JP2005113318A - Aqueous resin composition for artificial leather and artificial leather obtained by using the composition - Google Patents
Aqueous resin composition for artificial leather and artificial leather obtained by using the composition Download PDFInfo
- Publication number
- JP2005113318A JP2005113318A JP2003349397A JP2003349397A JP2005113318A JP 2005113318 A JP2005113318 A JP 2005113318A JP 2003349397 A JP2003349397 A JP 2003349397A JP 2003349397 A JP2003349397 A JP 2003349397A JP 2005113318 A JP2005113318 A JP 2005113318A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- artificial leather
- resin
- aqueous
- adhesive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Description
本発明は、有機溶剤の含有量を微量に抑え、環境に考慮した人工皮革用水性樹脂組成物に関し、更に詳しくは、スポーツ靴、衣料、家具等の用途において、耐摩耗性に優れた樹脂皮膜を形成する人工皮革用水性樹脂組成物及びそれを用いた人工皮革に関する。 The present invention relates to an aqueous resin composition for artificial leather that suppresses the organic solvent content to a very small amount and is environmentally friendly. More specifically, the present invention provides a resin film having excellent wear resistance in applications such as sports shoes, clothing, and furniture. The present invention relates to a water-based resin composition for artificial leather and an artificial leather using the same.
従来の人工皮革用樹脂組成物は、有機溶剤を用いた溶剤型のものが主流であった。この溶剤型の人工皮革用樹脂組成物を用いた場合、乾燥工程で有機溶剤が揮散し、そのほとんどが大気中に放出されるため、環境を悪化させていた。また、有機溶剤が揮散するため作業環境も良好ではなく、作業者の健康が懸念されている。さらに、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）等の沸点の高い有機溶剤を用いた場合、その一部が乾燥後も人工皮革中に残留し、その残留溶剤の人体への影響が懸念されている。この問題を解決する方法として、有機溶剤の含有量を微量に抑えた水性樹脂組成物を用いた人工皮革の開発が進められている。 Conventional resin compositions for artificial leather have been mainly solvent-type using organic solvents. When this solvent-type resin composition for artificial leather was used, the organic solvent was volatilized in the drying process, and most of it was released into the atmosphere, which deteriorated the environment. In addition, since the organic solvent is volatilized, the working environment is not good, and there is concern about the health of workers. Further, when an organic solvent having a high boiling point such as N, N-dimethylformamide (DMF) is used, a part of the organic solvent remains in the artificial leather after drying, and there is a concern about the influence of the residual solvent on the human body. . As a method for solving this problem, development of artificial leather using an aqueous resin composition in which the content of an organic solvent is suppressed to a very small amount is underway.
さらに、水性樹脂組成物を用いた人工皮革においても、スポーツ靴、衣料、家具等の用途では、高い摩耗強さ（ＪＩＳ Ｌ １０９６「一般織物試験方法」に規定されている摩耗強さのＡ法（ユニバーサル形法）のＡ−１法（平面法）で試験した場合の人工皮革の基布が見えるまでの耐摩耗性。以下、耐ストール摩耗性と略す。）が求められる。しかし、水性樹脂組成物を用いた人工皮革は、溶剤型の樹脂組成物を用いた人工皮革に比べ、耐ストール摩耗性が劣るという問題があった。これは、水性樹脂組成物を用いた人工皮革は、造膜性不良が発生しやすく樹脂皮膜が脆弱なため、摩耗時に樹脂皮膜が脱落しやすいためと考えられる。 Furthermore, even in artificial leather using an aqueous resin composition, it is used for sports shoes, clothing, furniture and the like with high wear strength (A method of wear strength defined in JIS L 1096 “General Textile Test Method”). (Abrasion resistance until the artificial leather base fabric is seen when tested by A-1 method (planar method) of (Universal Form Method), hereinafter abbreviated as stall wear resistance). However, the artificial leather using the aqueous resin composition has a problem that the stall wear resistance is inferior to the artificial leather using the solvent-type resin composition. This is presumably because the artificial leather using the aqueous resin composition is likely to cause poor film-forming properties and the resin film is fragile, so that the resin film tends to fall off during wear.
耐摩耗性を向上させた水性樹脂組成物としては、オレフィン系樹脂水分散体及び水性ポリウレタン樹脂を含有するものが提案されている。しかし、この樹脂組成物の耐ストール摩耗性は、不充分であった（例えば、特許文献１参照。）。 As an aqueous resin composition with improved wear resistance, an aqueous resin composition containing an aqueous olefin resin dispersion and an aqueous polyurethane resin has been proposed. However, the stall wear resistance of this resin composition was insufficient (see, for example, Patent Document 1).
また、造膜性及び耐摩耗性を向上させた人工皮革用水性樹脂組成物として、酸価が５〜４０であるポリウレタン樹脂で、かつ乳化剤を含有しない水性ポリウレタン樹脂分散体と架橋剤を含有する水性樹脂組成物が提案されている。この樹脂組成物では、造膜性が高く、耐摩耗性の向上は見られたが、耐ストール摩耗性は、不充分であった（例えば、特許文献２参照。）。 Further, as an aqueous resin composition for artificial leather with improved film-forming properties and abrasion resistance, it contains a polyurethane resin having an acid value of 5 to 40 and an aqueous polyurethane resin dispersion containing no emulsifier and a crosslinking agent. An aqueous resin composition has been proposed. In this resin composition, the film forming property was high and the wear resistance was improved, but the stall wear resistance was insufficient (see, for example, Patent Document 2).
本発明が解決しようとする課題は、有機溶剤の含有量を微量に抑え、環境に考慮した人工皮革用水性樹脂組成物であって、スポーツ靴、衣料、家具等の用途において、耐摩耗性に優れた樹脂皮膜を形成する人工皮革用水性樹脂組成物及びそれを用いた人工皮革を提供することである。 The problem to be solved by the present invention is a water-based resin composition for artificial leather that takes the organic solvent content to a minimum and considers the environment, and is resistant to wear in applications such as sports shoes, clothing, and furniture. An aqueous resin composition for artificial leather that forms an excellent resin film and an artificial leather using the same.
