JP2003166181A - Synthetic resin leather - Google Patents

Synthetic resin leather

Info

Publication number
JP2003166181A
JP2003166181A JP2002263598A JP2002263598A JP2003166181A JP 2003166181 A JP2003166181 A JP 2003166181A JP 2002263598 A JP2002263598 A JP 2002263598A JP 2002263598 A JP2002263598 A JP 2002263598A JP 2003166181 A JP2003166181 A JP 2003166181A
Authority
JP
Japan
Prior art keywords
weight
leather
resin
hardness
shore
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.)
Granted
Application number
JP2002263598A
Other languages
Japanese (ja)
Other versions
JP4190236B2 (en
Inventor
Takashige Hatori
尊成 羽鳥
Toshimasa Mori
敏雅 森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Okamoto Industries Inc
Original Assignee
Okamoto Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Okamoto Industries Inc filed Critical Okamoto Industries Inc
Priority to JP2002263598A priority Critical patent/JP4190236B2/en
Publication of JP2003166181A publication Critical patent/JP2003166181A/en
Application granted granted Critical
Publication of JP4190236B2 publication Critical patent/JP4190236B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic resin leather having flexibility, excellent in resistance to surface damage, capable of carrying out welding by a high-frequency welder, having frame retardance and not causing spreading of seam. <P>SOLUTION: This synthetic resin leather is obtained by providing a mixed resin layer having 60-80 Shore A hardness and composed of 50-95 wt.% thermoplastic polyurethane having 65-90 Shore A hardness and 50-95 wt.% acrylic flexible resin having 50-80 Shore A hardness on at least one side of a base. A woven fabric, a knitted fabric or a nonwoven fabric is used as the base. A flexible foam sheet or a laminate of the woven fabric, the knitted fabric or the nonwoven fabric with the flexible foam sheet can be used as the base. <P>COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【発明の属する技術分野】本発明は、熱可塑性ポリウレ
タンとアクリル系軟質樹脂との混合樹脂を用いた合成樹
脂レザーに関する。
TECHNICAL FIELD The present invention relates to a synthetic resin leather using a mixed resin of thermoplastic polyurethane and an acrylic soft resin.

【0002】[0002]

【従来技術】自動車の車両内装材、袋物素材、家具の表
皮材などに用いる合成樹脂レザーは、柔軟で強度を持つ
ことが要求されるが、従来は、織物、編物又は不織布、
或はポリオレフィンフォームなどのシート基材の表面に
軟質ポリ塩化ビニル層を形成させたものが一般的であ
る。この軟質ポリ塩化ビニルは様々な硬さのものがあっ
て、一般的なフィルム用途の場合はポリ塩化ビニル10
0重量部に可塑剤(フタル酸ジエチルヘキシル)を30
〜50重量部配合した硬さのものであるが、レザーに用
いる場合は可塑剤を70〜100重量部配合したときの
硬さのもの、すなわち相当に軟らかいものが求められて
いる。ところで、近年リサイクル問題で、軟質ポリ塩化
ビニルに替えて、ランダムポリプロピレン、エチレン−
酢酸ビニル樹脂、水素添加スチレンブタジエンラバーな
どを用いたポリオレフィン系樹脂レザーが提案されてい
る。
2. Description of the Related Art Synthetic resin leather used for automobile interior materials, bag materials, furniture skin materials, etc. is required to be flexible and strong.
Alternatively, it is general that a soft polyvinyl chloride layer is formed on the surface of a sheet base material such as a polyolefin foam. This soft polyvinyl chloride has various hardness, and for general film use, polyvinyl chloride 10
30 parts of plasticizer (diethylhexyl phthalate) in 0 parts by weight
The hardness is about 50 to 50 parts by weight, but when used for leather, the hardness is about 70 to 100 parts by weight of the plasticizer, that is, the one is considerably soft. By the way, due to the recycling problem in recent years, instead of soft polyvinyl chloride, random polypropylene, ethylene-
A polyolefin resin leather using vinyl acetate resin, hydrogenated styrene butadiene rubber, etc. has been proposed.

