JP2004036011A - Sueded fibrous structure having excellent flameproofness - Google Patents
Sueded fibrous structure having excellent flameproofness Download PDFInfo
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- JP2004036011A JP2004036011A JP2002191762A JP2002191762A JP2004036011A JP 2004036011 A JP2004036011 A JP 2004036011A JP 2002191762 A JP2002191762 A JP 2002191762A JP 2002191762 A JP2002191762 A JP 2002191762A JP 2004036011 A JP2004036011 A JP 2004036011A
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- Prior art keywords
- suede
- resin composition
- sueded
- fibrous structure
- fiber structure
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- 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.)
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、その表面に立毛部を有し、柔軟で防炎性に優れたスエード状繊維構造物に関するものである。
【0002】
【従来の技術】
ホテル、旅館、学校、病院等公共の建物に使用されるカーテン、敷物、合板類は消防法により防炎物品対象物として防炎規制を受けている。また、寝具類、布張家具、防災頭巾は防炎製品として認定されることが必要である。
【0003】
従来、ポリエステル、ポリアミドなどの熱溶融性繊維製品に防炎性を付与する方法としては、リン化合物、ハロゲン化合物などを防炎剤として用い、バインダーとして熱溶融性のポリウレタン樹脂、ポリエステル樹脂を用いて、熱溶融を促進することにより消防法の45°ミクロバーナー法、コイル法、垂直法などの防炎規格をクリアーさせる方法が採用されてきた。
【0004】
しかしながら近年、立毛を有する熱可塑性合成繊維布帛にポリウレタン樹脂を含浸した、スエードのような高級感のある布張家具、椅子張地などのニーズが非常に高くなって来ており、このような布張家具、椅子張地においては裏面にウレタンフォームを積層した状態でミクロバーナーで30秒間接炎するという特殊な防炎試験方法が採用されるので、上記のような熱溶融を促進させる防炎性付与方法を適用した場合には、裏面のウレタンフォームまで炎が貫通し易くなって逆に防炎性が低下するという問題が発生することが判明した。
【0005】
このような問題を解決するため、例えば、特開昭56−85478号公報には、スエード状繊維構造物の裏面に難燃性シートを張り合わせる方法が開示されているが、該方法においては、スエード状繊維構造物の風合が粗剛化するため、その用途が著しく制限されるという問題があった。
【0006】
また、特公昭60−4306号公報、或いは特開昭58−13786号公報には、ハロゲンを含む脂肪族リン酸エステル化合物を防炎剤として使用する方法が開示されているが、該方法においては、防炎剤が繊維表面に移行し易い為、ベタツキ感を生ずると共に、染料が滲み出し、摩擦堅牢度を低下させたり、汗や濡れた衣服の接触等により防炎剤が溶出して防炎性が低下する上、焼却時にダイオキシンなどの有害ガスが発生したり、ケミカルリサイクルが困難になると言う問題もあった。
【0007】
【発明が解決しようとする課題】
本発明の目的は上記従来技術の有する問題点を解消し、自己消化性を有する優れた防炎性を有し、且つ風合が良好で染色堅牢度の低下が無く、しかも焼却時にダイオキシンなどの有毒ガスが発生し難いスエード状繊維構造物を提供することにある。
【0008】
【課題を解決するための手段】
本発明者らは上記目的を達成するために鋭意検討した結果、スエード状繊維構造物に、芳香族リン酸エステル化合物及び金属系酸化物を防炎剤として固着させるとき、所望のスエード状繊維構造物が得られることを究明した。
【0009】
かくして本発明によれば、その表面に立毛部を有する熱可塑性合成繊維布帛の裏面に、アクリル酸エステル樹脂を主成分とする樹脂組成物が付与されてなるスエード状繊維構造物であって、該樹脂組成物が、芳香族リン酸エステル化合物及び金属系酸化物を含むことを特徴とする防炎性に優れたスエード状繊維構造物が提供される。
【0010】
【発明の実施の形態】
本発明で使用するスエード状繊維構造物としては、熱可塑性合成繊維布帛に湿式法または乾式法でポリウレタン樹脂を含浸した後、表面を起毛したものなどを挙げることができ、例えば、前述の特公昭60−4306号公報や、特公平3−13356号公報、或いは特公平3−20514号公報などに記載のスウエード状繊維構造物などが例示される。
