JP4353600B2 - Method for producing porous body - Google Patents
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- JP4353600B2 JP4353600B2 JP37679799A JP37679799A JP4353600B2 JP 4353600 B2 JP4353600 B2 JP 4353600B2 JP 37679799 A JP37679799 A JP 37679799A JP 37679799 A JP37679799 A JP 37679799A JP 4353600 B2 JP4353600 B2 JP 4353600B2
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- water
- porous body
- urethane resin
- resin emulsion
- artificial leather
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- Compositions Of Macromolecular Compounds (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、人工皮革に適した多孔体を有機溶剤を使用しない非溶剤系の工程で成型するために使用する薬剤に関するものであり、本薬剤を使用することにより乾燥後に水分が存在していた部分を多孔体とすることが可能となる。
【０００２】
【従来の技術】
従来の人工皮革は、ポリウレタンのジメチルホルムアミド（ＤＭＦ）等の有機溶剤溶液に着色剤を含む各種添加剤を加えた処理液を繊維製品に含浸及びコーティングした後、使用している有機溶剤を水で抽出して多孔体を成型する湿式法人工皮革製造方法ともしくは有機溶剤の持つ揮発性を活用して多孔体を成型する乾式法人工皮革製造方法とによって生産されている。
これらの製造方法では生産時に多量の有機溶剤を取り扱うためにその作業環境と環境汚染の問題があり、更に生産された人工皮革から完全に有機溶剤を除去する必要がある。有機溶剤の除去が不充分な場合にはそれを取り扱う作業者、更に使用者、着用者に対しての影響を考慮しなければならず、水質汚濁、大気汚染の防止、更に作業者、着用者に対する影響を防ぐために多大なエネルギーと労力、経費が必要となる。
【０００３】
これに対して水系ウレタン樹脂エマルジョンを使用した製造方法では有機溶剤を使用しないためにそれらの回収を必要とせず、作業環境が改善され、水質汚濁や大気汚染を生じることは無い。更に有機溶剤の残留による作業者、使用者、着用者への影響も著しく低減できる特徴を備えている。
しかし、水系ウレタン樹脂エマルジョンを使用した従来の製造方法の発泡法では空気の泡を多孔体とするスポンジ状の独立泡多孔体しか得られなかった。
これは人工皮革には適さない多孔体であり、かつ発泡法によらなければ多孔体は得られず、水系ウレタン樹脂エマルジョンを使用した人工皮革が使用される用途、分野に制限を生じさせていた。
【０００４】
【発明が解決しようとする課題】
本発明は水系ウレタン樹脂エマルジョンを使用して人工皮革に適した連続泡多孔体を成型することにより、前述した有機溶剤系ウレタン樹脂溶液を使用する製造方法での環境汚染問題、有機溶剤の残留による人に対しての悪影響を解決し且つ、水系ウレタン樹脂エマルジョンを使用することによる多孔状態の差異による問題点を解決して、従来の有機溶剤系ウレタン樹脂溶液を使用した人工皮革に適した多孔体と遜色無い多孔体を提供するものである。
【０００５】
【課題を解決するための手段】
本発明者らは、ウレタン樹脂エマルジョンを使用して連続泡多孔体を成型する目的で鋭意研究を重ねた結果、水系ウレタン樹脂エマルジョンにキトサン、アルカリカゼイン、カルボキシメチルセルロース、メチルセルロース等の水溶性の高結晶天然物を添加し、これらの高結晶天然物を更に架橋剤及び添加剤を併用することにより湿熱加熱凝固過程で水不溶性の核とした後、乾燥して水分を除去することにより水分が存在していた部分を人工皮革に適した連続泡多孔体とする方法でかかる目的を達成できることを見出し、この知見により本発明を完成するに至った。
【０００６】
即ち、本発明は不織布、織物、編物またはフィルムに水系ウレタン樹脂エマルジョンを含浸、コーティング処理を行い、次に湿熱凝固処理を行った後、加熱乾燥して水分を除去する人工皮革に適した多孔体の製造方法において、水系ウレタン樹脂エマルジョンに前述の水溶性の高結晶天然物を加えたものを湿熱加熱凝固させて核とし、得られた核が水分を除去する乾燥の際に前述の２価金属塩やケイ酸及びケイ酸塩の作用で水不溶性の状態で存在することにより水分が存在していた部分と水系ウレタン樹脂部分を絶縁隔離し更に前述の水に対して溶解度の低いシリコーンオイル及びグライコール変性シリコーンオイルがその絶縁隔離作用を補助することで水が存在していた部分を人工皮革に適した連続泡多孔体とする製造方法を提供するものである。
【０００７】
水系ウレタン樹脂エマルジョンを使用した人工皮革用に適した多孔体を製造する本発明方法においてキトサン、アルカリカゼイン、カルボキシメチルセルロース、メチルセルロースの水溶性の高結晶天然物のうち水系ウレタン樹脂エマルジョンと併用性が優れたものを水系ウレタン樹脂エマルジョン純分に対して２〜２０重量％添加する。