【0003】しかし、ポリオレフィン系レザーは、軟質
ポリ塩化ビニルレザーに比し、表面が傷付き易いこと、
高周波ウェルダー性がないこと、軟らかさが不充分であ
るなどの問題点があり、更に難燃性に劣るためリン酸系
や硼酸系の難燃剤を配合しないと規制に耐える難燃性を
持たないという問題点がある。そこで、本出願人は先に
柔軟性があり、耐表面傷付き性に優れ、高周波ウェルダ
ーで溶着加工が行なえる合成樹脂レザーとして、基材の
少なくとも片面にアクリル系軟質樹脂層を設けてなるア
クリル系樹脂レザーを提案した(特許文献1参照)。こ
のアクリル系樹脂レザーは、従来の軟質ポリ塩化ビニル
レザーに代替できる合成樹脂レザーとして優れている
が、ミシンなどで縫製したとき、縫い目が広がったり、
縫い目から裂け易いという問題点を有することを知っ
た。また、熱可塑性ポリウレタンレザーも知られている
が、これはゴムライクで反発性が強く、軟質ポリ塩化ビ
ニルのような遅延弾性による自然な軟らかさがないので
感触が劣る。また、軟らかさを出すためには可塑剤を大
量に配合する必要があり、可塑剤の移行、ブルームなど
の問題があり、またカレンダー加工性が低い。
However, the surface of polyolefin-based leather is more easily scratched than that of soft polyvinyl chloride leather,
There are problems such as lack of high-frequency welder property and insufficient softness. Furthermore, since it is inferior in flame retardance, it does not have flame retardance to withstand regulation unless phosphoric acid type or boric acid type flame retardant is blended. There is a problem. Therefore, the present applicant has previously proposed an acrylic soft resin layer provided on at least one side of a base material as a synthetic resin leather which is flexible and has excellent surface scratch resistance and can be welded by a high frequency welder. A resin resin leather has been proposed (see Patent Document 1). This acrylic resin leather is excellent as a synthetic resin leather that can replace conventional soft polyvinyl chloride leather, but when sewn with a sewing machine, the seams spread,
I learned that it has a problem that it is easy to tear from the seam. Thermoplastic polyurethane leather is also known, but it is rubber-like, has a high resilience, and does not have a natural softness due to delayed elasticity such as soft polyvinyl chloride, and thus has a poor feel. Further, in order to obtain the softness, it is necessary to add a large amount of a plasticizer, there are problems such as migration of the plasticizer and bloom, and calender processability is low.

【0004】[0004]

【特許文献1】特開2002−155477号公報[Patent Document 1] Japanese Patent Laid-Open No. 2002-155477

【特許文献2】特開平6−263828号公報[Patent Document 2] Japanese Patent Laid-Open No. 6-263828

【特許文献3】特開平9−100385号公報[Patent Document 3] Japanese Unexamined Patent Publication No. 9-100385

【特許文献4】特開平11−71437号公報[Patent Document 4] Japanese Unexamined Patent Publication No. 11-71437

【0005】[0005]

【発明が解決しようとする課題】本発明は、かかる事情
に鑑みなされたもので、上記のアクリル系樹脂レザーの
優れた性質を損なうことなく、引裂強度が高く、ミシン
などで縫製したときに、縫い目が広がったり、縫い目か
ら裂け易い欠点を解消した合成樹脂レザーを提供するこ
とを目的とする。
SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has a high tear strength without impairing the excellent properties of the acrylic resin leather described above, and when sewn with a sewing machine or the like, It is an object of the present invention to provide a synthetic resin leather in which defects such as widened seams and easy tears from the seams are eliminated.

【0006】[0006]

【課題を解決するための手段】すなわち、本発明は、基
材の少なくとも片面に、ショアA硬度65〜90の熱可
塑性ポリウレタン50〜95重量%とショアA硬度50
〜80のアクリル系軟質樹脂50〜5重量%との混合樹
脂層を設けてなり、且つ混合樹脂層のショアA硬度が6
0〜80であることを特徴とする合成樹脂レザーであ
る。上記の基材としては、織物、編物又は不織布が用い
られる。また、基材は軟質発泡体シートでもよいし、織
物、編物又は不織布と軟質発泡体シートとの積層物でも
よい。
That is, according to the present invention, 50 to 95% by weight of a thermoplastic polyurethane having a Shore A hardness of 65 to 90 and a Shore A hardness of 50 are provided on at least one surface of a substrate.
A mixed resin layer with 50 to 5% by weight of acrylic soft resin of 80 to 80, and the Shore A hardness of the mixed resin layer is 6
It is a synthetic resin leather characterized by being 0 to 80. A woven fabric, a knitted fabric, or a non-woven fabric is used as the substrate. The base material may be a soft foam sheet, or a laminate of a woven fabric, a knitted fabric or a non-woven fabric and a soft foam sheet.

【0007】また、本発明は、ショアA硬度65〜90
の熱可塑性ポリウレタン50〜95重量%とショアA硬
度50〜80のアクリル系軟質樹脂50〜5重量%との
混合樹脂をカレンダー加工してシートに成形し、該シー
トと基材とを積層一体化することを特徴とする上記の合
成樹脂レザーの製造方法である。このカレンダー加工を
円滑にするために、混合樹脂に(メタ)アクリル系重合
体を配合したり、炭酸カルシウムを配合してもよい。
The present invention also has a Shore A hardness of 65 to 90.
Of 50 to 95% by weight of thermoplastic polyurethane and 50 to 5% by weight of acrylic soft resin having Shore A hardness of 50 to 80 are calendered to form a sheet, and the sheet and the base material are laminated and integrated. The method for producing a synthetic resin leather described above is characterized by the following. In order to facilitate this calendering, a (meth) acrylic polymer or calcium carbonate may be added to the mixed resin.

