JP5925914B2 - 積層シート及びその製造方法 - Google Patents
積層シート及びその製造方法 Download PDFInfo
- Publication number
- JP5925914B2 JP5925914B2 JP2014553117A JP2014553117A JP5925914B2 JP 5925914 B2 JP5925914 B2 JP 5925914B2 JP 2014553117 A JP2014553117 A JP 2014553117A JP 2014553117 A JP2014553117 A JP 2014553117A JP 5925914 B2 JP5925914 B2 JP 5925914B2
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- JP
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- Prior art keywords
- layer
- laminated sheet
- resin
- woven fabric
- base fabric
- 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.)
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Classifications
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
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Landscapes
- Engineering & Computer Science (AREA)
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- Laminated Bodies (AREA)
Description
穿孔加工を施すことにより、乾式合成皮革では基布の種類により孔の歪み、強度の著しい低下が起こり易い。
湿式合成皮革においても、基材となる基布の物性により強度が十分得られない場合があり、また、孔を開けたことにより通気性が上がり、それに伴い難燃性能が低下する傾向になる。また、基布にウレタン樹脂を含浸させて湿式ベースとする場合、ウレタン樹脂が基布に入り込むため、難燃性能が低下する傾向がある。
また、基布に表皮層を貼り合わせる前に粗面化加工(バフ加工)を施す際、基布を構成する糸が傷つくことにより、強度が低下する場合がある。
更に、磨耗耐久性の面において、孔の縁が擦れることにより、耐摩耗性が不十分となり易い。
すなわち、上記目的を達成するため、以下の発明が提供される。
<2> 前記織布が、縦糸として5〜30番手の単糸を、横糸として10〜40番手の二本〜四本撚り糸を用いて綾織した織布である<1>に記載の積層シート。
<3> 前記有機難燃剤が、有機リン酸系難燃剤である<1>又は<2>に記載の積層シート。
<4> 前記表皮層上にさらに耐摩耗層を有する<1>〜<3>のいずれかに記載の積層シート。
<5> 前記耐摩耗層は、樹脂、滑剤、及び架橋剤を含む層である<4>に記載の積層シート。
<6> 前記基布層における前記ポリウレタン系樹脂100質量部に対する前記有機難燃剤の含有量が、10〜30質量部である<1>〜<5>のいずれかに記載の積層シート。
<7> <1>〜<6>のいずれかに記載の積層シートを備えた自動車内装材。
<8> ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液をトラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させる工程と、
前記樹脂溶液が含浸した前記織布を水中に浸漬して前記織布に含まれる前記溶媒を除去するとともに前記ポリウレタン系樹脂を凝固させる工程と、
前記ポリウレタン系樹脂を凝固させた前記織布を乾燥させて多孔質構造を有する基布層を形成する工程と、
前記基布層の片面を粗面化する工程と、
前記基布層の粗面化した面上に表皮層が積層した積層体を形成する工程と、
前記積層体の厚さ方向に貫通し、孔径が1.0mm〜2.0mmである複数の通気孔を穿孔する工程と、
を有する積層シートの製造方法。
[積層シート]
本発明の積層シートは、ポリウレタン系樹脂及び有機難燃剤を含む樹脂組成物を、トラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させてなる多孔質構造を有する基布層と、前記基布層上に積層された表皮層と、を有し、厚さ方向に貫通する複数の通気孔を有する。