このうち特に好ましいものはアルカリカゼインであり、添加される重量％が水系ウレタン樹脂エマルジョン純分に対して２％以下の場合は目的とする作用効果が得られず、一方２０％以上の場合は添加した水溶性の高結晶天然物の性質が発現してウレタン樹脂の特徴を損なう。
【０００８】
架橋剤としての金属塩類が水系ウレタン樹脂エマルジョン純分に対して０．１〜４．０重量％添加され、塩化物、硫酸化物、その他無機酸、有機酸の塩類が好ましく又、ケイ酸塩はアルカリ金属塩で使用することが好ましい。
このうち特に好ましいものは塩化マグネシウムとコロイダルシリカと呼ばれているケイ酸化合物であり、添加される重量％が水系ウレタン樹脂エマルジョン純分に対して０．１％以下の場合は目的とする作用効果が得られず、４．０％以上の場合は添加した金属塩やケイ酸及びケイ酸塩がウレタン樹脂内部で析出してその特徴を損なう。
【０００９】
添加剤として、好ましくはシリコーンオイル及びグライコール変性シリコーンが水系ウレタン樹脂エマルジョン純分に対して１〜１０重量％使用され、金属塩類やケイ酸及びケイ酸塩と共に添加されることが好ましい。
このうち特に好ましいものは１０ｃｍ２／ｓ以下の粘度の低いジメチルポリシロキサン及び水に溶解した場合完全な水溶性を示さないグライコールの重量比が６０％以下のグライコール変性シリコーンである。添加される重量％が水系ウレタン樹脂エマルジョン純分に対して１％以下の場合は目的とする十分な作用効果が得られず、１０％以上の場合は添加したシリコーンオイル及びグライコール変性シリコーンが析出して連続泡多孔体表面に汚れを発生させその品位を低下させるので好ましくない。
【００１０】
本発明に使用される水系ウレタン樹脂エマルジョンとしてはアニオン系、ノニオン系のものが使用でき、目的とする人工皮革の適性に合致したものを選択することができる。
本発明に使用される人工皮革の基布としては従来の方法でも使用されていた不織布、織物、編物またはフィルムを使用することができる。
【００１１】
本発明の含浸、コーティングは従来の生産設備と同様の機械装置を使用することができ、水系ウレタン樹脂エマルジョンにキトサン、アルカリカゼイン、カルボキシメチルセルロース、メチルセルロースの水溶性高結晶天然物のうち水系ウレタン樹脂エマルジョンと併用性が優れたものを添加し、次に架橋剤としての金属塩類、ケイ酸もしくはケイ酸塩を添加し、更に添加剤としてシリコーンオイル、グライコール変性シリコーンを添加し、適切な混合機で均一状態として使用する。尚、これらの混合液は含浸、コーティングに適した粘度とする目的でアクリル系増粘剤、界面活性剤系増粘剤を適当量使用することができる。
湿熱加熱凝固処理は常圧スチーマーの条件、６０〜１００℃の飽和水蒸気圧の環境下で行うことができ、次の乾燥工程は一般的なピンテンター等による乾熱乾燥、遠赤外線を使用した乾燥を行うことができる。
【００１２】
【実施例】
以下に、実施例をあげて本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものでない。尚、実施例中の「部」は特記しない限り重量部を示す。
評価に使用したポリエステル不織布は厚み：１．３ｍｍ、密度：０．２７ｇ／ｃｍ２のものを使用し、本発明の特性値の測定は以下の評価方法に従った。
電子顕微鏡写真：実施例、比較例で得られた人工皮革の表皮部分の電子顕微鏡写真を撮影し、多孔状態の評価の資料とした。
厚み：株式会社尾崎製作所製ピーコック厚み計タイプＨ（最小目盛：０．０１ｍｍ）を使用した。
密度：ＪＩＳ−Ｋ−６５０５に規定された方法に従った。
剛軟度：ＪＩＳ−Ｌ−１０７９に規定された方法に従った。数値が小さいほど柔らかい。
【００１３】
実施例１
フィルム状態での連続泡多孔体を確認する目的で厚さ１００μのポリエステルフィルムに表１に記載の処方の原液をクリアランス＝１．０ｍｍでコーティングし、９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、次に９５℃の乾熱環境下で６０分間乾燥処理を行って多孔体フィルムを得た。
【００１４】
実施例２
ポリエステル不織布（厚み：１．３ｍｍ、密度：０．２７ｇ／ｃｍ２）をメチルハイドロジェンポリシロキサンエマルジョン（松本油脂製薬株式会社製品：ゲラネックスＳ−３）とその触媒である亜鉛系化合物の乳化分散物（松本油脂製薬株式会社製品：触媒ＴＳＣ−４５０）とを水に各々３％、１％重量比の濃度で溶解させた溶液に浸漬し、マングルで過剰の溶液を絞り、１２０℃にて乾燥させた前処理済みの不織布を作成した。
マングルによる搾液で水溶液の付着量は不織布の重量比で１３０％、即ち不織布１００ｇに対して水溶液が１３０ｇ付着した。
次にこの前処理済みの不織布に表１に記載の処方の原液をクリアランス＝１．０ｍｍでコーティングし、９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、更に９５℃の乾熱環境下で１２０分間乾燥処理を行って人工皮革状の物を得た。
【００１５】
実施例３
ポリエステル不織布（厚み：１．３ｍｍ、密度：０．２７ｇ／ｃｍ２）をメチルハイドロジェンポリシロキサンエマルジョン（松本油脂製薬株式会社製品：ゲラネックスＳ−３）とその触媒である亜鉛系化合物の乳化分散物（松本油脂製薬株式会社製品：触媒ＴＳＣ−４５０）とを水に各々３％、１％重量比の濃度で溶解させた溶液に浸漬し、マングルで過剰の溶液を絞り、１２０℃にて乾燥させた前処理済みの不織布を作成した。