【0008】[0008]

【発明の実施の形態】本発明の合成樹脂レザーは、基材
の少なくとも片面に、熱可塑性ポリウレタン50〜95
重量%とアクリル系軟質樹脂50〜5重量%との混合樹
脂層を設けた合成樹脂レザーである。上記の基材として
は、織物、編物又は不織布が用いられる。これらの編織
物の素材はポリアミド繊維、ポリエステル繊維、アクリ
ル繊維、ポリプロピレン繊維、綿、レーヨン、これらの
混紡糸などである。編物としては、両面編物、天竺編物
などであり、織物としては、平織物、綾織物、朱子織物
などである。また基材には軟質発泡体シートを用いるこ
ともできる。この軟質発泡体シートは、ポリプロピレン
フォーム、電子線架橋したポリプロピレンフォーム、ポ
リエチレンフォーム、電子線架橋したポリエチレンフォ
ーム、ポリウレタンフォームなどである。また基材には
織物、編物又は不織布と軟質発泡体シートとの積層物を
用いることもできる。この場合は、織物、編物又は不織
布−軟質発泡体シート−混合樹脂層の構成を採るのが好
ましい。
BEST MODE FOR CARRYING OUT THE INVENTION The synthetic resin leather of the present invention comprises thermoplastic polyurethane 50-95 on at least one side of a substrate.
It is a synthetic resin leather provided with a mixed resin layer of 50% by weight of acrylic soft resin and 50% by weight of acrylic soft resin. A woven fabric, a knitted fabric, or a non-woven fabric is used as the substrate. Materials for these knitted fabrics include polyamide fibers, polyester fibers, acrylic fibers, polypropylene fibers, cotton, rayon, and mixed yarns of these. The knitted fabric may be a double-sided knitted fabric, a plain knitted fabric, or the like, and the woven fabric may be a plain woven fabric, a twilled fabric, a satin woven fabric, or the like. A soft foam sheet can also be used as the base material. This soft foam sheet is polypropylene foam, electron beam crosslinked polypropylene foam, polyethylene foam, electron beam crosslinked polyethylene foam, polyurethane foam, or the like. Further, a woven fabric, a knitted fabric, or a laminate of a soft foam sheet can be used as the substrate. In this case, it is preferable to adopt a structure of woven fabric, knitted fabric or nonwoven fabric-soft foam sheet-mixed resin layer.

【0009】本発明で用いる熱可塑性ポリウレタンは、
ジイソシアネート化合物と、ヒドロキシル基を2個以上
有する化合物とを反応させて得ることができる。中で
も、長鎖ポリオール、ジイソシアネート、鎖伸長剤から
構成された、いわゆるソフトセグメントとハードセグメ
ントからなるポリウレタン系熱可塑性エラストマー(T
PU)が好ましく使用できる。これらはショアA硬度で
65〜90の樹脂硬度、特に70〜80の樹脂硬度を有
するものが好ましい。なお、本発明におけるショアA硬
度は、ASTM D 2240で測定した値(測定温度2
3℃)である。
The thermoplastic polyurethane used in the present invention is
It can be obtained by reacting a diisocyanate compound with a compound having two or more hydroxyl groups. Above all, a polyurethane-based thermoplastic elastomer (T containing a so-called soft segment and a hard segment, which is composed of a long-chain polyol, a diisocyanate, and a chain extender (T
PU) can be preferably used. Those having a Shore A hardness of 65 to 90, particularly 70 to 80, are preferable. The Shore A hardness in the present invention is a value measured by ASTM D 2240 (measurement temperature 2
3 ° C).

【0010】熱可塑性ポリウレタンを合成するためのジ
イソシアネート化合物としては、トリレンジイソシアネ
ート、ジフェニルメタンジイソシアネート、ナフタリン
ジイソシアネート、トリジンジイソシアネート、ヘキサ
メチレンジイソシアネート、キシリレンジイソシアネー
ト、水添キシリレンジイソシアネート、水添ジシクロヘ
キシルメタンジイソシアネート、イソホロンジイソイア
ネートなどが用いられる。
Examples of diisocyanate compounds for synthesizing thermoplastic polyurethane include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated dicyclohexylmethane diisocyanate and isophorone. Diisoianate or the like is used.

【0011】また、ヒドロキシル基を2個以上有する化
合物としては、アジピン酸、フタル酸等の二塩基酸とエ
チレングリコール、1,4−ブタンジオール等のグリコ
ールとの縮合反応物であるポリエステル系ポリオール;
エチレンカーボネート等のカーボネートとグリコーとの
反応物であるポリカーボネート系ポリオール;ポリエチ
レングリコール、ポリプロピレングリコール、ポリテト
ラメチレングリコール、ポリエチレングリコール−ポリ
プロピレングリコール等のポリエーテル系ポリオール等
が用いられる。本発明の合成樹脂レザーにおいては、そ
の物性からポリエーテル系ポリオールを用いるのが好ま
しい。また、ポリエーテル系ポリオールを原料とする熱
可塑性ポリウレタンは、耐老化性、カレンダー加工性が
良いので、この観点からも好ましい。
As the compound having two or more hydroxyl groups, a polyester polyol which is a condensation reaction product of a dibasic acid such as adipic acid or phthalic acid with a glycol such as ethylene glycol or 1,4-butanediol;
A polycarbonate-based polyol which is a reaction product of a carbonate such as ethylene carbonate and a glycol; a polyether-based polyol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol, or the like is used. In the synthetic resin leather of the present invention, it is preferable to use a polyether polyol because of its physical properties. Further, the thermoplastic polyurethane using a polyether polyol as a raw material has good aging resistance and calender processability, and is also preferable from this viewpoint.