【0011】
上記のポリウレタン樹脂としては、ポリエステルジオール、ポリエーテルジオール、ポリカーボネートジオール、ポリカプロラクトンジオール等のポリマージオールと、芳香族ジイソシアネート、脂肪族若しくは脂環族ジイソシアネートなどの有機ジイソシアネートとを、活性水素原子を少なくとも2個以上有する低分子化合物を鎖伸長剤として反応させたポリウレタンエラストマーなど、任意のものが使用できるが、指向する用途によって柔軟性、耐加水分解性、耐光性、耐熱性などの各種性能を満たす組成のものを適宜選ぶことができる。
【0012】
また、起毛に際して、起毛密度、立毛長などの制限は特になく、従来公知の条件が任意に採用できる。
【0013】
上記スウエード状繊維構造物の裏面(一方面)には、アクリル酸エステル樹脂を主成分とする樹脂組成物が付与されている。
【0014】
ここで、アクリル酸エステル樹脂としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸2エチルヘキシルなどの単量体の重合体や、該重合体とアクリルアミド、酢酸ビニール、スチレン、ブタジェン、メタクリル酸メチル、N−メチロールアクリルアミド、ヒドロキシアルキルアクリレート、アクリル酸グリジルアクリレートなどとの共重合体組成物が例示される。また、重合方法としては通常の懸濁重合、乳化重合、溶液重合が任意に採用できる。
【0015】
本発明においては、上記樹脂組成物に、芳香族リン酸エステル化合物及び金属系酸化物が含まれていることが肝要である。
【0016】
ここで、芳香族リン酸エステル化合物とは、レゾルシンとオキシ塩化燐を反応させて脱塩酸した後、フェノール、ビスフェノール等とエステル交換し、縮合させることにより製造可能な化合物であり、具体的には、トリクレジルホスフェート、トリフェニルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェートなどのモノマータイプの芳香族リン酸エステル化合物、レゾシノールジホスフェートなどの芳香族縮合リン酸エステル化合物などが挙げられるがこれらに限定されものではない。
【0017】
また、金属系酸化物としては、酸化アンチモン、硼酸亜鉛、酸化モリブデン、水酸化アルミニウム、水酸化マグネシウムなどの化合物が例示できる。これら金属系酸化物の粒径はアクリル酸エステル樹脂との混和性を良くするために10μm以下が望ましい。
【0018】
上記芳香族リン酸エステル化合物と金属系酸化物との配合比率は2:1〜1:2の範囲が望ましい。ここで、芳香族リン酸エステル化合物の比率が多くなり過ぎると熱溶融性が高くなりすぎて結果的に防炎性が不良となり、一方、金属系酸化物の比率が高くなり過ぎるとやはり防炎効果が低くなることがある。
【0019】
また、アクリル酸エステル樹脂と、芳香族リン酸エステル化合物及び金属系酸化物との配合比率は1:1〜2:1の範囲が好ましい。ここで、アクリル酸エステル樹脂の比率が多くなり過ぎると防炎性が不良となり、一方、芳香族リン酸エステル化合物及び金属系酸化物の比率が多くなり過ぎると接着性が不良となる。
【0020】
本発明においては、上記のアクリル酸エステル樹脂に、芳香族リン酸エステル化合物及び金属刑酸化物とを配合し、それにさらにCMC、アクリル酸アンモニウムなどの増粘剤を適量添加して粘度調整を行って得た樹脂組成物を、スエード状繊維構造物の裏面(一方面)にナイフコーター法、グラビアロラー法などの方法を用いて付与する。
【0021】
この際の樹脂組成物の付着量は100〜180g/m2であることが好ましい。該付着量が100g/m2未満の場合は、防炎試験時に裏面のウレタンフォーム層迄バーナーの炎が達し防炎性が不良となる。一方、該付着量が180g/m2を越える場合は、スウエード状繊維構造物の風合いが粗硬になる。
【0022】
【実施例】
以下、本発明を実施例により更に詳細に説明する。なお、実施例及び比較例において用いた各特性値の測定方法は下記の通りである。
【0023】
(1)防炎性
消防法布張家具などのクレビスバーナー法により判定した。残炎、残じんが120秒以下が合格である。
【0024】
(2)摩擦堅牢度
JIS L 1079に準じ、試料を105℃で24時間、熱風乾燥機により加熱した後の染料のブリードアウトをグレースケールにより判定した。
【0025】
(3)風合
熟練者により良好(○)、不良(×)の2段階で官能判定した。
【0026】
[実施例1〜3]
71dtex/144フィラメント、83dtex/24フィラメント、及び83dtex/36フィラメントの6ナイロン繊維よりなるインターロック丸編地の片面を起毛機で起毛処理し、染色後さらに起毛を施して目付320g/m2、厚さ1.2mmの起毛編地を得た。
【0027】
該編地を、無黄変型ポリカーボネート系ポリウレタンエラストマーを20重量%含有するDMF溶液(大日本インキ(株)製:クリスボンMP―303)に浸漬した後、マングルでピックアップ70%となるように絞液した後、150℃で3分間乾燥してスエード状繊維構造物を得た。
【0028】
該繊維構造物の裏面に、表1に示す組成を有し、アクリル酸とアンモニア水を少量添加して、その粘度を12,000cpsに調整した樹脂組成物をドクターナイフで塗工した後、130℃で15分間加熱処理し、樹脂組成物が付与されたスエード状繊維構造物を得た。
