた値を示す。 The weight average molecular weight of the urethane resin (A) obtained by the above method is preferably in the range of 5,000 to 1,000,000 from the viewpoint of the mechanical strength and flexibility of the porous body. The range of 000 to 500,000 is more preferable. The weight average molecular weight of the urethane resin (A) indicates a value obtained by measuring in the same manner as the number average molecular weight of the polyol (a1).

前記ウレタン樹脂（Ａ）の含有量としては、例えば、ウレタン樹脂組成物中１０〜９０質量部の範囲が挙げられる。 Examples of the content of the urethane resin (A) include a range of 10 to 90 parts by mass in the urethane resin composition.

前記溶剤（Ｂ）としては、例えば、酢酸エチル、酢酸メチル、酢酸ブチル、アセトン、メチルエチルケトン、メチルイソブチルケトン、ヘプタン、ヘキサン、シクロヘキサン、メチルシクロヘキサン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、メタノール、エタノール、イソプロピルアルコール、イソブタノール、ｓｅｃ−ブタノール、ターシャリーブタノール、Ｎ，Ｎ，２−トリメチルプロピオンアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルプロピオンアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジエチルアクリルアミド、１，３−ジメチル−２−イミダゾリジノン、Ｎ−エチルピロリドン、２−ピロリドン等を用いることができる。これらの有機溶媒は単独で用いても２種以上を併用してもよい。 Examples of the solvent (B) include ethyl acetate, methyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, heptane, hexane, cyclohexane, methylcyclohexane, toluene, o-xylene, m-xylene, p-xylene, and the like. Methanol, ethanol, isopropyl alcohol, isobutanol, sec-butanol, tertiary butanol, N, N, 2-trimethylpropionamide, N, N-dimethylacrylamide, N, N-dimethylpropionamide, N, N-diethylacetamide, N, N-diethylacrylamide, 1,3-dimethyl-2-imidazolidinone, N-ethylpyrrolidone, 2-pyrrolidone and the like can be used. These organic solvents may be used alone or in combination of two or more.

前記溶剤（Ｂ）の含有量としては、例えば、ウレタン樹脂組成物中１０〜９０質量％の範囲が挙げられる。 Examples of the content of the solvent (B) include a range of 10 to 90% by mass in the urethane resin composition.

前記ウレタン樹脂組成物は、前記ウレタン樹脂（Ａ）、前記溶剤（Ｂ）、及び、前記成膜助剤（Ｃ）を必須成分として含有するが、必要に応じて、その他の添加剤を含有してもよい。 The urethane resin composition contains the urethane resin (A), the solvent (B), and the film forming aid (C) as essential components, but also contains other additives, if necessary. You may.

前記その他の添加剤としては、例えば、前記（ｃ１）以外の成膜助剤、顔料、難燃剤、可塑剤、軟化剤、安定剤、ワックス、消泡剤、分散剤、浸透剤、界面活性剤、フィラー、防黴剤、抗菌剤、紫外線吸収剤、酸化防止剤、耐候安定剤、蛍光増白剤、老化防止剤、増粘剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。 Examples of the other additives include film forming aids, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, and surfactants other than those (c1). , Fillers, antifungal agents, antibacterial agents, ultraviolet absorbers, antioxidants, weather stabilizers, fluorescent whitening agents, antiaging agents, thickeners and the like can be used. These additives may be used alone or in combination of two or more.

次に、前記ウレタン樹脂組成物を湿式成膜法により多孔体を製造する方法について説明する。 Next, a method for producing a porous body from the urethane resin composition by a wet film forming method will be described.

前記湿式成膜法とは、前記ウレタン樹脂組成物を、基材表面に塗布または含浸し、次いで、該塗布面または含浸面に水や水蒸気等を接触させることによって前記ウレタン樹脂（Ａ）を凝固させ多孔体を製造する方法である。 In the wet film forming method, the urethane resin composition is applied or impregnated on the surface of a base material, and then water, water vapor or the like is brought into contact with the coated surface or the impregnated surface to solidify the urethane resin (A). This is a method for producing a porous body.