マングルによる搾液で水溶液の付着量は不織布の重量比で１３０％、即ち不織布１００ｇに対して水溶液が１３０ｇ付着した。
次にこの前処理済み不織布に表２に記載の処方の原液を含浸した後９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、更に９５℃の乾熱環境下で１２０分間乾燥処理を行って不織布内部にポリウレタン樹脂を含む試験布を得た。
次にこの内部にポリウレタン樹脂が含まれる不織布に表１に記載の処方の原液をクリアランス＝１．０ｍｍでコーティングし、９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、更に９５℃の乾熱環境下で１２０分間乾燥処理を行って人工皮革状の物を得た。
【００１６】
【表１】
【表２】
比較例１
フィルム状態での連続泡多孔体を確認する目的で厚さ１００μのポリエステルフィルムに表１に記載の処方の原液をクリアランス＝１．０ｍｍでコーティングし、９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、次に９５℃の乾熱環境下で６０分間乾燥処理を行って多孔体フィルムを得た。
【００１９】
比較例２
ポリエステル不織布（厚み：１．３ｍｍ、密度：０．２７ｇ／ｃｍ２）をメチルハイドロジェンポリシロキサンエマルジョン（松本油脂製薬株式会社製品：ゲラネックスＳ−３）とその触媒である亜鉛系化合物の乳化分散物（松本油脂製薬株式会社製品：触媒ＴＳＣ−４５０）とを水に各々３％、１％重量比の濃度で溶解させた溶液に浸漬し、マングルで過剰の溶液を絞り、１２０℃にて乾燥させた前処理済みの不織布を作成した。
マングルによる搾液で水溶液の付着量は不織布の重量比で１３０％、即ち不織布１００ｇに対して水溶液が１３０ｇ付着した。
次にこの前処理済みの不織布に表１に記載の処方の原液をクリアランス＝１．０ｍｍでコーティングし、９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、更に９５℃の乾熱環境下で１２０分間乾燥処理を行って人工皮革状の物を得た。
【００２０】
比較例３
ポリエステル不織布（厚み：１．３ｍｍ、密度：０．２７ｇ／ｃｍ２）をメチルハイドロジェンポリシロキサンエマルジョン（松本油脂製薬株式会社製品：ゲラネックスＳ−３）とその触媒である亜鉛系化合物の乳化分散物（松本油脂製薬株式会社製品：触媒ＴＳＣ−４５０）とを水に各々３％、１％重量比の濃度で溶解させた溶液に浸漬し、マングルで過剰の溶液を絞り、１２０℃にて乾燥させた前処理済みの不織布を作成した。
マングルによる搾液で水溶液の付着量は不織布の重量比で１３０％、即ち不織布１００ｇに対して水溶液が１３０ｇ付着した。
次にこの前処理済み不織布に表３に記載の処方の原液を含浸した後９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、更に９５℃の乾熱環境下で１２０分間乾燥処理を行って不織布内部にポリウレタン樹脂を含む試験布を得た。
次にこの内部にポリウレタン樹脂が含まれる不織布に表１に記載の処方の原液をクリアランス＝１．０ｍｍでコーティングし、９０℃の飽和水蒸気圧の環境下で３０分間の湿熱加熱凝固処理を行い、更に９５℃の乾熱環境下で１２０分間乾燥処理を行って人工皮革状の物を得た。
【００２１】
【表３】
【発明の効果】
本発明の方法によれば、水系ウレタン樹脂エマルジョンを使用して良好な多孔状態を成型できるため、厚みが厚くて密度が低い人工皮革に適した連続泡多孔体が成型でき、本発明によって得られるものは本発明によらないものと比較してより軽量で柔軟なものを有機溶剤を使用せずに得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a drug used for molding a porous material suitable for artificial leather in a non-solvent system process that does not use an organic solvent, and moisture was present after drying by using this drug. It becomes possible to make the portion porous.
[0002]
[Prior art]
In conventional artificial leather, fiber products are impregnated and coated with a processing solution in which various additives including colorants are added to an organic solvent solution such as dimethylformamide (DMF) of polyurethane, and then the organic solvent used is washed with water. It is produced by a wet method artificial leather manufacturing method in which a porous body is extracted by extraction, or a dry method artificial leather manufacturing method in which a porous body is molded by utilizing the volatility of an organic solvent.