本発明者は、上記の課題を解決すべく鋭意検討した結果、以下の発明を完成するに至った。すなわち、本発明は、（Ａ）架橋型水性ウレタン樹脂、
（Ｂ）架橋剤及び
（Ｃ）有機微粒子
を含有することを特徴とする人工皮革用水性樹脂組成物を提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have completed the following invention. That is, the present invention provides (A) a cross-linked aqueous urethane resin,
The present invention provides an aqueous resin composition for artificial leather, which contains (B) a crosslinking agent and (C) organic fine particles.
本発明の人工皮革用水性樹脂組成物は、耐ストール摩耗性に優れた人工皮革の材料として有用である。また、本発明の人工皮革用水性樹脂組成物からなる人工皮革は、高い耐摩耗性を有するため、スポーツ靴、家具、車両等の用途に好適である。 The aqueous resin composition for artificial leather of the present invention is useful as a material for artificial leather having excellent stall wear resistance. In addition, the artificial leather comprising the aqueous resin composition for artificial leather of the present invention has high wear resistance and is therefore suitable for uses such as sports shoes, furniture, and vehicles.
本発明を以下に詳しく説明する。本発明で用いられる架橋型水性ウレタン樹脂（Ａ）は、本発明で用いられる架橋剤（Ｂ）と架橋することができる活性水素を有する官能基を有し、かつ水性媒体中に溶解又は分散することができる親水基を有するものであれば、特に限定なしに用いることができる。このような架橋型水性ウレタン樹脂としては、例えば、ポリカーボネート系ウレタン樹脂、ポリカーボネート／エーテル系ウレタン樹脂、ポリエーテル系ウレタン樹脂、ポリエステル系ウレタン樹脂及びこれらの変性物等が挙げられる。これらの中でも、スポーツ靴用途で柔軟性が必要な場合、ポリエーテル系ウレタン樹脂が好適である。また、家具、車両等の用途で長期耐久性が必要な場合、ポリカーボネート系ウレタン樹脂、ポリカーボネート／エーテル系ウレタン樹脂が好適である。 The present invention is described in detail below. The cross-linked aqueous urethane resin (A) used in the present invention has a functional group having active hydrogen capable of cross-linking with the cross-linking agent (B) used in the present invention, and is dissolved or dispersed in an aqueous medium. Any hydrophilic group can be used without particular limitation. Examples of such cross-linked aqueous urethane resins include polycarbonate urethane resins, polycarbonate / ether urethane resins, polyether urethane resins, polyester urethane resins, and modified products thereof. Among these, when a softness | flexibility is required for sports shoes use, a polyether-type urethane resin is suitable. Moreover, when long-term durability is required for applications such as furniture and vehicles, polycarbonate-based urethane resins and polycarbonate / ether-based urethane resins are suitable.
本発明に用いられる架橋剤（Ｂ）は、ポリイソシアネート、又はポリカルボジイミドが好ましい。また、これらの中でも、有機溶剤を含有していないものが好ましく、更には、前記架橋型水性ウレタン樹脂（Ａ）の水系分散液への分散性が良いのものが、より好ましい。 The crosslinking agent (B) used in the present invention is preferably polyisocyanate or polycarbodiimide. Among these, those not containing an organic solvent are preferable, and those having good dispersibility in the aqueous dispersion of the cross-linked aqueous urethane resin (A) are more preferable.
前記架橋剤（Ｂ）に用いられるポリイソシアネートとしては、前記架橋型水性ウレタン樹脂（Ａ）の原料として用いたイソシアネート基を有する化合物、これらのイソシアヌレート型、ビューレット型又はアロファネート型の３官能以上のポリイソシアネート、２官能以上のポリオール等の活性水素を有する化合物とイソシアネート基を有する化合物との反応により得られる末端にイソシアネート基を有するウレタンプレポリマー等の疎水性ポリイソシアネート類；これらのポリイソシアネート類に乳化剤を配合して水に分散できるようにしたもの；カルボキシル基を有する化合物、スルホン酸基を有する化合物、又は前記ノニオン性親水基を有する化合物とポリイソシアネート類とを共重合して得られる自己乳化性を有する水分散性ポリイソシアネート類；及びこれらの混合物が挙げられる。これらの中でも、脂肪族又は脂環式のポリイソシアネートからなり、かつ架橋型水性ウレタン樹脂（Ａ）の水系分散液に分散する疎水性ポリイソシアネートは、耐水性が向上するので好ましい。また、脂肪族又は脂環式のポリイソシアネートとノニオン性親水基を有する化合物とを反応して得られる水分散性ポリイソシアネートは、架橋型水性ウレタン樹脂（Ａ）の水系分散液への分散が向上するので好ましい。 As the polyisocyanate used in the crosslinking agent (B), a compound having an isocyanate group used as a raw material of the crosslinked aqueous urethane resin (A), an isocyanurate type, a biuret type or an allophanate type trifunctional or higher Polyisocyanates, hydrophobic polyisocyanates such as urethane prepolymers having isocyanate groups at the ends obtained by reaction of compounds having active hydrogen such as difunctional or higher functional polyols and compounds having isocyanate groups; these polyisocyanates Emulsifier added to water so that it can be dispersed in water; a compound obtained by copolymerizing a compound having a carboxyl group, a compound having a sulfonic acid group, or a compound having a nonionic hydrophilic group and a polyisocyanate Water dispersible polyy with emulsifying properties Cyanates; and mixtures thereof. Among these, a hydrophobic polyisocyanate which is composed of an aliphatic or alicyclic polyisocyanate and is dispersed in an aqueous dispersion of the cross-linked aqueous urethane resin (A) is preferable because water resistance is improved. In addition, the water-dispersible polyisocyanate obtained by reacting an aliphatic or alicyclic polyisocyanate with a compound having a nonionic hydrophilic group improves the dispersion of the cross-linked aqueous urethane resin (A) in an aqueous dispersion. This is preferable.