【0012】鎖伸長剤としては、エチレングリコール、
1,2−プロピレングリコール、1,3−プロピレング
リコール、ブタン1,2ジオール、ブタン1,3ジオー
ル、ブタン1,4ジオール、ブタン2,3ジオール、ヘ
キサンジオールなどの低分子多価アルコール、或いはジ
アミン、水が用いられる。
As the chain extender, ethylene glycol,
Low molecular weight polyhydric alcohol such as 1,2-propylene glycol, 1,3-propylene glycol, butane 1,2 diol, butane 1,3 diol, butane 1,4 diol, butane 2,3 diol, hexane diol, or diamine , Water is used.

【0013】本発明で用いるアクリル系軟質樹脂は、常
温で軟質ポリ塩化ビニルの如く柔軟性を示す樹脂であ
る。このアクリル系軟質樹脂には、硬度がショアAで5
0〜80のもの、なかんずく55〜65のものが好まし
く用いられる。このアクリル系軟質樹脂は、多層構造重
合体、すなわち2種以上のアクリル系重合体がコア−シ
ェル型の多層構造を形成している粒子状の重合体が好ま
しい。これらのアクリル系軟質樹脂は、常温で良好な柔
軟性を示し、屈曲耐久性を有し、耐候性に優れている。
The acrylic soft resin used in the present invention is a resin having flexibility like ordinary polyvinyl chloride at room temperature. This acrylic soft resin has a Shore A hardness of 5
Those of 0 to 80, and especially those of 55 to 65 are preferably used. The acrylic soft resin is preferably a multi-layered polymer, that is, a particulate polymer in which two or more kinds of acrylic polymers form a core-shell type multi-layered structure. These acrylic soft resins exhibit good flexibility at room temperature, have bending durability, and are excellent in weather resistance.

【0014】本発明で用いるアクリル系軟質樹脂の一例
を示す。炭素数1〜12のアルキル基を持つ少なくとも
一種のアクリル酸アルキルエステル30〜99.9重量
%、炭素数1〜8のアルキル基を持つ少なくとも一種の
メタクリル酸アルキルエステル0〜70重量%、共重合
可能な不飽和単量体0〜30重量%、多官能架橋性単量
体及び/又は多官能性グラフト単量体0.1〜10重量
%からなる単量体混合物を重合してなるTgが30℃以
下である少なくとも1層の重合体層[A]10〜90重
量部と、炭素数1〜12のアルキル基を持つ少なくとも
一種のアクリル酸アルキルエステル30〜99重量%、
炭素数1〜8のアルキル基を持つ少なくとも一種のメタ
クリル酸アルキルエステル1〜70重量%、共重合可能
な不飽和単量体0〜30重量%からなる単量体混合物を
重合してなるTgが−20〜50℃である少なくとも1
層の重合体層[B]90〜10重量部との組合せからな
る多層構造重合体であり、且つ最外層が重合体層[B]
であるアクリル系軟質多層構造樹脂である(特許文献2
参照)。
An example of the acrylic soft resin used in the present invention will be shown. 30 to 99.9% by weight of at least one alkyl acrylate ester having an alkyl group having 1 to 12 carbon atoms, 0 to 70% by weight of at least one methacrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms, copolymerization The Tg obtained by polymerizing a monomer mixture composed of 0 to 30% by weight of an unsaturated monomer and 0.1 to 10% by weight of a polyfunctional crosslinking monomer and / or a polyfunctional grafting monomer is possible. 10 to 90 parts by weight of at least one polymer layer [A] at 30 ° C. or lower, and 30 to 99% by weight of at least one alkyl acrylate ester having an alkyl group having 1 to 12 carbon atoms,
The Tg obtained by polymerizing a monomer mixture consisting of 1 to 70% by weight of at least one alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms and 0 to 30% by weight of a copolymerizable unsaturated monomer is At least 1 which is -20 to 50 ° C
The polymer layer [B] is a multi-layered polymer comprising a combination of 90 to 10 parts by weight, and the outermost layer is the polymer layer [B].
Is an acrylic soft multi-layer structure resin (Patent Document 2)
reference).