基布層12はポリウレタン系樹脂及び有機難燃剤を含む樹脂組成物を、トラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させてなる多孔質構造を有する。
基布層12を構成する基布として、JIS L1096 8.15.4 C法(トラペゾイド法)による引裂き強度がタテ150N以上かつヨコ100N以上の強度が高い織布を用いる。織布は、引裂き強度がタテ180N以上かつヨコ120N以上であることが好ましく、タテ200N以上かつヨコ150N以上であることがより好ましい。
ここで、JIS L1096:1999 8.15.4 C法(トラペゾイド法)による引裂き強度は、具体的には以下のようにして測定される。
7.5cm×15cmの試料片をタテ方向及びヨコ方向にそれぞれ3枚採取し、試験片上に図6のように等脚台形の印を付け、この印の短辺の中央に辺と直角に1cmの切れ目を入れ、幅7.5cm以上のクランプをもつ引張試験機を用い、図7に示すように試験片のつかみ間隔を2.5cmとして、等脚台形の印(点線部分)に沿って、試験片の台形の短辺を張り、長辺は緩めてクランプに挟む。引張速度は、1分間当たり20cmとし、タテ方向及びヨコ方向に引き裂くときに示す最大荷重(引裂強さ)(N{kgf})を測り、横糸引裂強さ及び縦糸引裂強さ(N{kgf})のそれぞれの平均値を算出し、小数点以下1けたに丸める。
例えば、縦糸として5〜30番手の単糸を用い、横糸として10〜40番手の二本〜四本撚り糸を用いて綾織した織布が好適である。横糸として二本〜四本撚り糸を用いれば、基布の引裂強度が110N以上となり、孔をあけても十分な引裂き強度が得られ易い。
横糸として二本〜四本撚り糸を用いて綾織した織布であれば、十分な引裂き強度が得られるとともに、五本撚り糸を用いた場合に比べ、基布の凹凸(うねり)が小さく、表面の摩耗性の低下が抑制される。また、五本撚り糸を用いた織布に場合に比べ、穿孔しやすく、毛羽やほつれ糸が出難いため、外観の良い孔を形成し易い。
また、織布における糸の本数は、糸の材質、太さ(番手)にもよるが、タテ150N以上かつヨコ100N以上の引裂き強度を達成するため、例えば、縦糸は40〜80本/インチであり、横糸は20〜50本/インチであることが好ましい。
基布層12に含まれるポリウレタン系樹脂は前記織布に含浸されて織布とともに多孔質構造を形成する。基布層12に含まれるポリウレタン系樹脂としては、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、及びポリエステル系ポリウレタンが挙げられる。耐加水分解性、耐熱劣化性等の点から、ポリカーボネート系ポリウレタン、及びポリエーテル系ポリウレタンが好ましい。
ポリウレタン系樹脂の含有量が、織布100質量部に対して10質量部以上であれば基布層12に適度な硬さを与え、孔30を開ける際に孔30の変形を防ぐことができ、40質量部以下であれば基布層12の柔軟性を保つことができる。
上記観点から、基布層12におけるポリウレタン系樹脂の含有量は、織布100質量部に対して15〜35質量部であることがより好ましく、20〜30質量部であることが特に好ましい。
基布層12に含まれる難燃剤としては、有機難燃剤を用いる。例えば、リン系難燃剤、窒素−リン系難燃剤、ハロゲン系難燃剤などが挙げられ、有機リン酸系難燃剤が好ましく、有機リン酸塩化物がより好ましい。
なお、難燃剤としては、水酸化アルミニウムなどの無機難燃剤があるが、無機難燃剤を用いた場合には、燃焼温度を低下させる効果は得られるものの、通気孔を有し、燃焼し易い積層シートにおいては燃焼を抑制する効果は小さい。一方、有機難燃剤であれば樹脂溶液中に溶解又は分散し易く、樹脂溶液を織布に含浸させたときにポリウレタン系樹脂とともに織布全体に行きわたって積層シートの燃焼を抑制する高い効果が得られる。また、有機難燃剤を用いることで、無機難燃剤を用いた場合に比べて基布層の強度が高くなり易い。
有機難燃剤は市販品としても入手可能であり、例えば、トリフェニルホスフェートやトリクレジルホスフェートなどを用いた市販品が挙げられる。
上記観点から、基布層12における有機難燃剤の含有量は、ポリウレタン系樹脂100質量部に対して15〜25質量部であることがより好ましく、17〜23質量部であることが特に好ましい。
基布層12は、織布、ポリウレタン系樹脂、有機難燃剤のほかに、他の添加剤を含んでもよい。例えば、顔料等の着色剤、レベリング剤などが挙げられる。
このような着色樹脂粒子の平均粒径は、一般的には、0.5μm〜100μmの範囲であることが好ましく、より好ましくは、3μm〜50μmの範囲である。
上記観点から、基布層12の厚みは0.7〜1.3mmであることがより好ましく、0.9〜1.1mmであることが特に好ましい。