前記ウレタン樹脂組成物を塗布する基材としては、例えば、不織布、織布、編み物からなる基材；樹脂フィルム等を用いることができる。前記基材を構成するものとしては、例えば、ポリエステル繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維等の化学繊維；綿、麻、絹、羊毛、これらの混紡繊維などを用いることができる。 As the base material to which the urethane resin composition is applied, for example, a base material made of a non-woven fabric, a woven fabric, a knitted fabric; a resin film or the like can be used. Examples of the base material are chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, and polylactic acid fiber; cotton, linen, silk, wool, and a blended fiber thereof. Etc. can be used.

前記基材の表面には、必要に応じて制電加工、離型処理加工、撥水加工、吸水加工、抗菌防臭加工、制菌加工、紫外線遮断加工等の処理が施されていてもよい。 The surface of the base material may be subjected to antistatic treatment, mold release treatment, water repellent treatment, water absorption treatment, antibacterial deodorization treatment, antibacterial treatment, ultraviolet ray blocking treatment and the like, if necessary.

前記基材表面に前記ウレタン樹脂組成物を塗布または含浸する方法としては、例えば、グラビアコーター法、ナイフコーター法、パイプコーター法、コンマコーター法が挙げられる。その際、ウレタン樹脂組成物の粘度を調整し塗工作業性を向上するため、必要に応じて、有機溶剤（Ｂ）の使用量を調節して良い。 Examples of the method of applying or impregnating the urethane resin composition on the surface of the base material include a gravure coater method, a knife coater method, a pipe coater method, and a comma coater method. At that time, in order to adjust the viscosity of the urethane resin composition and improve the coating workability, the amount of the organic solvent (B) used may be adjusted as necessary.

前記方法により塗布または含浸された前記ウレタン樹脂組成物からなる塗膜の膜厚としては、０．５〜５ｍｍの範囲であることが好ましく、０．５〜３ｍｍの範囲がより好ましい。 The film thickness of the coating film made of the urethane resin composition coated or impregnated by the method is preferably in the range of 0.5 to 5 mm, more preferably in the range of 0.5 to 3 mm.

前記ウレタン樹脂組成物が塗布または含浸され形成した塗布面に水または水蒸気を接触させる方法としては、例えば、前記ウレタン樹脂組成物からなる塗布層や含浸層の設けられた基材を水浴中に浸漬する方法；前記塗布面上にスプレー等を用いて水を噴霧する方法などが挙げられる。前記浸漬は、例えば、５〜６０℃の水浴中に、２〜２０分間行うことが挙げられる。 As a method of bringing water or water vapor into contact with the coated surface formed by coating or impregnating the urethane resin composition, for example, a coating layer made of the urethane resin composition or a base material provided with an impregnated layer is immersed in a water bath. Method; A method of spraying water on the coated surface using a spray or the like can be mentioned. The immersion may be carried out, for example, in a water bath at 5 to 60 ° C. for 2 to 20 minutes.

前記方法によって得られた多孔体は、常温の水や温水を用いてその表面を洗浄して溶剤（Ｂ）を抽出除去し、次いで乾燥することが好ましい。前記洗浄は、例えば、５〜６０℃の水で２０〜１２０分間行うことが挙げられ、洗浄に用いる水は１回以上入れ替えるか、あるいは、流水で連続して入れ替えるのが好ましい。前記乾燥は、例えば、８０〜１２０℃に調整した乾燥機等を使用して、１０〜６０分間行うことが好ましい。 It is preferable that the surface of the porous body obtained by the above method is washed with water at room temperature or warm water to extract and remove the solvent (B), and then dried. The washing may be carried out with water at 5 to 60 ° C. for 20 to 120 minutes, and the water used for washing is preferably replaced once or more, or continuously with running water. The drying is preferably carried out for 10 to 60 minutes using, for example, a dryer adjusted to 80 to 120 ° C.