In these production methods, since a large amount of organic solvent is handled during production, there are problems of working environment and environmental pollution, and it is necessary to completely remove the organic solvent from the produced artificial leather. If the removal of organic solvent is insufficient, the impact on workers, users, and wearers must be considered. Water pollution, air pollution prevention, and workers and wearers. A great deal of energy, labor, and expenses are required to prevent the impact on the environment.
[0003]
On the other hand, in the manufacturing method using a water-based urethane resin emulsion, since organic solvents are not used, they are not required to be collected, the working environment is improved, and water pollution and air pollution do not occur. Furthermore, it has the feature that the influence on the worker, the user, and the wearer due to the remaining organic solvent can be remarkably reduced.
However, in the foaming method of the conventional manufacturing method using an aqueous urethane resin emulsion, only a sponge-like closed-cell porous body having air bubbles as a porous body can be obtained.
This is a porous body that is not suitable for artificial leather, and if the foaming method is not used, a porous body cannot be obtained, which has limited the applications and fields in which artificial leather using an aqueous urethane resin emulsion is used. .
[0004]
[Problems to be solved by the invention]
The present invention uses a water-based urethane resin emulsion to mold a continuous foam porous body suitable for artificial leather, thereby causing environmental pollution problems in the production method using the organic solvent-based urethane resin solution described above, due to residual organic solvent. A porous material suitable for artificial leather using conventional organic solvent-based urethane resin solutions that solves the adverse effects on humans and solves the problems caused by the difference in the porous state due to the use of water-based urethane resin emulsions It provides a porous body comparable to the above.