接着層14は接着剤によって構成され、基布層12と表皮層16を接着する。接着層14を構成する材料としては、ポリウレタン系樹脂、難燃剤、顔料等が挙げられる。
表皮層16は、主に積層シート10に意匠性や強度、耐摩耗性などを付与するために設けられるものであり、樹脂及び着色剤を含んで構成される。
着色剤として用いられる有機樹脂微粒子の平均粒径は、一般的には、0.5μm〜100μmの範囲であることが好ましく、より好ましくは、3μm〜50μmの範囲である。
なお、表皮層16における着色剤の含有量は、積層シート10の使用目的に応じて選択すればよい。
耐摩耗層18は、主に耐摩耗性を付与するために必要に応じて設けられる。耐摩耗層18は、例えば、樹脂、滑剤、及び架橋剤を含み、さらに必要に応じて艶消し剤などの他の添加剤を含んで構成される。
耐摩耗層18における滑剤の含有量は、例えば、5〜15質量%である。
耐摩耗層18における架橋剤の含有量は、架橋前の添加量として、例えば、5〜20質量%である。
耐摩耗層18における艶消し剤及びその他の添加剤の総含有量は、例えば、5〜30質量%である。
触感処理層20は、滑らかな肌触りを付与するために必要に応じて設けられる。触感処理層20は、樹脂、滑剤、艶消し剤を含んで構成される。
積層シート10には、厚さ方向に貫通する通気孔30が複数設けられている。
各通気孔30の形状は特に限定されず、使用目的に応じて、平面視において円形でもよいし、多角形でもよい。なお、積層シート10により高い強度を発揮させる観点から平面視において円形、すなわち、積層シート10の厚さ方向に円筒形の通気孔30が設けられていることが好ましい。
通気孔30の間隔Pは、用途にもよるが、積層シート全体の通気性と強度を両立させる観点から、3.0〜8.0mmであることが好ましく、4.0〜7.0mmであることがより好ましい。
次に、本実施形態に係る積層シート10を製造する方法について説明する。本実施形態に係る積層シート10の製造方法は特に限定されないが、ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液を引裂き強度(トラペゾイド法による)がタテ150N以上かつヨコ100N以上の織布に含浸させる工程と、前記樹脂溶液が含浸した前記織布を水中に浸漬して前記織布に含まれる前記溶媒を除去するとともに前記ポリウレタン系樹脂を凝固させる工程と、前記ポリウレタン系樹脂を凝固させた前記織布を乾燥させて多孔質構造を有する基布層12を形成する工程と、前記基布層12の片面を粗面化する工程と、前記基布層12の粗面化した面上に表皮層16が積層した積層体を形成する工程と、前記積層体の厚さ方向に貫通する複数の通気孔30を穿孔する工程と、を有する方法によって好適に製造することがきる。
まず、ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液をトラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させる。
樹脂溶液を織布に含浸させる方法は限定されず、例えば、樹脂溶液を織布に公知の方法により塗布して含浸させてもよいし、樹脂溶液を収容した容器内に織布を入れて含浸させてもよい。
ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液が含浸した織布を水中に浸漬することで、織布に含まれる樹脂溶液中の溶媒が水と置換して除去(脱溶媒)されるとともにポリウレタン系樹脂が凝固する。
次いで、含浸したポリウレタン系樹脂を凝固させた織布を乾燥させて多孔質構造を有する基布層12を形成する。例えば、凝固したポリウレタン系樹脂と水を含む織布をマングルによって脱水した後、100℃〜120℃の熱風下で乾燥させることで多孔質構造を有する基布層(湿式ミクロポーラス層)12が形成される。
次いで、前記基布層12の片面を粗面化する。例えば、基布層12の片面をバッフィングマシンによって粗面化することにより基布層12の片面がわずかに起毛する。
次いで、前記基布層12の粗面化した面上に表皮層16が積層した積層体を形成する。
例えば絞付き離型紙上にシリコン変性ポリウレタンを塗布し、加熱乾燥して所望の厚みのシリコン変性ポリウレタン表皮層16を形成する。
次にこの表皮層16の上にポリウレタン系接着剤を塗布した後、加熱乾燥し所望の厚みのポリウレタン接着層14を形成する。
なお、接着層14と表皮層16との間に弾力性あるいは柔軟性を付与する中間層を設ける場合は、接着層14を形成する前に、表皮層16上に中間層を形成する。
必要に応じて、表皮層16上に耐摩耗層18を設ける。例えば、溶媒にポリウレタン系樹脂、滑剤、架橋剤、艶消し剤、その他の添加剤をそれぞれ所望の量で添加した耐摩耗層形成用塗布液を調製し、ロールコート等の公知の塗布方法によって表皮層16上に塗布した後、乾燥させる。