以上、本発明によれば、特定の成膜助剤を用いることで、湿式成膜法により、細かく均一なセルを有し、ボリューム感がありソフトな風合いを有する多孔体を製造することができる。よって、本発明は、研磨パッド、人工皮革・合成皮革の製造に特に好適に使用することができる。 As described above, according to the present invention, by using a specific film-forming auxiliary, it is possible to produce a porous body having fine and uniform cells, a voluminous feel, and a soft texture by a wet film-forming method. .. Therefore, the present invention can be particularly suitably used for the production of polishing pads, artificial leather and synthetic leather.

以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.

［合成例１］ウレタン樹脂（Ａ−１）の合成
攪拌機、還流器、温度計を有する反応装置に、ポリエステルポリオール（エチレングリコール及びアジピン酸の反応物、数平均分子量；２，０００）を１００質量部、１，４−ブタンジオールを２０質量部、Ｎ，Ｎ−ジメチルホルムアミドを５６４質量部、及び、４，４’−ジフェニルメタンジイソシアネートを６８質量部投入し、撹拌下６０℃で６時間反応させ、引き続き、イソプロピルアルコールを１質量部投入して、更に６０℃で１時間撹拌することによって、ウレタン樹脂組成物を得た。
得られたウレタン樹脂組成物は、固形分；２５質量％、粘度；６００ｄＰａ・ｓ、ウレタン樹脂の重量平均分子量は１８８，１００であった。 [Synthesis Example 1] Synthesis of Urethane Resin (A-1) 100 mass of polyester polyol (reactant of ethylene glycol and adipic acid, number average molecular weight; 2,000) in a reactor having a stirrer, a recirculator, and a thermometer. 20 parts by mass of 1,4-butanediol, 564 parts by mass of N, N-dimethylformamide, and 68 parts by mass of 4,4'-diphenylmethane diisocyanate were added and reacted at 60 ° C. for 6 hours under stirring. Subsequently, 1 part by mass of isopropyl alcohol was added, and the mixture was further stirred at 60 ° C. for 1 hour to obtain a urethane resin composition.
The obtained urethane resin composition had a solid content of 25% by mass, a viscosity of 600 dPa · s, and a weight average molecular weight of the urethane resin of 188,100.

［合成例２］ウレタン樹脂（Ａ−２）の合成
攪拌機、還流器、温度計を有する反応装置に、ポリテトラメチレングリコール（数平均分子量；２，０００）を１００質量部、エチレングリコールを１０質量部、Ｎ，Ｎ−ジメチルホルムアミドを３８０質量部、及び、４，４’−ジフェニルメタンジイソシアネートを５３質量部投入し、撹拌下６０℃で６時間反応させ、引き続き、イソプロピルアルコールを１質量部投入して、更に６０℃で１時間撹拌することによって、ウレタン樹脂組成物を得た。
得られたウレタン樹脂組成物は、固形分；３０質量％、粘度；８００ｄＰａ・ｓ、ウレタン樹脂の重量平均分子量は１２０，５００であった。 [Synthesis Example 2] Synthesis of Urethane Resin (A-2) 100 parts by mass of polytetramethylene glycol (number average molecular weight; 2,000) and 10 parts by mass of ethylene glycol are added to a reactor having a stirrer, a recirculator, and a thermometer. 380 parts by mass of N, N-dimethylformamide and 53 parts by mass of 4,4'-diphenylmethane diisocyanate were added and reacted at 60 ° C. for 6 hours with stirring, and then 1 part by mass of isopropyl alcohol was added. Further, the mixture was further stirred at 60 ° C. for 1 hour to obtain a urethane resin composition.
The obtained urethane resin composition had a solid content of 30% by mass, a viscosity of 800 dPa · s, and a weight average molecular weight of the urethane resin of 120,500.