また、前記架橋剤（Ｂ）に用いられるポリカルボジイミドとしては、例えば、１種以上のイソシアネートとカルボジイミド類とを反応させて得られる疎水性ポリカルボジイミド類；カルボキシル基を有する化合物、スルホン酸基を有する化合物、又はノニオン性親水基を有する化合物とカルボジイミド類とを反応させて得られる水分散性ポリカルボジイミド類；及びこれらの混合物が挙げられる。これらの中でも、ジシクロヘキシルメタンジイソシアネート又はテトラメチルキシリレンジイソシアネートとカルボジイミド類とを反応させて得られ、かつ架橋型水性ウレタン樹脂（Ａ）の水系分散液に分散する疎水性ポリカルボジイミドは、耐水性が向上するので好ましい。更に、ジシクロヘキシルメタンジイソシアネート又はテトラメチルキシリレンジイソシアネートと前記ノニオン性親水基を有する化合物及びカルボジイミド類とを反応させて得られる水分散性ポリカルボジイミドは、架橋型水性ウレタン樹脂（Ａ）の水系分散液への分散性が向上するので好ましい。 Examples of the polycarbodiimide used in the crosslinking agent (B) include hydrophobic polycarbodiimides obtained by reacting one or more isocyanates with carbodiimides; compounds having a carboxyl group, and sulfonic acid groups. And water-dispersible polycarbodiimides obtained by reacting a compound or a compound having a nonionic hydrophilic group with carbodiimides; and mixtures thereof. Among these, hydrophobic polycarbodiimide obtained by reacting dicyclohexylmethane diisocyanate or tetramethylxylylene diisocyanate with carbodiimides and dispersed in an aqueous dispersion of the crosslinked aqueous urethane resin (A) has improved water resistance. This is preferable. Furthermore, the water-dispersible polycarbodiimide obtained by reacting dicyclohexylmethane diisocyanate or tetramethylxylylene diisocyanate with the nonionic hydrophilic group-containing compound and carbodiimide is converted into an aqueous dispersion of the crosslinked aqueous urethane resin (A). This is preferable because the dispersibility of the resin is improved.
前記ポリイソシアネート、及び前記ポリカルボジイミドは、単独で用いることも、２種類以上を併用することもできる。 The polyisocyanate and the polycarbodiimide can be used alone or in combination of two or more.
本発明の人工皮革用水性樹脂組成物を表皮層に用いた場合、前記架橋剤（Ｂ）を添加することによって、耐水性及び耐摩耗性が付与できる。また、本発明の人工皮革用水性樹脂組成物を接着層に用いた場合、前記架橋剤（Ｂ）を添加することによって、基布と表皮層との間の初期接着性及び接着耐久性が付与できる。 When the aqueous resin composition for artificial leather of the present invention is used for the skin layer, water resistance and abrasion resistance can be imparted by adding the crosslinking agent (B). Moreover, when the aqueous resin composition for artificial leather of the present invention is used for an adhesive layer, the addition of the cross-linking agent (B) provides initial adhesion and adhesion durability between the base fabric and the skin layer. it can.
本発明の人工皮革用水性樹脂組成物を塗工する際に、各種塗工方法に応じた粘度調整が必要な場合には、増粘剤を添加しても構わない。このような増粘剤は、架橋型水性ウレタン樹脂（Ａ）に相溶する増粘剤であれば特に限定されないが、例えば、ヒドロキシエチルセルロース（ＨＥＣ）、メチルセルロース（ＭＣ）、カルボキシメチルセルロース（ＣＭＣ）等のセルロース誘導体；ポリアクリル酸塩、ポリビニルピロリドン（ＰＶＰ）、ウレタン系又はポリエーテル系等の会合型高分子界面活性剤等が挙げられる。 When applying the aqueous resin composition for artificial leather of the present invention, a thickener may be added when viscosity adjustment according to various coating methods is required. Such a thickener is not particularly limited as long as it is compatible with the cross-linked aqueous urethane resin (A). For example, hydroxyethyl cellulose (HEC), methyl cellulose (MC), carboxymethyl cellulose (CMC) and the like. Cellulose derivatives: Polyacrylate, polyvinyl pyrrolidone (PVP), urethane type or polyether type associative polymer surfactants and the like.
これらの中でも、会合型高分子界面活性剤は、架橋型水性ウレタン樹脂（Ａ）との相溶性が良く、高剪断から低剪断力下の広範囲で比較的一定の粘度、すなわちニュートン流動性の粘性特性を付与できるで好ましい。更に、会合型高分子界面活性剤は、樹脂組成物を基材へ塗工する際のレベリング性、膜厚調整等のハンドリング性の点で優れている。これらの増粘剤は、単独で用いても２種以上併用しても構わない。 Among these, the associative polymer surfactant has good compatibility with the cross-linked aqueous urethane resin (A) and has a relatively constant viscosity in a wide range from high shear to low shear force, that is, Newtonian fluid viscosity. It is preferable because it can impart characteristics. Furthermore, the associative polymer surfactant is excellent in terms of leveling properties when the resin composition is applied to a substrate, and handling properties such as film thickness adjustment. These thickeners may be used alone or in combination of two or more.
本発明の人工皮革用水性樹脂組成物は、有機微粒子（Ｃ）を添加することによって、得られる人工皮革の耐ストール摩耗性が向上する。 In the aqueous resin composition for artificial leather of the present invention, the stall wear resistance of the resulting artificial leather is improved by adding the organic fine particles (C).
前記有機微粒子（Ｃ）の平均粒子径は、０．５〜５０μｍの範囲が好ましく、１〜３０μｍの範囲が特に好ましく、５〜２０μｍの範囲が更に好ましい。有機微粒子の平均粒子径がこの範囲にあれば、耐ストール摩耗性が良好となる。 The average particle diameter of the organic fine particles (C) is preferably in the range of 0.5 to 50 μm, particularly preferably in the range of 1 to 30 μm, and further preferably in the range of 5 to 20 μm. When the average particle diameter of the organic fine particles is within this range, the stall wear resistance is good.
また、前記有機微粒子（Ｃ）の荷重１０ｍＮにおけるユニバーサル硬さは、０．０５〜５Ｎ／ｍｍ２の範囲が好ましく、０．１〜３Ｎ／ｍｍ２の範囲が特に好ましい。有機微粒子の荷重１０ｍＮにおけるユニバーサル硬さがこの範囲にあれば、耐ストール摩耗性が良好となる。 In addition, the universal hardness at a load 10mN organic fine particles (C) is preferably in the range of 0.05~5N / mm 2, the range of 0.1~3N / mm 2 is particularly preferred. If the universal hardness of organic fine particles at a load of 10 mN is within this range, the stall wear resistance will be good.