【0029】
[比較例1〜3]
実施例1において、芳香族リン酸エステル化合物に代えて、燐酸グアニジン又はトリスジクロロプロピルホスフェートを用い、また、アクリル酸エステル樹脂に代えて表1に示すポリウレタン樹脂を使用した以外は実施例1と同様に実施した。
【0030】
得られたスエード状繊維構造物の評価結果を表1に併せて示す。
【0031】
【表1】
【0032】
【発明の効果】
本発明によれば、自己消化性を有する優れた防炎性を有し、且つ風合が良好で染色堅牢度の低下が無く、しかも焼却時にダイオキシンなどの有毒ガスが発生し難いスエード状繊維構造物が提供される。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a suede-like fiber structure having a raised portion on its surface, which is flexible and excellent in flame resistance.
[0002]
[Prior art]
Curtains, rugs, and plywood used in public buildings such as hotels, inns, schools, and hospitals are subject to flameproofing regulations as fireproofing objects according to the Fire Service Law. Also, bedding, upholstered furniture, and disaster hoods need to be certified as flameproof products.
[0003]
Conventionally, as a method of imparting flame retardancy to heat-meltable fiber products such as polyester and polyamide, a phosphorus compound, a halogen compound or the like is used as a flame retardant, and a heat-meltable polyurethane resin or polyester resin is used as a binder. In addition, a method of clearing a flameproof standard such as a 45 ° micro burner method, a coil method, and a vertical method of the firefighting method by promoting heat melting has been adopted.
[0004]
However, in recent years, the need for high-quality upholstered furniture, such as suede, and chair upholstery, in which a thermoplastic synthetic fiber cloth having naps is impregnated with a polyurethane resin, has become extremely high. In the case of upholstered furniture and chair upholstery, a special flameproofing test method is adopted in which a micro burner indirectly flames for 30 seconds with urethane foam laminated on the back side, so the flameproofing properties that promote thermal melting as described above It has been found that when the application method is applied, a problem occurs in that the flame easily penetrates to the urethane foam on the back surface, and conversely, the flame resistance is reduced.
[0005]
In order to solve such a problem, for example, JP-A-56-85478 discloses a method of attaching a flame-retardant sheet to the back surface of a suede-like fiber structure. Since the hand of the suede-like fiber structure becomes rough and stiff, there has been a problem that its use is significantly restricted.