【0015】アクリル系軟質樹脂の他の例を示す。炭素
数1〜8のアルキル基を持つアクリル酸アルキルエステ
ル60〜99.5重量%、共重合可能ビニル基を1個有
する単官能性単量体0〜39.5重量%、及びビニル基
又はビニリデン基を少なくとも2個有する多官能性単量
体0.5〜5重量%を重合して得られるゴム層30〜8
0重量部と、メタアクリル酸メチル40〜100重量
%、炭素数1〜8のアルキル基を持つアクリル酸アルキ
ルエステル0〜60重量%、及び共重合可能なビニル基
又はビニリデン基を有する単量体0〜20重量%を重合
して得られる硬質樹脂層20〜70重量部とから構成さ
れ、且つ最外層が硬質樹脂層であるアクリル系軟質多層
構造樹脂である(特許文献3参照)。
Another example of the acrylic soft resin will be shown. 60 to 99.5% by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, 0 to 39.5% by weight of a monofunctional monomer having one copolymerizable vinyl group, and a vinyl group or vinylidene. Rubber layers 30 to 8 obtained by polymerizing 0.5 to 5% by weight of a polyfunctional monomer having at least two groups
Monomers having 0 parts by weight, 40 to 100% by weight of methyl methacrylate, 0 to 60% by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, and a copolymerizable vinyl group or vinylidene group. It is an acrylic soft multilayer structure resin composed of 20 to 70 parts by weight of a hard resin layer obtained by polymerizing 0 to 20% by weight, and the outermost layer is a hard resin layer (see Patent Document 3).

【0016】更に、アクリル系軟質樹脂の他の例を示
す。(A)メチルメタクリレート80〜98.99重量
%、炭素数1〜8のアルキル基を持つアクリル酸アルキ
ルエステル1〜20重量%、多官能性グラフト剤0.0
1〜1重量%及び多官能性架橋剤0〜0.5重量%から
なる単量体混合物を重合してなる最内層の硬質重合体層
5〜30重量部;(B)炭素数1〜8のアルキル基を持
つアクリル酸アルキルエステル70〜99.5重量%、
メチルメタクリレート0〜30重量%、多官能性グラフ
ト剤0.5〜5重量%及び多官能性架橋剤0〜5重量%
からなる単量体混合物を重合してなる中間層の硬質重合
体層20〜45重量部;(C)メチルメタクリレート9
0〜99重量%及び炭素数1〜8のアルキル基を持つア
クリル酸アルキルエステル10〜1重量%からなる単量
体混合物を重合してなる最外層の硬質重合体層50〜7
5重量部からなり、平均粒度が0.01〜0.3μmの
アクリル系軟質多層構造樹脂である(特許文献4参
照)。
Further, another example of the acrylic soft resin will be shown. (A) 80 to 98.99% by weight of methyl methacrylate, 1 to 20% by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, and a polyfunctional grafting agent of 0.0
5 to 30 parts by weight of the innermost hard polymer layer obtained by polymerizing a monomer mixture consisting of 1 to 1% by weight and a polyfunctional crosslinking agent 0 to 0.5% by weight; (B) a carbon number of 1 to 8 70 to 99.5% by weight of alkyl acrylate having an alkyl group of
Methyl methacrylate 0-30% by weight, polyfunctional grafting agent 0.5-5% by weight and polyfunctional crosslinking agent 0-5% by weight
20 to 45 parts by weight of a hard polymer layer as an intermediate layer obtained by polymerizing a monomer mixture consisting of: (C) methyl methacrylate 9
The outermost hard polymer layers 50 to 7 obtained by polymerizing a monomer mixture of 0 to 99% by weight and 10 to 1% by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms.
It is an acrylic soft multilayer structure resin composed of 5 parts by weight and having an average particle size of 0.01 to 0.3 μm (see Patent Document 4).

【0017】本発明の合成樹脂レザーにおいては、熱可
塑性ポリウレタンとアクリル系軟質樹脂との配合割合
は、熱可塑性ポリウレタン50〜95重量%、アクリル
系軟質樹脂60〜5重量%、好ましくは熱可塑性ポリウ
レタン60〜90重量%、アクリル系軟質樹脂40〜1
0重量%、より好ましくは熱可塑性ポリウレタン70〜
90重量%、アクリル系軟質樹脂30〜10重量%であ
る。熱可塑性ポリウレタンが50重量%未満では引裂強
度が十分でなく、縫い目が広がったり、裂けやすく、一
方熱可塑性ポリウレタンが95重量%を越えると硬い感
触となりレザーとしての使用に適さなくなり、またカレ
ンダー加工の加工温度が高くなり分解する支障がある。
In the synthetic resin leather of the present invention, the blending ratio of the thermoplastic polyurethane and the acrylic soft resin is 50 to 95% by weight of the thermoplastic polyurethane, 60 to 5% by weight of the acrylic soft resin, and preferably the thermoplastic polyurethane. 60-90% by weight, acrylic soft resin 40-1
0% by weight, more preferably thermoplastic polyurethane 70-
90% by weight and 30 to 10% by weight of the acrylic soft resin. If the thermoplastic polyurethane is less than 50% by weight, the tear strength is not sufficient and the seams are widened or easily torn, while if the thermoplastic polyurethane exceeds 95% by weight, it has a hard feel and is not suitable for use as a leather. There is a problem that the processing temperature rises and it decomposes.