前記有機微粒子（Ｃ）を構成する樹脂としては、例えば、ベンゾグアナミン樹脂、メラミン樹脂、ベンゾグアナミン−メラミン樹脂、シリコーン樹脂、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン樹脂、ポリオレフィン樹脂、エチレン−アクリル共重合体、ポリスチレン、架橋ポリスチレン、ポリジビニルベンゼン、スチレン−ジビニルベンゼン共重合体、アクリル共重合体、架橋アクリル樹脂、ポリメチルメタクリレート、塩化ビニリデン樹脂、フッ素樹脂、ナイロン、フェノール樹脂、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂等が挙げられる。これらの樹脂の製造方法は、特にこだわらないが、例えば、乳化重合、縣濁重合、乳化分散、分散重合、Ｗ／Ｏマイクロエマルション重合、上記樹脂フィルムを粉砕し、微粒子化したもの等が挙げられ、必要に応じて粉砕等の後処理を施しても構わない。また、これらの樹脂は、ハロゲン基、エポキシ基、アミノ基、水酸基、チオール基、アミド基、カルボキシル基、リン酸基、スルホン酸基等の官能基を有していても構わない。 Examples of the resin constituting the organic fine particles (C) include benzoguanamine resin, melamine resin, benzoguanamine-melamine resin, silicone resin, low density polyethylene, high density polyethylene, polypropylene resin, polyolefin resin, ethylene-acrylic copolymer, Polystyrene, crosslinked polystyrene, polydivinylbenzene, styrene-divinylbenzene copolymer, acrylic copolymer, crosslinked acrylic resin, polymethyl methacrylate, vinylidene chloride resin, fluororesin, nylon, phenol resin, epoxy resin, urethane resin, polyimide resin Etc. The production method of these resins is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, emulsion dispersion, dispersion polymerization, W / O microemulsion polymerization, pulverized resin particles, and the like. If necessary, post-treatment such as pulverization may be performed. Further, these resins may have a functional group such as a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group.
本発明に用いる前記有機微粒子（Ｃ）としては、例えば、フッ素樹脂パウダー、ウレタン樹脂パウダー、ポリエチレン樹脂パウダー、アクリル樹脂パウダー、シリコーン樹脂パウダーが、耐ストール摩耗性が向上するので好ましい。これらの有機微粒子は、単独で用いることも、２種類以上を併用することもできる。 As the organic fine particles (C) used in the present invention, for example, fluororesin powder, urethane resin powder, polyethylene resin powder, acrylic resin powder, and silicone resin powder are preferable because the stall wear resistance is improved. These organic fine particles can be used alone or in combination of two or more.
本発明で用いられる有機微粒子（Ｃ）の配合量は、架橋型ウレタン樹脂（Ａ）１００質量部に対して、１〜５０質量部の範囲が好ましく、３〜３０質量部の範囲が特に好ましい。有機微粒子の配合量がこの範囲にあれば、人工皮革の耐ストール摩耗性が充分になり、さらに、本発明の人工皮革用水性樹脂組成物を接着層に用いた場合、接着層と基布との接着強度が充分なものとなる。 The compounding amount of the organic fine particles (C) used in the present invention is preferably in the range of 1 to 50 parts by mass, particularly preferably in the range of 3 to 30 parts by mass with respect to 100 parts by mass of the cross-linked urethane resin (A). If the blending amount of the organic fine particles is within this range, the artificial leather has sufficient stall wear resistance. Further, when the aqueous resin composition for artificial leather of the present invention is used for the adhesive layer, the adhesive layer and the base fabric Adhesive strength is sufficient.
本発明の人工皮革用水性樹脂組成物の溶媒として用いられる水の配合量は、樹脂組成物の固形分濃度が５〜６０質量％となる範囲が好ましい。 The amount of water used as the solvent for the aqueous resin composition for artificial leather of the present invention is preferably in the range where the solid content concentration of the resin composition is 5 to 60% by mass.
本発明の人工皮革用水性樹脂組成物には、本発明の趣旨を損なわない範囲で、架橋促進剤、有機顔料等の着色剤、難燃剤、酸化防止剤等の各種添加剤、架橋型ウレタン樹脂以外の樹脂等を加えることができる。 The aqueous resin composition for artificial leather of the present invention includes various additives such as a crosslinking accelerator, a colorant such as an organic pigment, a flame retardant, and an antioxidant, and a crosslinked urethane resin, as long as the gist of the present invention is not impaired. Other resins can be added.
本発明の人工皮革用水性樹脂組成物を用いた人工皮革は、公知の乾式成膜法によって製造することができる。また、成膜した塗膜と基布との貼り合わせは、接着層を乾燥させないで貼り合わせるウェットラミネート法では、乾燥不良、接着強度不良等のトラブルが発生しやすいため、接着層を一旦乾燥させた後に繊維基材と貼り合わせるドライラミネート法がより好ましい。ドライラミネート法による人工皮革の作製方法としては、例えば、以下の方法が挙げられる。 Artificial leather using the aqueous resin composition for artificial leather of the present invention can be produced by a known dry film forming method. In addition, the wet laminating method in which the coating film and the base fabric are laminated without drying the adhesive layer is likely to cause problems such as poor drying and poor adhesive strength. After that, a dry laminating method of bonding to a fiber base material is more preferable. Examples of the method for producing artificial leather by the dry laminating method include the following methods.
離型紙上に表皮層用樹脂組成物をドクターナイフで塗布し、乾燥させる。次に、その表皮層乾燥塗膜上に接着層用樹脂組成物をドクターナイフで塗布し、予備乾燥させる。更に基布と貼り合わせた後、乾燥させる。その後、エージングし、離型紙を剥がすことにより、人工皮革が得られる。 The resin composition for the skin layer is applied onto the release paper with a doctor knife and dried. Next, the adhesive layer resin composition is applied onto the dried skin layer coating film with a doctor knife and preliminarily dried. Furthermore, it is made to dry after bonding with a base fabric. Thereafter, the artificial leather is obtained by aging and removing the release paper.
前記基布としては、例えば、綿、麻等の天然繊維；レーヨン、スフ、アセテート等の再生繊維；ポリエステル、ポリアミド、ポリアクリルニトリル等の合成繊維等の単独又は各種混紡繊維を編成、繊成あるいは交絡させた編布、織り布、不織布等が用いられる。 Examples of the base fabric include natural fibers such as cotton and linen; regenerated fibers such as rayon, sufu and acetate; and knitted, synthetic or synthetic fibers such as synthetic fibers such as polyester, polyamide and polyacrylonitrile. Entangled knitted fabric, woven fabric, non-woven fabric, etc. are used.