［数平均分子量・重量平均分子量の測定方法］
合成例で用いた原料ポリオールの数平均分子量、シリコーン化合物（ｃ１）の数平均分子量、ウレタン樹脂（Ａ）の重量平均分子量 は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。 [Measurement method of number average molecular weight / weight average molecular weight]
The number average molecular weight of the raw material polyol used in the synthesis example, the number average molecular weight of the silicone compound (c1), and the weight average molecular weight of the urethane resin (A) are determined by the gel permeation chromatography (GPC) method under the following conditions. Shows the measured value.

測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ−８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

（標準ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−５５０」 (Standard polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

［実施例１］
合成例１で得られたウレタン樹脂組成物１００質量部に対し、Ｎ，Ｎ−ジメチルホルムアミド（以下、「ＤＭＦ」と略記する。）を４０質量部、水酸基及びオキシエチレン構造（以下「ＥＯ構造」と略記する。）を有するシリコーン化合物（ダウ・東レコーニング株式会社製「ＳＦ−８４２７」、数平均分子量２，４００、以下「ｃ１−１」」と略記する。）を２質量部加えて配合液を作成し、厚さ（Ｗｅｔ）１ｍｍとなるようにポリエチレンテレフタレート（ＰＥＴ）フィルムに塗布した。次いで、凝固浴（２５℃の水）へ塗布基材を１０分間浸漬させ、ウレタン樹脂を凝固させた。その後、この基材を５０℃の水に６０分間浸漬させて溶剤を洗浄した。洗浄後、基材を１００℃で３０分間熱風乾燥させ、多孔体を得た。 [Example 1]
40 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as "DMF"), a hydroxyl group and an oxyethylene structure (hereinafter, "EO structure") with respect to 100 parts by mass of the urethane resin composition obtained in Synthesis Example 1. (Abbreviated as "SF-8427" manufactured by Dow Toray Corning Co., Ltd., number average molecular weight 2,400, hereinafter abbreviated as "c1-1") is added in an amount of 2 parts by mass. Was prepared and applied to a polyethylene terephthalate (PET) film so as to have a thickness (Wet) of 1 mm. Next, the coating base material was immersed in a coagulation bath (water at 25 ° C.) for 10 minutes to solidify the urethane resin. Then, this base material was immersed in water at 50 ° C. for 60 minutes to wash the solvent. After washing, the substrate was dried with hot air at 100 ° C. for 30 minutes to obtain a porous body.

［実施例２］
実施例１において、ｃ１−１に代えて、水酸基及びオキシエチレン構造を有するシリコーン化合物（信越化学工業株式会社製「ＫＦ−６１２３」、数平均分子量２，２００、以下「ｃ１−２」」と略記する。）を用いた以外は、実施例１と同様にして多孔体を得た。 [Example 2]
In Example 1, instead of c1-1, a silicone compound having a hydroxyl group and an oxyethylene structure (“KF-6123” manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,200, hereinafter abbreviated as “c1-2””. A porous body was obtained in the same manner as in Example 1 except that the above was used.

［実施例３］
実施例１において、合成例１で得られたウレタン樹脂組成物に代えて、合成例２で得られたウレタン樹脂組成物を用いた以外は、実施例１と同様にして多孔体を得た。 [Example 3]
In Example 1, a porous body was obtained in the same manner as in Example 1 except that the urethane resin composition obtained in Synthesis Example 2 was used instead of the urethane resin composition obtained in Synthesis Example 1.

［比較例１］
実施例１において、ｃ１−１に代えて、水酸基を有するシリコーン化合物（信越化学工業株式会社製「ＫＦ−６００１」、数平均分子量１，８００、以下「ｃＲ１−１」」と略記する。）を用いた以外は、実施例１と同様にして多孔体を得た。 [Comparative Example 1]
In Example 1, a silicone compound having a hydroxyl group (“KF-6001” manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,800, hereinafter abbreviated as “cR1-1”) is used instead of c1-1. A porous body was obtained in the same manner as in Example 1 except that it was used.