【0018】混合樹脂層に可塑剤を配合すると、製品の
柔軟性、手触りを改善できる。また、可塑剤の配合は混
合樹脂のカレンダー加工の加工温度を下げることがで
き、そのため熱可塑性ポリウレタンの加工時の分解を抑
制できる。可塑剤としては、フタル酸ジ2−エチルヘキ
シル、フタル酸イソブチル、フタル酸ジイソデシルなど
のフタル酸エステル;トリメリット酸トリ−2エチルヘ
キシルなどのトリメリット酸エステル;ジ−2エチルヘ
キシルアジペート、ジ−イソノニルアジペート、ジ−2
エチルヘキシルセバケートなどの脂肪族二塩基酸エステ
ル;エポキシ化大豆油、エポキシステアリン酸ブチルな
どのエポキシ系可塑剤、リン酸トリクレジルなどのリン
酸エステル系、アセチルクエン酸トリブチルなどのクエ
ン酸エステルなどが用いられる。このうち、可塑化効率
が高く、且つブリード等の問題が少ないという観点か
ら、特に、フタル酸エステル、トリメリット酸エステル
などの芳香族カルボン酸エステルが好ましく用いられ
る。可塑剤の配合量は、混合樹脂100重量部に対し0
〜50重量部、好ましくは3〜20重量部である。大量
に配合すると移行、ブリードを起こすので好ましくな
い。
By incorporating a plasticizer into the mixed resin layer, the flexibility and feel of the product can be improved. In addition, the blending of the plasticizer can lower the processing temperature of the calendar processing of the mixed resin, and therefore can suppress the decomposition of the thermoplastic polyurethane during processing. Examples of the plasticizer include phthalic acid esters such as di-2-ethylhexyl phthalate, isobutyl phthalate and diisodecyl phthalate; trimellitic acid esters such as tri-2 ethylhexyl trimellitate; di-2 ethylhexyl adipate and di-isononyl adipate. , Di-2
Aliphatic dibasic acid esters such as ethylhexyl sebacate; epoxidized soybean oil, epoxy plasticizers such as butyl epoxystearate, phosphate ester systems such as tricresyl phosphate, and citric acid esters such as tributyl acetylcitrate To be Among these, aromatic carboxylic acid esters such as phthalic acid esters and trimellitic acid esters are particularly preferably used from the viewpoints of high plasticization efficiency and less problems such as bleeding. The blending amount of the plasticizer is 0 based on 100 parts by weight of the mixed resin.
-50 parts by weight, preferably 3-20 parts by weight. Mixing in a large amount is not preferable because it causes migration and bleeding.

【0019】混合樹脂層には、更に必要に応じて、通常
合成樹脂の配合に使用される滑剤、紫外線吸収剤、光安
定剤、顔料、抗菌剤などが配合されていてもよい。滑剤
としてはステアリン酸のカルシウム、マグネシウム、亜
鉛、バリウムなどの脂肪族金属塩、ポリエチレンワック
ス、ステアリン酸、アルキレンビス脂肪酸アミドなどが
用いられる。紫外線吸収剤としては2−(2’−ヒドロ
キシ−5’−メチルフェニル)ベンゾトリアゾールなど
のベンゾトリアゾール系紫外線吸収剤等が用いられる。
光安定剤としてはビス−(2,2,6,6−テトラメチ
ル−4−ピペリジル)セバケートなどのヒンダードアミ
ン系光安定剤等が用いられる。抗菌剤としては銀系無機
抗菌剤などが用いられる。
The mixed resin layer may further contain, if necessary, a lubricant, an ultraviolet absorber, a light stabilizer, a pigment, an antibacterial agent and the like which are usually used for compounding synthetic resins. As the lubricant, aliphatic metal salts of stearic acid such as calcium, magnesium, zinc and barium, polyethylene wax, stearic acid, alkylenebis fatty acid amide and the like are used. As the UV absorber, a benzotriazole-based UV absorber such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole is used.
As the light stabilizer, a hindered amine light stabilizer such as bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate is used. As the antibacterial agent, a silver-based inorganic antibacterial agent or the like is used.