[0006]
JP-B-60-4306 or JP-A-58-13786 discloses a method in which an aliphatic phosphate compound containing a halogen is used as a flame retardant. Because the flame retardant easily migrates to the fiber surface, it gives a sticky feeling, and the dye oozes out, lowers the fastness to friction, and the flame retardant elutes due to contact with sweat or wet clothes, etc. In addition, there is a problem that toxic gas such as dioxin is generated at the time of incineration, and that chemical recycling becomes difficult.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems of the prior art, to have excellent flame resistance having self-extinguishing property, and to have a good feeling without a decrease in dyeing fastness, and to reduce dioxin and the like during incineration. An object of the present invention is to provide a suede-like fibrous structure in which toxic gas is hardly generated.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, when fixing an aromatic phosphate compound and a metal oxide as a flameproofing agent to a suede-like fiber structure, a desired suede-like fiber structure was obtained. I determined that things could be obtained.
[0009]
Thus, according to the present invention, a suede-like fiber structure obtained by applying a resin composition containing an acrylate resin as a main component to the back surface of a thermoplastic synthetic fiber cloth having a napped portion on its surface, A suede-like fiber structure excellent in flame resistance, characterized in that the resin composition contains an aromatic phosphate compound and a metal-based oxide.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Examples of the suede-like fiber structure used in the present invention include those obtained by impregnating a thermoplastic synthetic fiber fabric with a polyurethane resin by a wet method or a dry method and then raising the surface thereof. Examples thereof include a suede-like fiber structure described in JP-A-60-4306, JP-B-3-13356, and JP-B-3-20514.
[0011]
Examples of the polyurethane resin include a polymer diol such as polyester diol, polyether diol, polycarbonate diol, and polycaprolactone diol, and an organic diisocyanate such as an aromatic diisocyanate, an aliphatic or alicyclic diisocyanate. Any material such as a polyurethane elastomer obtained by reacting a low molecular compound having at least one as a chain extender can be used, but a composition that satisfies various performances such as flexibility, hydrolysis resistance, light resistance, and heat resistance depending on the intended use. Can be appropriately selected.
[0012]
In raising the hair, there is no particular limitation on the raising density and the length of the raised hair, and conventionally known conditions can be arbitrarily adopted.
[0013]
A resin composition containing an acrylate resin as a main component is provided on the back surface (one surface) of the suede-like fiber structure.
[0014]
Here, as the acrylate resin, a polymer of a monomer such as methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, or 2-ethylhexyl acrylate, or a polymer of acrylamide, vinyl acetate, or styrene , Butadiene, methyl methacrylate, N-methylolacrylamide, hydroxyalkyl acrylate, glycidyl acrylate and the like. As the polymerization method, ordinary suspension polymerization, emulsion polymerization, and solution polymerization can be arbitrarily adopted.
[0015]
In the present invention, it is important that the resin composition contains an aromatic phosphate compound and a metal oxide.
[0016]
Here, the aromatic phosphate compound is a compound that can be produced by reacting resorcinol with phosphorus oxychloride and dehydrochlorinating, then transesterifying with phenol, bisphenol, and the like, and condensing it. Monomer-type aromatic phosphate compounds such as tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate and cresyl diphenyl phosphate, and aromatic condensed phosphate compounds such as resosinol diphosphate. It is not limited to these.
[0017]
Examples of the metal-based oxide include compounds such as antimony oxide, zinc borate, molybdenum oxide, aluminum hydroxide, and magnesium hydroxide. The particle size of these metal oxides is desirably 10 μm or less in order to improve the miscibility with the acrylate resin.
[0018]
The mixing ratio of the aromatic phosphate compound to the metal oxide is preferably in the range of 2: 1 to 1: 2. Here, if the ratio of the aromatic phosphate compound is too large, the heat melting property becomes too high, resulting in poor flame resistance. On the other hand, if the ratio of the metal oxide is too high, the flame resistance is also increased. The effect may be lower.
[0019]
The mixing ratio of the acrylate resin to the aromatic phosphate compound and the metal oxide is preferably in the range of 1: 1 to 2: 1. Here, when the ratio of the acrylate resin is too large, the flame resistance is poor, while when the ratio of the aromatic phosphate compound and the metal oxide is too large, the adhesiveness is poor.