[0005]
[Means for Solving the Problems]
As a result of intensive research for the purpose of forming a continuous foam porous body using a urethane resin emulsion, the present inventors have obtained water-soluble high crystals such as chitosan, alkali casein, carboxymethylcellulose, and methylcellulose in an aqueous urethane resin emulsion. After adding natural products, these high crystalline natural products are further combined with a crosslinking agent and additives to form water-insoluble nuclei in the heat and heat coagulation process, and then dried to remove the water so that moisture is present. The present inventors have found that this object can be achieved by a method in which the part that has been used is an open-cell porous body suitable for artificial leather, and this finding has led to the completion of the present invention.
[0006]
That is, the present invention is a porous body suitable for artificial leather in which a nonwoven fabric, woven fabric, knitted fabric or film is impregnated with a water-based urethane resin emulsion, subjected to coating treatment, then subjected to wet heat coagulation treatment, and then dried by heating to remove moisture. In the production method, a water-based urethane resin emulsion added with the above-mentioned water-soluble highly crystalline natural product is solidified by heating with heat and moist heat to form a core, and the resulting core removes moisture and the above-mentioned divalent metal is dried. The water-insoluble state due to the action of salts, silicic acid, and silicates isolates the water-existing portion from the water-based urethane resin portion, and further separates the above-mentioned silicone oil and silica with low solubility in water. A method for producing a continuous foam porous body suitable for artificial leather in a part where water was present by assisting the insulating and isolating action of equol-modified silicone oil A.
[0007]
Excellent compatibility with water-based urethane resin emulsion among water-soluble highly crystalline natural products of chitosan, alkali casein, carboxymethylcellulose, and methylcellulose in the method of the present invention for producing a porous material suitable for artificial leather using water-based urethane resin emulsion 2 to 20% by weight is added to the pure water-based urethane resin emulsion.
Of these, alkali casein is particularly preferable. When the added weight% is 2% or less with respect to the pure content of the water-based urethane resin emulsion, the desired effect cannot be obtained. The properties of the water-soluble highly crystalline natural product are manifested and the characteristics of the urethane resin are impaired.
[0008]
Metal salt as a crosslinking agent is added in an amount of 0.1 to 4.0% by weight based on the pure water-based urethane resin emulsion, and salts of chlorides, sulfates, other inorganic acids, and organic acids are preferable. It is preferable to use an alkali metal salt.
Of these, particularly preferred are silicate compounds called magnesium chloride and colloidal silica, and when the added weight% is 0.1% or less with respect to the pure content of the water-based urethane resin emulsion, the desired effect is obtained. In the case of 4.0% or more, the added metal salt, silicic acid and silicate are precipitated inside the urethane resin and the characteristics thereof are impaired.
[0009]
As additives, preferably, silicone oil and glycol-modified silicone are used in an amount of 1 to 10% by weight based on the pure water-based urethane resin emulsion, and are preferably added together with metal salts, silicic acid and silicate.
Among them, particularly preferred are dimethylpolysiloxane having a low viscosity of 10 cm 2 / s or less and a glycol-modified silicone having a weight ratio of 60% or less of glycol which does not show complete water solubility when dissolved in water. When the added weight% is 1% or less with respect to the pure amount of the water-based urethane resin emulsion, the desired effect cannot be obtained, and when it is 10% or more, the added silicone oil and glycol modified silicone are precipitated. Thus, it is not preferable because dirt is generated on the surface of the continuous foam porous body and its quality is lowered.
[0010]
As the water-based urethane resin emulsion used in the present invention, anionic and nonionic emulsions can be used, and those matching the suitability of the target artificial leather can be selected.
As the base fabric of the artificial leather used in the present invention, a nonwoven fabric, a woven fabric, a knitted fabric or a film which has been used in the conventional method can be used.
[0011]
The impregnation and coating of the present invention can use the same mechanical equipment as the conventional production equipment, and water-based urethane resin emulsion among water-soluble high-crystalline natural products of chitosan, alkali casein, carboxymethylcellulose, and methylcellulose in water-based urethane resin emulsion. Add a metal salt, silicic acid or silicate as a cross-linking agent, and add silicone oil or glycol modified silicone as an additive. Use as a uniform state. In addition, these mixed liquids can use an appropriate amount of an acrylic thickener and a surfactant thickener for the purpose of obtaining a viscosity suitable for impregnation and coating.