また、必要に応じて、表皮層16又は耐摩耗層18上に触感処理層20を設ける。例えば、溶媒にポリウレタン樹脂、溶剤、添加剤をそれぞれ所望の量で添加した触感処理層形成用塗布液を調製し、ロールコート等の公知の塗布方法によって表皮層16又は耐摩耗層18上に塗布した後、乾燥させる。
次いで、前記積層体の厚さ方向に貫通する複数の通気孔30を穿孔する。例えば、パンチングロールにより積層体に所望の間隔で所望の径を有する通気孔30を穿孔する。これにより厚さ方向に貫通した多数の通気孔30を有する積層シート10が製造される。
また、穿孔により基布層12の織布を構成する糸が切断されるが、固化したポリウレタン系樹脂によって補強されているため、切断されたほつれ糸が通気孔30の内部や外に飛び出して外観を損ねることが抑制される。
さらに、基布層12における通気孔30の内壁には有機難燃剤が存在するため、通気孔30においても高い難燃性を発揮する。
(基布層の形成)
基布として下記表1に示す構成の糸を用いて綾織した織布を用意した。この織布のトラぺゾイド法による引裂き強度をテンシロン試験機(オリエンテック社製、商品名:UNIVERSAL TESTING INSTRUMENT モデル RTG−1310)で測定したところ、タテ200N、ヨコ150Nであった。
・ポリカーボネート系ポリウレタン
(DIC社製、商品名:MP−865PS):40質量部
・有機リン酸塩化合物(難燃剤)
(アークロマジャパン社製、商品名:ペコフレームSTC、粒径:3μm):10質量部
・ジメチルホルムアミド:60質量部
次いで、120℃の熱風下で10分乾燥させることにより、多孔質構造を有する基布層(厚み:1.1mm)を形成した。
次いで、バッフィングマシン(名南製作所社製、商品名:A−5)を用い、基布層の片面にバフ加工を施して粗面化し、起毛面とした。
下記に示す構成の表皮層形成用塗布液を調製した。
・シリコン変性ポリウレタン樹脂(DIC社製、商品名: NY−373):60質量部
・顔料(DIC社製、商品名:DIALAC BLACK L−1770S):40質量部
・溶剤(日産化学工業社製、商品名:DMF):10質量部
下記に示す構成の接着層形成用塗布液を調製した。
・ポリカーボネート系ポリウレタン樹脂(DIC社製、商品名:クリスボンTA205FT)100質量部
・架橋剤(DIC社製、商品名:バーノックDN−950):12質量部
・架橋促進剤(DIC社製、商品名:クリスボンアクセルT−81E):1質量部
・溶剤(日産化学工業社製、商品名:DMF):60質量部
次に表皮層の上に上記接着層形成用塗布液を塗布した後、130℃で1分加熱乾燥してポリウレタン接着層(厚み:40μm、乾燥後の塗布量:35g/m2)を形成した。
接着剤を固化した後、表皮層から離型紙を剥離した。
下記表2に示す構成の耐摩耗層形成用塗布液を調製した。なお、各成分は以下の通りである。
・ポリカーボネート系ウレタン(主剤):スタール・ジャパン社製、商品名:WF−13−139
・シリコン(滑剤):ビックケミー・ジャパン社製、商品名:BYK−306
・カルボジイミド(架橋剤):日清紡ケミカル社製、商品名:E−02
上記工程を経て得られた基布層、接着層、表皮層、耐摩耗層が積層された積層体(合成皮革)にパンチングロールにより孔を開けて通気孔を有する積層シートを得た。
積層シートにおける通気孔の径、間隔P及び開孔率は以下の通りである。
孔径:1.4mm
ピッチP:5.0mm
開孔率:14%
得られた積層シートについて、孔の外観、引裂き強度、難燃性、通気性について以下の評価を行った。
積層シートに形成された通気孔のうち10個について開口部の円の歪を目視により1点〜5点の5段階で評価した。点数が高いほど本皮に穿孔加工した場合と同等の円形に近く、点数が低いほど歪が大きいことを示す。
積層シートに形成された通気孔のうち10個について通気孔の縁部の毛羽を目視で評価し、1点〜5点の5段階で評価した。点数が高いほど本皮に穿孔加工した場合と同等に毛羽が少なく、点数が低いほど毛羽を多いことを示す。
積層シートに形成された通気孔のうち10個について通気孔内のほつれ糸を目視で評価し、1点〜5点の5段階で評価した。点数が高いほどほつれ糸が少ないことを示す。
積層シートをJIS L1096 8.15.4 C法によって引裂き強度を測定し、以下の1点〜5点の5段階で評価した。
5点:引裂き強度が100N以上
4点:引裂き強度が80N以上100N未満
3点:引裂き強度が60N以上80N未満
2点:引裂き強度が40N以上60N未満
1点:引裂き強度が40N未満
積層シートの難燃性をFMVSS No.302 燃焼試験(ISO3795,JIS D1201)により測定し、1点〜5点の5段階で評価した。