また、本発明の人工皮革用水性樹脂組成物を用いた人工皮革において、高い耐摩耗性が要求される車両用途や色の深みが要求される用途等には、耐摩耗性や色の深みを向上させるため、表皮層と接着層との間に中間層を更に設けても構わない。この中間層用の樹脂組成物には、架橋型水性ウレタン樹脂を用いることができる。更に、中間層用樹脂組成物にも、本発明で用いられる有機微粒子（Ｃ）を添加すると、より耐ストール摩耗性が向上することができ好ましい。 In addition, in the artificial leather using the aqueous resin composition for artificial leather of the present invention, the wear resistance and the color depth are required for a vehicle application that requires high wear resistance or a color depth requirement. In order to improve, an intermediate layer may be further provided between the skin layer and the adhesive layer. A crosslinked water-based urethane resin can be used for the resin composition for the intermediate layer. Furthermore, it is preferable to add the organic fine particles (C) used in the present invention to the intermediate layer resin composition because the stall wear resistance can be further improved.
以下に実施例及び比較例を挙げて、本発明を更に具体的に説明するが、本発明はこれらの実施例の範囲に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples.
実施例及び比較例に用いた樹脂組成物は、以下の通り調製した。
（実施例１）
＜表皮層用樹脂組成物＞
ポリカーボネート系無黄変ウレタン樹脂（大日本インキ化学工業株式会社製の製品名「ハイドランＷＬＳ−２１０」、架橋型水性ウレタン樹脂、樹脂分：３５％）１００質量部、架橋剤（大日本インキ化学工業株式会社製の製品名「ハイドランアシスターＣ１」、水分散性ポリイソシアネート系架橋剤）４質量部、増粘剤（大日本インキ化学工業株式会社製の製品名「ハイドランアシスターＴ１」、会合型増粘剤）０．５質量部、着色剤（大日本インキ化学工業株式会社製の製品名「ダイラックホワイトＨＳ−７２１０」、顔料分：６０％）、フッ素樹脂パウダー（株式会社喜多村製の製品名「ＫＴＬ−８Ｎ」、平均粒子径：５μｍ）をホモミキサーで混合し、表皮層用樹脂組成物を得た。
＜接着層用樹脂組成物＞
ポリカーボネート系無黄変ウレタン樹脂（大日本インキ化学工業株式会社製の製品名「ハイドランＷＬＡ−３１１」、架橋型水性ウレタン樹脂、樹脂分：４５％）１００質量部、架橋剤（大日本インキ化学工業株式会社製の製品名「ハイドランアシスターＣ１」、水分散性ポリイソシアネート系架橋剤）４質量部、増粘剤（大日本インキ化学工業株式会社製の製品名「ハイドランアシスターＴ１」、会合型増粘剤）０．５質量部、着色剤（大日本インキ化学工業株式会社製の製品名「ダイラックホワイトＨＳ−７２１０」、顔料分：６０％）をホモミキサーで混合し、接着層用樹脂組成物を得た。
The resin compositions used in Examples and Comparative Examples were prepared as follows.
(Example 1)
<Resin composition for skin layer>
Polycarbonate-based non-yellowing urethane resin (product name “Hydran WLS-210” manufactured by Dainippon Ink and Chemicals, Ltd., cross-linked aqueous urethane resin, resin content: 35%), 100 parts by mass, cross-linking agent (Dainippon Ink and Chemicals, Inc.) Product name "Hydran Assister C1", 4 parts by mass of water-dispersible polyisocyanate crosslinking agent, thickener (Product name "Hydran Assister T1" manufactured by Dainippon Ink & Chemicals, Inc.) Thickener) 0.5 parts by weight, colorant (Dailac Ink Chemicals, Inc., product name “Dilack White HS-7210”, pigment content: 60%), fluororesin powder (product of Kitamura Co., Ltd.) The name “KTL-8N”, average particle size: 5 μm) was mixed with a homomixer to obtain a resin composition for the skin layer.
<Resin composition for adhesive layer>
Polycarbonate-based non-yellowing urethane resin (product name “Hydran WLA-311” manufactured by Dainippon Ink and Chemicals, Ltd., cross-linked aqueous urethane resin, resin content: 45%) 100 parts by mass, cross-linking agent (Dainippon Ink and Chemicals, Inc.) Product name "Hydran Assister C1", 4 parts by mass of water-dispersible polyisocyanate crosslinking agent, thickener (Product name "Hydran Assister T1" manufactured by Dainippon Ink & Chemicals, Inc.) Thickener) 0.5 parts by mass, colorant (Dailac Ink Chemical Co., Ltd. product name “Dilak White HS-7210”, pigment content: 60%) is mixed with a homomixer, and resin for adhesive layer A composition was obtained.
（実施例２）
＜表皮層用樹脂組成物＞
実施例１の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例１の接着層用樹脂組成物中にフッ素樹脂パウダー（株式会社喜多村製の製品名「ＫＴＬ−８Ｎ」、平均粒子径：５μｍ）を５質量部加え、ホモミキサーで混合し、接着層用樹脂組成物を得た。
(Example 2)
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 1 was used.
<Resin composition for adhesive layer>
5 parts by mass of fluororesin powder (product name “KTL-8N” manufactured by Kitamura Co., Ltd., average particle size: 5 μm) is added to the resin composition for the adhesive layer of Example 1, and the mixture is mixed with a homomixer. A resin composition was obtained.
（実施例３）
＜表皮層用樹脂組成物＞
実施例１の表皮層用樹脂組成物中のフッ素樹脂パウダーを配合しなかったものを用いた。
＜接着層用樹脂組成物＞
実施例２の接着層用樹脂組成物と同一のものを用いた。
(Example 3)
<Resin composition for skin layer>
What did not mix | blend the fluororesin powder in the resin composition for skin layers of Example 1 was used.
<Resin composition for adhesive layer>
The same resin composition for the adhesive layer of Example 2 was used.
（実施例４）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例３の接着層用樹脂組成物中のフッ素樹脂パウダーの配合量を５質量部から１０質量部として、同様にホモミキサーで混合し、接着層用樹脂組成物を得た。
Example 4
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 3 was used.