The wet heat heating coagulation treatment can be performed under the conditions of atmospheric steamer and saturated water vapor pressure of 60-100 ° C, and the next drying process is dry heat drying with a general pin tenter or the like, drying using far infrared rays. It can be carried out.
[0012]
【Example】
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means parts by weight unless otherwise specified.
The polyester nonwoven fabric used for the evaluation was one having a thickness of 1.3 mm and a density of 0.27 g / cm 2 , and the characteristic values of the present invention were measured according to the following evaluation method.
Electron micrograph: An electron micrograph of the skin portion of the artificial leather obtained in Examples and Comparative Examples was taken and used as a material for evaluating the porous state.
Thickness: Peacock thickness gauge type H (minimum scale: 0.01 mm) manufactured by Ozaki Mfg. Co., Ltd. was used.
Density: A method defined in JIS-K-6505 was followed.
Bending resistance: A method defined in JIS-L-1079 was followed. The smaller the value, the softer.
[0013]
Example 1
For the purpose of confirming a continuous foam porous body in a film state, a 100 μm-thick polyester film was coated with a stock solution of the formulation shown in Table 1 at a clearance = 1.0 mm, and was subjected to a saturated water vapor pressure of 90 ° C. for 30 minutes. The porous film was obtained by performing a wet heat heating coagulation treatment and then a drying treatment in a dry heat environment at 95 ° C. for 60 minutes.
[0014]
Example 2
Polyester nonwoven fabric (thickness: 1.3 mm, density: 0.27 g / cm 2 ) emulsified dispersion of methyl hydrogen polysiloxane emulsion (Matsumoto Yushi Seiyaku Co., Ltd. product: Gelanex S-3) and zinc-based compound as its catalyst (Matsumoto Yushi Seiyaku Co., Ltd. product: Catalyst TSC-450) was immersed in water at a concentration of 3% and 1% by weight, respectively, and the excess solution was squeezed with mangle and dried at 120 ° C. A pretreated non-woven fabric was prepared.
In the squeezing with mangle, the amount of the aqueous solution adhered was 130% by weight of the nonwoven fabric, that is, 130 g of the aqueous solution adhered to 100 g of the nonwoven fabric.
Next, the pretreated non-woven fabric was coated with a stock solution having the formulation shown in Table 1 with a clearance of 1.0 mm, and subjected to a heat-heat coagulation treatment for 30 minutes in an environment of saturated steam pressure at 90 ° C., and further 95 ° C. The artificial leather-like thing was obtained by performing a drying process for 120 minutes in a dry heat environment.
[0015]
Example 3
Polyester nonwoven fabric (thickness: 1.3 mm, density: 0.27 g / cm 2 ) emulsified dispersion of methyl hydrogen polysiloxane emulsion (Matsumoto Yushi Seiyaku Co., Ltd. product: Gelanex S-3) and zinc-based compound as its catalyst (Matsumoto Yushi Seiyaku Co., Ltd. product: Catalyst TSC-450) was immersed in water at a concentration of 3% and 1% by weight, respectively, and the excess solution was squeezed with mangle and dried at 120 ° C. A pretreated non-woven fabric was prepared.
In the squeezing with mangle, the amount of the aqueous solution adhered was 130% by weight of the nonwoven fabric, that is, 130 g of the aqueous solution adhered to 100 g of the nonwoven fabric.
Next, the pretreated non-woven fabric was impregnated with the stock solution of the formulation shown in Table 2, and then subjected to wet heat heating coagulation for 30 minutes in an environment of saturated steam pressure of 90 ° C., and further 120 ° A test cloth containing a polyurethane resin inside the nonwoven fabric was obtained by performing a drying treatment for a minute.
Next, a non-woven fabric containing a polyurethane resin is coated with a stock solution of the formulation shown in Table 1 with a clearance = 1.0 mm, and subjected to a wet heat heating coagulation treatment for 30 minutes in a 90 ° C. saturated water vapor pressure environment, Further, a drying process was performed for 120 minutes in a dry heat environment at 95 ° C. to obtain an artificial leather-like product.