【0020】本発明の基材の少なくとも片面に設けた混
合樹脂層はショアA硬度60〜80を有するものが好ま
しい。この硬度は、ショアA硬度65〜90の熱可塑性
ポリウレタンとショアA硬度50〜80のアクリル系軟
質樹脂とを使用することによって得ることができる。そ
して、この硬度にすることによって、ポリ塩化ビニル1
00重量部に可塑剤(フタル酸ジエチルヘキシル)を7
0〜100重量部配合した軟質ポリ塩化ビニル層を有す
るレザーと同様な柔軟さ、手触り、感触を有するレザー
が得られる。
The mixed resin layer provided on at least one surface of the base material of the present invention preferably has a Shore A hardness of 60-80. This hardness can be obtained by using a thermoplastic polyurethane having a Shore A hardness of 65 to 90 and an acrylic soft resin having a Shore A hardness of 50 to 80. Then, by setting this hardness, polyvinyl chloride 1
7 parts of plasticizer (diethylhexyl phthalate) to 00 parts by weight
A leather having the same softness, touch and feel as the leather having a soft polyvinyl chloride layer blended in an amount of 0 to 100 parts by weight can be obtained.

【0021】本発明の合成樹脂レザーは次のようにして
製造する。すなわち、例えば、熱可塑性ポリウレタンと
アクリル系軟質樹脂とを所定の割合で混合し、また必要
に応じて可塑剤、滑剤などの添加剤を配合し、良く混練
し、その後カレンダー成形或は押出し成形によって0.
1〜5mmの厚さのシートに成形して混合樹脂シートを
作成する。基材の編織物に接着剤を塗布し、その接着剤
塗布面に前記混合樹脂シートを重ね多少加熱加圧して、
ずれない程度に接着させる。次いで、必要に応じてマー
ブルプリントし、つや消し処理剤を塗布し、その後にシ
ートを150〜200℃に加熱し、絞ロールで加圧す
る。この加圧によって基材と混合樹脂シートが一体化
し、レザーが得られる。また、基材の編織物の両面に混
合樹脂層を設けてもよい。またポリプロピレンフォーム
シート、ポリウレタンフォームシートなどの軟質発泡体
シートに接着剤を塗布し、この軟質発泡体シート面に、
上記と同様にして混合樹脂層を形成させてレザーとして
もよい。特に、軟質発泡体シートとしてポリウレタンフ
ォームシートを用いた場合は、接着剤なしで一体化する
ことが可能である。
The synthetic resin leather of the present invention is manufactured as follows. That is, for example, thermoplastic polyurethane and acrylic soft resin are mixed in a predetermined ratio, and if necessary, additives such as a plasticizer and a lubricant are blended, kneaded well, and then calendered or extruded. 0.
A mixed resin sheet is prepared by molding into a sheet having a thickness of 1 to 5 mm. An adhesive is applied to the knitted fabric of the base material, and the mixed resin sheet is overlaid on the adhesive-applied surface and heated and pressed to some extent,
Adhere to the extent that it does not slip. Then, if necessary, marble printing is performed, a matting agent is applied, and then the sheet is heated to 150 to 200 ° C. and pressed by a squeeze roll. By this pressurization, the base material and the mixed resin sheet are integrated to obtain a leather. Moreover, you may provide a mixed resin layer on both surfaces of the knitted fabric of a base material. In addition, an adhesive is applied to a soft foam sheet such as a polypropylene foam sheet or a polyurethane foam sheet, and the soft foam sheet surface is
A leather may be formed by forming a mixed resin layer in the same manner as above. In particular, when a polyurethane foam sheet is used as the soft foam sheet, it can be integrated without an adhesive.

【0022】基材と混合樹脂シートの接着には、エチレ
ン−酢酸ビニル共重合体系エマルジョン、ポリ塩化ビニ
ルペースト、二液型ポリウレタン接着剤などが用いられ
る。この接着剤は、基布面に塗布しても、また混合樹脂
シート面に塗布してもよい。基材とポリプロピレンフォ
ームシート、及びポリプロピレンフォームシートと混合
樹脂シートを接着させるために、ポリプロピレンフォー
ムシートの積層面にポリウレタン系プライマー層又はエ
ポキシ系樹脂プライマー層などの接着性を良くするため
のプライマー層を設けてもよい。
To bond the base material to the mixed resin sheet, an ethylene-vinyl acetate copolymer emulsion, polyvinyl chloride paste, two-component polyurethane adhesive, etc. are used. This adhesive may be applied to the base cloth surface or the mixed resin sheet surface. In order to bond the base material and the polypropylene foam sheet, and the polypropylene foam sheet and the mixed resin sheet, a primer layer for improving adhesion such as a polyurethane primer layer or an epoxy resin primer layer is provided on the laminated surface of the polypropylene foam sheet. It may be provided.