<Resin composition for adhesive layer>
The blending amount of the fluororesin powder in the adhesive layer resin composition of Example 3 was changed from 5 parts by mass to 10 parts by mass, and was similarly mixed with a homomixer to obtain an adhesive layer resin composition.
（実施例５）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例３の接着層用樹脂組成物中のフッ素樹脂パウダーに代え、アクリル樹脂パウダー（ガンツ化成株式会社製の製品名「ガンツパールＧＢ−１０Ｓ」、平均粒子径：１０μｍ）を用いて、同様にホモミキサーで混合し、接着層用樹脂組成物を得た。
(Example 5)
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 3 was used.
<Resin composition for adhesive layer>
In place of the fluororesin powder in the resin composition for the adhesive layer of Example 3, acrylic resin powder (product name “Gantz Pearl GB-10S” manufactured by Ganz Kasei Co., Ltd., average particle size: 10 μm) was used in the same manner. It mixed with the homomixer and the resin composition for contact bonding layers was obtained.
（実施例６）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例３の接着層用樹脂組成物中のフッ素樹脂パウダーに代え、ウレタン樹脂パウダー（大日本インキ化学工業株式会社製の製品名「バーノックＣＦＢ−１００」、平均粒子径：１０μｍ）を用いて、同様にホモミキサーで混合し、接着層用樹脂組成物を得た。
(Example 6)
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 3 was used.
<Resin composition for adhesive layer>
Instead of the fluororesin powder in the adhesive layer resin composition of Example 3, urethane resin powder (product name “Bernock CFB-100” manufactured by Dainippon Ink & Chemicals, Inc., average particle size: 10 μm) was used. Similarly, it mixed with the homomixer and obtained the resin composition for contact bonding layers.
（実施例７）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例３の接着層用樹脂組成物中のフッ素樹脂パウダーに代え、ポリエチレン樹脂パウダー（住友精化株式会社製の製品名「フローセンＣＬ−２０８０」、平均粒子径：１５μｍ）を用いて、同様にホモミキサーで混合し、接着層用樹脂組成物を得た。
(Example 7)
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 3 was used.
<Resin composition for adhesive layer>
In place of the fluororesin powder in the resin composition for the adhesive layer of Example 3, polyethylene resin powder (product name “Flowsen CL-2080” manufactured by Sumitomo Seika Co., Ltd., average particle size: 15 μm) was used in the same manner. It mixed with the homomixer and the resin composition for contact bonding layers was obtained.
（実施例８）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例３の接着層用樹脂組成物中のフッ素樹脂パウダーに代え、シリコーン樹脂パウダー（ＧＥ東芝シリコーン株式会社製の製品名「トスパール１４５」、平均粒子径：４．５μｍ）を用いて、同様にホモミキサーで混合し、接着層用樹脂組成物を得た。
(Example 8)
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 3 was used.
<Resin composition for adhesive layer>
In place of the fluororesin powder in the resin composition for the adhesive layer of Example 3, silicone resin powder (product name “Tospearl 145” manufactured by GE Toshiba Silicone Co., Ltd., average particle diameter: 4.5 μm) was used in the same manner. It mixed with the homomixer and the resin composition for contact bonding layers was obtained.
（比較例１）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例１の接着層用樹脂組成物と同一のものを用いた。
(Comparative Example 1)
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 3 was used.
<Resin composition for adhesive layer>
The same resin composition for the adhesive layer of Example 1 was used.
（比較例２）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層用樹脂組成物＞
実施例２の接着層用樹脂組成物中のフッ素樹脂パウダーに代え、無機微粒子（キララ株式会社製の製品名「Ｙ５０００Ｍ」、白雲母、平均粒子径：７．５μｍ）を用いて、同様にホモミキサーで混合し、接着層用樹脂組成物を得た。
(Comparative Example 2)
<Resin composition for skin layer>
The same resin composition for the skin layer of Example 3 was used.
<Resin composition for adhesive layer>
In place of the fluororesin powder in the resin composition for the adhesive layer of Example 2, inorganic fine particles (product name “Y5000M” manufactured by Kirara Co., Ltd., muscovite, average particle size: 7.5 μm) are used in the same manner. It mixed with the mixer and the resin composition for contact bonding layers was obtained.
（比較例３）
＜表皮層用樹脂組成物＞
実施例３の表皮層用樹脂組成物に無機微粒子（キララ株式会社製の製品名「Ｙ５０００Ｍ」、白雲母、平均粒子径：７．５μｍ）を５質量部配合したものを用いた。
＜接着層用樹脂組成物＞
実施例１の接着層用樹脂組成物と同一のものを用いた。
(Comparative Example 3)
<Resin composition for skin layer>
The resin composition for skin layer of Example 3 was blended with 5 parts by mass of inorganic fine particles (product name “Y5000M” manufactured by Kirara Co., Ltd., muscovite, average particle diameter: 7.5 μm).
<Resin composition for adhesive layer>
The same resin composition for the adhesive layer of Example 1 was used.
（比較例４）
＜表皮層用樹脂組成物＞
比較例３の表皮層用樹脂組成物と同一のものを用いた。
＜接着層樹脂組成物＞
比較例２の接着層用樹脂組成物と同一のものを用いた。
(Comparative Example 4)
<Resin composition for skin layer>
The same resin composition for the skin layer of Comparative Example 3 was used.
<Adhesive layer resin composition>
The same adhesive layer resin composition as that of Comparative Example 2 was used.
（評価用人工皮革の作製）
上記で得られた樹脂組成物を用いて、以下の乾式成膜法によって評価用人工皮革を作製した。
(Production of artificial leather for evaluation)
Using the resin composition obtained above, an artificial leather for evaluation was produced by the following dry film forming method.