5点:燃焼速度=0mm/min
4点:0mm/min<燃焼速度≦50mm/min
3点:50mm/min<燃焼速度≦80mm/min
2点:80mm/min<燃焼速度≦100mm/min
1点:100mm/min<燃焼速度
積層シートの通気性をJIS L1096 8.27.1 A法により測定し、1点〜5点の5段階で評価した。
5点:130cc/cm2・s以上
4点:100cc/cm2・s以上130cc/cm2・s未満
3点:80cc/cm2・s以上100cc/cm2・s未満
2点:60cc/cm2・s以上80cc/cm2・s未満
1点:60cc/cm2・s未満
縦糸を20番手から30番手に、横糸を20番手4本撚りから20番手3本撚りにそれぞれ変更して基布を作製したこと以外は実施例1と同様にして積層シートを作製した。なお、基布として用いた織布のトラぺゾイド法による引裂き強度は、タテ160N、ヨコ130Nであった。
得られた積層シートについて実施例1と同様に評価した。
織布に含浸させる樹脂溶液において、粒径3μmの難燃剤を粒径20μmの難燃剤(アークロマジャパン社製、商品名:ペコフレームATC)に変更したこと以外は実施例1と同様にして積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
表皮層上に耐摩耗層を形成しないこと以外は実施例1と同様にして積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
織布に含浸させる樹脂溶液において、有機リン酸塩化合物を水酸化アルミニウムに変更したこと以外は実施例1と同様にして積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
実施例1で用いた織布に含浸させる樹脂溶液から有機リン酸塩化物を除いた樹脂溶液を調製して実施例1と同様に織布に含浸させ、裏面に難燃剤(リン系化合物、商品名:ノンネンR031-5、製造元:丸菱油化工業株式会社)を塗工したこと以外は実施例1と同様にして合皮を作製した。
得られた積層シートについて実施例1と同様に評価した。
基布をトリコットサテン組織(コース/ウェル=53/45、トラペゾイド法による引裂き強度がタテ170N以上かつヨコ150N以上)に変更したこと以外は実施例1と同様して積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
また、図3、図4、図5に、実施例1、比較例2、比較例3でそれぞれ作製した積層シートの通気孔の外観を示す。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (8)
- ポリウレタン系樹脂及び有機難燃剤を含む樹脂組成物を、トラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させてなる多孔質構造を有する基布層と、前記基布層上に積層された表皮層と、を有し、厚さ方向に貫通し、孔径が1.0mm〜2.0mmである複数の通気孔を有する積層シート。
- 前記織布が、縦糸として5〜30番手の単糸を、横糸として10〜40番手の二本〜四本撚り糸を用いて綾織した織布である請求項1に記載の積層シート。
- 前記有機難燃剤が、有機リン酸系難燃剤である請求項1又は請求項2に記載の積層シート。
- 前記表皮層上にさらに耐摩耗層を有する請求項1〜請求項3のいずれか一項に記載の積層シート。
- 前記耐摩耗層は、樹脂、滑剤、及び架橋剤を含む層である請求項4に記載の積層シート。
- 前記基布層における前記ポリウレタン系樹脂100質量部に対する前記有機難燃剤の含有量が、10〜30質量部である請求項1〜請求項5のいずれか一項に記載の積層シート。
- 請求項1〜請求項6のいずれか一項に記載の積層シートを備えた自動車内装材。
- ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液をトラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させる工程と、
前記樹脂溶液が含浸した前記織布を水中に浸漬して前記織布に含まれる前記溶媒を除去するとともに前記ポリウレタン系樹脂を凝固させる工程と、
前記ポリウレタン系樹脂を凝固させた前記織布を乾燥させて多孔質構造を有する基布層を形成する工程と、
前記基布層の片面を粗面化する工程と、
前記基布層の粗面化した面上に表皮層が積層した積層体を形成する工程と、
前記積層体の厚さ方向に貫通し、孔径が1.0mm〜2.0mmである複数の通気孔を穿孔する工程と、
を有する積層シートの製造方法。
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