[0020]
In the present invention, an aromatic phosphate compound and a metal oxide are blended with the above-mentioned acrylate resin, and the viscosity thereof is adjusted by adding an appropriate amount of a thickener such as CMC and ammonium acrylate thereto. The resin composition obtained as described above is applied to the back surface (one surface) of the suede-like fiber structure using a method such as a knife coater method or a gravure roller method.
[0021]
At this time, the amount of the resin composition attached is preferably 100 to 180 g / m 2 . If the amount of adhesion is less than 100 g / m 2 , the flame of the burner reaches the urethane foam layer on the back surface during the flameproof test, resulting in poor flameproofing. On the other hand, when the adhesion amount exceeds 180 g / m 2 , the texture of the suede-like fiber structure becomes coarse and hard.
[0022]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, the measuring method of each characteristic value used in the example and the comparative example is as follows.
[0023]
(1) Flameproof Fire Fighting Method Judged by the clevis burner method for upholstered furniture. A residual flame and dust of 120 seconds or less pass.
[0024]
(2) Fastness to friction According to JIS L 1079, the bleed out of the dye after the sample was heated at 105 ° C for 24 hours by a hot air drier was determined by gray scale.
[0025]
(3) Sensory judgment was made by a skilled hand expert in two stages: good (O) and poor (X).
[0026]
[Examples 1 to 3]
One surface of an interlock circular knitted fabric composed of 6 nylon fibers of 71 dtex / 144 filament, 83 dtex / 24 filament, and 83 dtex / 36 filament is brushed with a napping machine, and after dying, further napping is performed to give a basis weight of 320 g / m 2 and a thickness of 320 g / m 2 . A brushed knitted fabric having a thickness of 1.2 mm was obtained.
[0027]
The knitted fabric is immersed in a DMF solution containing 20% by weight of a non-yellowing type polycarbonate-based polyurethane elastomer (manufactured by Dainippon Ink Co., Ltd .: Chrisbon MP-303), and then squeezed with a mangle so that the pickup becomes 70%. After that, it was dried at 150 ° C. for 3 minutes to obtain a suede-like fiber structure.
[0028]
After applying a resin composition having the composition shown in Table 1 and adding a small amount of acrylic acid and aqueous ammonia to adjust the viscosity thereof to 12,000 cps on the back surface of the fiber structure using a doctor knife, 130 A heat treatment was performed at 15 ° C. for 15 minutes to obtain a suede-like fiber structure provided with the resin composition.
[0029]
[Comparative Examples 1 to 3]
In the same manner as in Example 1 except that guanidine phosphate or trisdichloropropyl phosphate was used instead of the aromatic phosphate compound, and the polyurethane resin shown in Table 1 was used instead of the acrylate resin. Was carried out.
[0030]
The evaluation results of the obtained suede-like fiber structure are also shown in Table 1.
[0031]
[Table 1]
[0032]
【The invention's effect】
According to the present invention, a suede-like fiber structure having an excellent flameproofing property having self-digesting property, having a good feeling without a decrease in color fastness, and hardly generating a toxic gas such as dioxin when incinerated. Things are provided.
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JP2002191762A JP4065729B2 (en) | 2002-07-01 | 2002-07-01 | Suede-like fiber structure with excellent flame resistance |
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JP2002191762A JP4065729B2 (en) | 2002-07-01 | 2002-07-01 | Suede-like fiber structure with excellent flame resistance |
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JP2004036011A true JP2004036011A (en) | 2004-02-05 |
JP4065729B2 JP4065729B2 (en) | 2008-03-26 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1916329A4 (en) * | 2005-07-08 | 2011-07-06 | Toray Industries | Artificial sueded leather being excellent in flame retardance and method of producing the same |
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Publication number | Priority date | Publication date | Assignee | Title |
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KR102375461B1 (en) | 2016-06-28 | 2022-03-21 | 도레이 카부시키가이샤 | Composite sheet-like article and manufacturing method thereof |
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2002
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1916329A4 (en) * | 2005-07-08 | 2011-07-06 | Toray Industries | Artificial sueded leather being excellent in flame retardance and method of producing the same |
US10774265B2 (en) | 2005-07-08 | 2020-09-15 | Toray Industries, Inc. | Artificial sueded leather being excellent in flame retardance and method of producing the same |
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