離型紙（大日本印刷株式会社製の製品名「ＤＮ−ＴＰ−ＡＰＷＤＥ−７」）上に表皮層用樹脂組成物を厚み８０μｍ（乾燥時膜厚約３０μｍ）になるようにドクターナイフで塗布した後、直ちに乾燥機（ワーナーマチス）で７０℃で１分予備乾燥し、その後１２０℃で２分乾燥を行った。次に、その上に接着層用樹脂組成物を厚み１１０μｍ（乾燥時膜厚約５０μｍ）になるようにドクターナイフで塗布した後、直ちに乾燥機（ワーナーマチス）で７０℃で１分乾燥を行い、乾燥直後にポリアミド系繊維よりなる不織布との貼り合わせ（ドライラミネート）を行った。その後、１２０℃で２分間キュアリングを行い、さらに４０℃で２日間エージングを行い、作製した人工皮革を離型紙から剥離した。 The release layer (Dai Nippon Printing Co., Ltd. product name “DN-TP-APWDE-7”) was coated with a doctor knife so that the thickness of the resin composition for the skin layer was 80 μm (the film thickness was about 30 μm when dried). After that, it was immediately preliminarily dried at 70 ° C. for 1 minute with a dryer (Warner Mathis), and then dried at 120 ° C. for 2 minutes. Next, the resin composition for the adhesive layer is applied thereon with a doctor knife so that the thickness becomes 110 μm (the film thickness when dried is about 50 μm), and then immediately dried at 70 ° C. for 1 minute with a dryer (Warner Mathis). Immediately after drying, bonding (dry lamination) with a nonwoven fabric made of polyamide fiber was performed. Thereafter, curing was performed at 120 ° C. for 2 minutes, and further aging was performed at 40 ° C. for 2 days, and the produced artificial leather was peeled from the release paper.
実施例及び比較例で調製した樹脂組成物を用いた人工皮革の評価は、以下の方法によって行った。なお、実施例の評価結果は、表１及び２に、比較例の評価結果は、表３に示す。 Evaluation of artificial leather using the resin compositions prepared in Examples and Comparative Examples was performed by the following method. The evaluation results of the examples are shown in Tables 1 and 2, and the evaluation results of the comparative examples are shown in Table 3.
１）微粒子のユニバーサル硬さ
表面被膜物性試験機（フィッシャー・インストルメンツ株式会社製の製品名「フィッシャースコープＨ１００Ｃ」、直径５０μｍの平面圧子を使用）を用いて、各微粒子の１０ｍＮ加重時のユニバーサル硬さを測定した。
1) Universal hardness of fine particles Using a surface coating property tester (product name “Fischer Scope H100C” manufactured by Fischer Instruments Co., Ltd., using a flat indenter with a diameter of 50 μm), universal hardness of each fine particle at 10 mN load. Was measured.
２）耐ストール摩耗性
得られた評価用人工皮革の耐ストール摩耗性試験を、ＪＩＳ Ｌ １０９６「一般織物試験方法」の摩耗強さ（Ａ法（ユニバーサル形法）のＡ−１法（平面法））に準拠して、カストム式織物摩耗試験機（大栄科学精器製作所製の装置名「ＣＡＴ−１２５型」）で行い、表皮層及び接着層が摩耗して、１ｃｍ２の面積の基布が露出するまでの摩擦回数から、以下の基準で評価した。
○：１４００回以上、×：１４００回未満、
2) Stall wear resistance Stall wear resistance test of the obtained artificial leather for evaluation was conducted using the A-1 method (planar method) of the wear strength (Method A (Universal Form Method) of JIS L 1096 "General Textile Test Method". )) in compliance with, performed in Kasutomu formula fabric abrasion tester (Daiei Kagaku Seiki Seisakusho device name "CAT-125 model"), and wear skin layer and the adhesive layer, the base fabric of the area of 1 cm 2 From the number of frictions until the exposure, the following criteria were evaluated.
○: 1400 times or more, ×: less than 1400 times,
実施例１〜８で得た本発明の樹脂組成物で作製した本発明の人工皮革は、充分な耐ストール摩耗性を有することが分かった。 It turned out that the artificial leather of this invention produced with the resin composition of this invention obtained in Examples 1-8 has sufficient stall abrasion resistance.
比較例１は、表皮層及び接着層に有機微粒子を添加しなかった例である。この人工皮革では、耐ストール摩耗性が不充分であった。 Comparative Example 1 is an example in which organic fine particles were not added to the skin layer and the adhesive layer. This artificial leather has insufficient stall wear resistance.
比較例２は、接着層に無機微粒子を添加した例である。この人工皮革では、耐ストール摩耗性が不充分であった。 Comparative Example 2 is an example in which inorganic fine particles are added to the adhesive layer. This artificial leather has insufficient stall wear resistance.
比較例３は、表皮層に無機微粒子を添加した例である。この人工皮革では、耐ストール摩耗性が不充分であった。 Comparative Example 3 is an example in which inorganic fine particles are added to the skin layer. This artificial leather has insufficient stall wear resistance.
比較例４は、表皮層及び接着層に無機微粒子を添加した例である。この人工皮革では、耐ストール摩耗性が不充分であった。
Comparative Example 4 is an example in which inorganic fine particles are added to the skin layer and the adhesive layer. This artificial leather has insufficient stall wear resistance.
Claims (6)
（Ｂ）架橋剤及び
（Ｃ）有機微粒子
を含有することを特徴とする人工皮革用水性樹脂組成物。 (A) Crosslinkable water-based urethane resin,
An aqueous resin composition for artificial leather comprising (B) a crosslinking agent and (C) organic fine particles.