[0016]
[Table 1]
[Table 2]
Comparative Example 1
For the purpose of confirming a continuous foam porous body in a film state, a 100 μm-thick polyester film was coated with a stock solution of the formulation described in Table 1 at a clearance = 1.0 mm, and was subjected to a saturated water vapor pressure of 90 ° C. for 30 minutes The porous film was obtained by performing a wet heat heating coagulation treatment and then a drying treatment in a dry heat environment at 95 ° C. for 60 minutes.
[0019]
Comparative Example 2
Polyester nonwoven fabric (thickness: 1.3 mm, density: 0.27 g / cm 2 ) emulsified dispersion of methyl hydrogen polysiloxane emulsion (Matsumoto Yushi Seiyaku Co., Ltd. product: Gelanex S-3) and zinc-based compound as its catalyst (Matsumoto Yushi Seiyaku Co., Ltd. product: Catalyst TSC-450) was immersed in water at a concentration of 3% and 1% by weight, respectively, and the excess solution was squeezed with mangle and dried at 120 ° C. A pretreated non-woven fabric was prepared.
In the squeezing with mangle, the amount of the aqueous solution adhered was 130% by weight of the nonwoven fabric, that is, 130 g of the aqueous solution adhered to 100 g of the nonwoven fabric.
Next, the pretreated non-woven fabric was coated with a stock solution having the formulation shown in Table 1 with a clearance of 1.0 mm, and subjected to a heat-heat coagulation treatment for 30 minutes in an environment of saturated steam pressure at 90 ° C., and further 95 ° C. The artificial leather-like thing was obtained by performing a drying process for 120 minutes in a dry heat environment.
[0020]
Comparative Example 3
Polyester nonwoven fabric (thickness: 1.3 mm, density: 0.27 g / cm 2 ) emulsified dispersion of methyl hydrogen polysiloxane emulsion (Matsumoto Yushi Seiyaku Co., Ltd. product: Gelanex S-3) and zinc-based compound as its catalyst (Matsumoto Yushi Seiyaku Co., Ltd. product: Catalyst TSC-450) was immersed in water at a concentration of 3% and 1% by weight, respectively, and the excess solution was squeezed with mangle and dried at 120 ° C. A pretreated non-woven fabric was prepared.
In the squeezing with mangle, the amount of the aqueous solution adhered was 130% by weight of the nonwoven fabric, that is, 130 g of the aqueous solution adhered to 100 g of the nonwoven fabric.
Next, the pretreated non-woven fabric was impregnated with the stock solution of the formulation shown in Table 3, and then subjected to wet heat heating coagulation for 30 minutes in an environment of saturated steam pressure of 90 ° C., and further 120 ° A test cloth containing a polyurethane resin inside the nonwoven fabric was obtained by performing a drying treatment for a minute.
Next, a non-woven fabric containing a polyurethane resin is coated with a stock solution of the formulation shown in Table 1 with a clearance = 1.0 mm, and subjected to a wet heat heating coagulation treatment for 30 minutes in a 90 ° C. saturated water vapor pressure environment, Further, a drying process was performed for 120 minutes in a dry heat environment at 95 ° C. to obtain an artificial leather-like product.
[0021]
[Table 3]
【The invention's effect】
According to the method of the present invention, since a good porous state can be molded using an aqueous urethane resin emulsion, a continuous foam porous body suitable for artificial leather having a high thickness and a low density can be molded, and is obtained by the present invention. What is lighter and more flexible than those not according to the present invention can be obtained without using organic solvents.
Claims (3)
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| JP4532758B2 (en) * | 2001-02-20 | 2010-08-25 | 日華化学株式会社 | Method for producing porous structure |
| KR20030062176A (en) * | 2002-01-16 | 2003-07-23 | 김인기 | Manufacturing methods of fabrous polymers emulsion |
| IT1397868B1 (en) * | 2010-02-11 | 2013-02-04 | Same S R L | PROCEDURE FOR THE PRODUCTION OF COVERED POLYURETHANE COATED FABRICS. |
| JP6229918B1 (en) * | 2016-06-01 | 2017-11-15 | Dic株式会社 | Method for producing porous body |
| WO2017208681A1 (en) * | 2016-06-01 | 2017-12-07 | Dic株式会社 | Method of producing porous body |
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