［比較例２］
実施例１において、ｃ１−１に代えて、ドデシルベンゼンスルホン酸（以下「ＤＢＳ」と略記する。）を用いた以外は、実施例１と同様にして多孔体を得た。 [Comparative Example 2]
A porous body was obtained in the same manner as in Example 1 except that dodecylbenzenesulfonic acid (hereinafter abbreviated as “DBS”) was used instead of c1-1 in Example 1.

［湿式成膜性の評価方法］
実施例で得られた多孔体の断面状態を、日本電子株式会社製走査型電子顕微鏡「ＪＳＭ−ＩＴ５００」（倍率：１００倍）で観察し、セル形状（細さ、均一性）を確認し、最大横幅が７０μｍ以下のセルが全体の６０％を占めていれば「○」、それ以外は「×」と評価した。 [Evaluation method for wet film formation]
The cross-sectional state of the porous body obtained in the examples was observed with a scanning electron microscope "JSM-IT500" (magnification: 100 times) manufactured by JEOL Ltd., and the cell shape (thinness, uniformity) was confirmed. If cells with a maximum width of 70 μm or less occupy 60% of the total, it was evaluated as “◯”, otherwise it was evaluated as “x”.

［風合いの評価方法］
実施例で得られた多孔体について、指触により風合いを確認し、ボリューム感、及び、反発感がある場合には「○」、それ以外は「×」と評価した。 [Texture evaluation method]
The texture of the porous body obtained in the examples was confirmed by touching with a finger, and was evaluated as “◯” when there was a feeling of volume and repulsion, and “×” in other cases.

Figure 2020186353
Figure 2020186353

本発明の製造方法により得られた多孔体は、セルが細かく均一であり、風合いにも優れることが分かった。 It was found that the porous body obtained by the production method of the present invention had fine and uniform cells and was excellent in texture.

一方、比較例１は成膜助剤として、シリコーン化合物（ｃ１）の代わりに、オキシエチレン構造を有さないシリコーン化合物を用いた態様であるが、多孔セル形成が不良であり、風合いも不良であった。 On the other hand, Comparative Example 1 uses a silicone compound having no oxyethylene structure instead of the silicone compound (c1) as a film forming aid, but the porous cell formation is poor and the texture is also poor. there were.

比較例２は成膜助剤として、シリコーン化合物（ｃ１）の代わりに、ドデシルベンゼンスルホン酸を用いた態様であるが、多孔セル形成が不良であり、風合いも不良であった。 Comparative Example 2 was an embodiment in which dodecylbenzenesulfonic acid was used instead of the silicone compound (c1) as the film forming aid, but the porous cell formation was poor and the texture was also poor.

Claims (4)

ウレタン樹脂（Ａ）、溶剤（Ｂ）、及び、成膜助剤（Ｃ）を含有するウレタン樹脂組成物を湿式成膜して多孔体を製造する方法であって、
前記成膜助剤（Ｃ）が、オキシエチレン構造を有するシリコーン化合物（ｃ１）であることを特徴とする多孔体の製造方法。 A method for producing a porous body by wet-forming a urethane resin composition containing a urethane resin (A), a solvent (B), and a film forming aid (C).
A method for producing a porous body, wherein the film-forming auxiliary (C) is a silicone compound (c1) having an oxyethylene structure. 前記シリコーン化合物（ｃ１）が、更に、水酸基を有するものである請求項１記載の多孔体の製造方法。 The method for producing a porous body according to claim 1, wherein the silicone compound (c1) further has a hydroxyl group. 前記シリコーン化合物（ｃ１）の数平均分子量が、５００〜５，０００の範囲である請求項１又は２記載の多孔体の製造方法。 The method for producing a porous body according to claim 1 or 2, wherein the number average molecular weight of the silicone compound (c1) is in the range of 500 to 5,000. 前記シリコーン化合物（ｃ１）の含有量が、前記ウレタン樹脂（Ａ）１００質量部に対して、０．１〜３０質量部の範囲である請求項１又は２記載の多孔体の製造方法。 The method for producing a porous body according to claim 1 or 2, wherein the content of the silicone compound (c1) is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A).
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