In the artificial leather having an adhesive layer, an intermediate layer and a skin layer on a base fabric, at least one of the adhesive layer, the intermediate layer and the skin layer is made of the resin composition according to any one of claims 1 to 4. Artificial leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003349397A JP2005113318A (en) | 2003-10-08 | 2003-10-08 | Aqueous resin composition for artificial leather and artificial leather obtained by using the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003349397A JP2005113318A (en) | 2003-10-08 | 2003-10-08 | Aqueous resin composition for artificial leather and artificial leather obtained by using the composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005113318A true JP2005113318A (en) | 2005-04-28 |
Family
ID=34541274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003349397A Pending JP2005113318A (en) | 2003-10-08 | 2003-10-08 | Aqueous resin composition for artificial leather and artificial leather obtained by using the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005113318A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006322113A (en) * | 2005-05-20 | 2006-11-30 | Achilles Corp | Synthetic leather having excellent abrasion resistance |
| JP2007138326A (en) * | 2005-11-17 | 2007-06-07 | Okamoto Ind Inc | Synthetic leather |
| JP2007191820A (en) * | 2006-01-18 | 2007-08-02 | Komatsu Seiren Co Ltd | Stain-proof synthetic leather |
| JP2008308785A (en) * | 2007-06-14 | 2008-12-25 | Komatsu Seiren Co Ltd | Synthetic leather and method for producing the same |
| WO2010004951A1 (en) | 2008-07-11 | 2010-01-14 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, manufacturing method for same, and paint composition containing same |
| US8552109B2 (en) | 2008-05-29 | 2013-10-08 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same |
| JP2014080713A (en) * | 2012-09-27 | 2014-05-08 | Seiren Co Ltd | Synthetic leather and method for manufacturing the same |
| US8841381B2 (en) | 2009-08-20 | 2014-09-23 | Ube Industries Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8859676B2 (en) | 2009-02-26 | 2014-10-14 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8912280B2 (en) | 2009-02-26 | 2014-12-16 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| WO2015142340A1 (en) * | 2014-03-20 | 2015-09-24 | Honeywell International Inc. | Textile articles including a polymeric layer and methods of forming the same |
| KR101774135B1 (en) * | 2016-01-04 | 2017-09-01 | 엘지전자 주식회사 | Refrigerator |
| JP2019533772A (en) * | 2016-10-27 | 2019-11-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Fabric having a cut resistant coating comprising para-aramid particles |
| EP4083313A4 (en) * | 2019-12-25 | 2024-05-15 | Kuraray Co., Ltd. | Leather-like sheet |
-
2003
- 2003-10-08 JP JP2003349397A patent/JP2005113318A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006322113A (en) * | 2005-05-20 | 2006-11-30 | Achilles Corp | Synthetic leather having excellent abrasion resistance |
| JP4634219B2 (en) * | 2005-05-20 | 2011-02-16 | アキレス株式会社 | Synthetic leather with excellent wear resistance |
| JP2007138326A (en) * | 2005-11-17 | 2007-06-07 | Okamoto Ind Inc | Synthetic leather |
| JP4727394B2 (en) * | 2005-11-17 | 2011-07-20 | オカモト株式会社 | Synthetic leather |
| JP2007191820A (en) * | 2006-01-18 | 2007-08-02 | Komatsu Seiren Co Ltd | Stain-proof synthetic leather |
| JP4726636B2 (en) * | 2006-01-18 | 2011-07-20 | 小松精練株式会社 | Antifouling synthetic leather |
| JP2008308785A (en) * | 2007-06-14 | 2008-12-25 | Komatsu Seiren Co Ltd | Synthetic leather and method for producing the same |
| US8552109B2 (en) | 2008-05-29 | 2013-10-08 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same |
| WO2010004951A1 (en) | 2008-07-11 | 2010-01-14 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, manufacturing method for same, and paint composition containing same |
| US8859676B2 (en) | 2009-02-26 | 2014-10-14 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8912280B2 (en) | 2009-02-26 | 2014-12-16 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8841381B2 (en) | 2009-08-20 | 2014-09-23 | Ube Industries Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| JP2014080713A (en) * | 2012-09-27 | 2014-05-08 | Seiren Co Ltd | Synthetic leather and method for manufacturing the same |
| WO2015142340A1 (en) * | 2014-03-20 | 2015-09-24 | Honeywell International Inc. | Textile articles including a polymeric layer and methods of forming the same |
| KR101774135B1 (en) * | 2016-01-04 | 2017-09-01 | 엘지전자 주식회사 | Refrigerator |
| JP2019533772A (en) * | 2016-10-27 | 2019-11-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Fabric having a cut resistant coating comprising para-aramid particles |
| JP7109716B2 (en) | 2016-10-27 | 2022-08-01 | デュポン セイフティー アンド コンストラクション インコーポレイテッド | Fabric with a cut-resistant coating containing para-aramid particles |
| EP4083313A4 (en) * | 2019-12-25 | 2024-05-15 | Kuraray Co., Ltd. | Leather-like sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2005113318A (en) | Aqueous resin composition for artificial leather and artificial leather obtained by using the composition | |
| KR100822641B1 (en) | Textile coating method with water urethane emulsion | |
| CN106029976B (en) | Tablet and its manufacturing method | |
| US6660667B2 (en) | Fabric coating containing energy absorbing phase change material and method of manufacturing same | |
| JP4918481B2 (en) | Fiber fabric and fiber processing method | |
| EP0293482A1 (en) | Gas-permeable and waterproof nonwoven fabric and process for its production | |
| JP5070262B2 (en) | Method for producing leather material and leather material | |
| EP1405947A1 (en) | POROUS SHEET&comma; FIBER COMPOSITE SHEET&comma; AND PROCESSES FOR PRODUCING THESE | |
| TWI833903B (en) | Urethane resin aqueous dispersion, leather sheet, and method for manufacturing leather sheet | |
| JP2010255132A (en) | Moisture-permeable and water-proof fabric and process for production of same | |
| EP0454391A2 (en) | Film-forming copolymers and their use in water vapour permeable coatings | |
| TW201414901A (en) | Suede-type coated fabric and method of manufacturing the same | |
| KR102326355B1 (en) | Method for producing leather material | |
| JP6061561B2 (en) | Sheet material and article | |
| JP4403684B2 (en) | Aqueous dry laminate adhesive composition for synthetic leather and method for producing synthetic leather using the same | |
| JP4563041B2 (en) | Porous structure manufacturing method, porous structure and leather-like structure | |
| JP2006036960A (en) | Method for producing leather material and leather material therefrom | |
| JP2000248472A (en) | Abrasion-resistant leather-like sheet | |
| JP2003119677A (en) | Aqueous resin composition for forming skin layer of fiber laminate and artificial leather using the same | |
| JP2688779B2 (en) | Synthetic leather | |
| JP2809804B2 (en) | Leather-like sheet | |
| EP3819341B1 (en) | Urethane resin composition and layered product | |
| JP2006307414A (en) | Synthetic leather and method for producing the same | |
| JP2020075479A (en) | PET synthetic paper | |
| JP2005220499A (en) | Resin composition for artificial leather and the artificial leather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20050825 |
|
| A621 | Written request for application examination |
Effective date: 20061003 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090601 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20090604 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Effective date: 20090731 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090910 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091109 |
|
| A02 | Decision of refusal |
Effective date: 20100121 Free format text: JAPANESE INTERMEDIATE CODE: A02 |