【0023】上記の混合樹脂をシートに成形するにはカ
レンダー加工によるのが好ましいが、混合樹脂に(メ
タ)アクリル系重合体を配合することによってカレンダ
ー加工時の溶融張力が調整でき、カレンダー加工を円滑
にすることができる。この(メタ)アクリル系重合体
は、例えば、メタクリル酸メチル50〜90重量%及び
これと共重合可能な他のエチレン系不飽和単量体50〜
5重量%を共重合して得られる分子量50〜500万の
共重合体が好ましい。他のエチレン系不飽和単量体は、
例えば、炭素数2〜18のアルコールのメタクリル酸エ
ステル、炭素数2〜18のアルコールのアクリル酸エス
テル、スチレン、α−メチルスチレン、アクリロニトリ
ル、マレイン酸、イタコン酸などである。(メタ)アク
リル系重合体の配合量は、混合樹脂100重量部に対し
0〜30重量部、好ましくは2〜10重量部である。
The above-mentioned mixed resin is preferably formed into a sheet by calendering. However, by blending the mixed resin with a (meth) acrylic polymer, the melt tension during calendering can be adjusted and calendering can be performed. Can be smooth. The (meth) acrylic polymer is, for example, 50 to 90% by weight of methyl methacrylate and 50 to 90% of another ethylenically unsaturated monomer copolymerizable therewith.
A copolymer having a molecular weight of 500 to 5,000,000 obtained by copolymerizing 5% by weight is preferable. Other ethylenically unsaturated monomers are
For example, methacrylic acid ester of alcohol having 2 to 18 carbon atoms, acrylic acid ester of alcohol having 2 to 18 carbon atoms, styrene, α-methylstyrene, acrylonitrile, maleic acid, itaconic acid and the like. The blending amount of the (meth) acrylic polymer is 0 to 30 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the mixed resin.

【0024】更に、混合樹脂層に、炭酸カルシウム、酸
化アンチモン、コロイド状シリカ、ケイ酸マグネシウ
ム、水酸化マグネシウムどの無機物質粉末を配合するこ
とにより、カレンダー加工時の粘着性を低下させて、カ
レンダー加工を円滑にすることができる。特に炭酸カル
シウムが好ましい。無機質の配合量は、混合樹脂100
重量部に対し0〜30重量部、好ましくは5〜20重量
部である。
Further, by mixing inorganic carbonate powder such as calcium carbonate, antimony oxide, colloidal silica, magnesium silicate and magnesium hydroxide into the mixed resin layer, the tackiness during calendering is reduced and calendering is performed. Can be smoothed. Calcium carbonate is particularly preferable. The amount of the inorganic compound is 100% of the mixed resin.
The amount is 0 to 30 parts by weight, preferably 5 to 20 parts by weight.

【0025】本発明の合成樹脂レザーは、自動車などの
車両内装(座席、ヘッドレスト、トノカバー、サンバイ
ザー、天井など)、室内の内装材、二輪車のサドルの表
皮材、家具(椅子、ソファーなど)の表皮材、バッグな
ど袋物の素材、カッパ、前掛けなどに用いられる。また
基材の編織物の両面に混合樹脂層を設けたものはフレキ
シブルコンテナーの材料に用いられる。また、軟質発泡
シートを基材としたレザーも車両内装(インストルメン
トパネル、ドア、天井等)に用いられる。
The synthetic resin leather of the present invention is used for vehicle interiors such as automobiles (seats, headrests, tonneau covers, sun visors, ceilings, etc.), interior interior materials, motorcycle saddle skin materials, furniture (chairs, sofas, etc.). It is used for skin materials, bag materials such as bags, kappa, and apron. Further, a base material having a mixed resin layer on both sides of a knitted fabric is used as a material for a flexible container. In addition, leather using a soft foam sheet as a base material is also used for vehicle interiors (instrument panels, doors, ceilings, etc.).

【0026】[0026]

【実施例】次に実施例、比較例を示し、本発明を更に詳
しく説明する。 実施例1〜5、比較例1〜2 実施例1〜5として、熱可塑性ポリウレタン(UHE−
75A:三菱化学株式会社製、特殊エーテル系ポリオー
ルを使用したポリウレタン、ショアA硬度77)、熱可
塑性ポリウレタン(UE−80:三菱化学社製、エーテ
ル系ポリオール使用、ショアA硬度80)、アクリル系
軟質樹脂(SA−1000P:株式会社クラレ製、ショ
ア硬度70)、メタクリル酸メチル−アクリル酸アルキ
ル共重合体(メタブレンP−530A:三菱レイヨン株
式会社製)、炭酸カルシウム(NS−A:日東粉化工業
社製)、抗酸化剤(PEP−36:旭電化工業株式会社
製)、可塑剤(#124:花王株式会社製、フタル酸エ
ステル)、滑剤(ポリエチレンワックス)、紫外線吸収
剤(ベンゾトリアゾール系)、光安定剤(HALS)及
び顔料を表1の実施例1〜5及び比較例1〜2に示す割
合(数字は重量部を示す)で配合し、カレンダー成形によ
って厚さ0.25mmのシートを成形した。レーヨンと
ポリエステル繊維の7:3混紡糸の天竺編物にエチレン
−酢酸ビニル系エマルジョン接着剤を塗布した。この接
着剤塗布面に前記シートを重ね多少加熱加圧して、ずれ
ない程度に接着させた。その後にシートを180℃に加
熱し、常温の絞ロールとゴムロールとで加圧した。天竺
編物と混合樹脂シートが一体化し、絞模様がある合成樹
脂レザーが得られた。この実施例、比較例で製造したレ
ザーについて、表面傷付き性、耐寒性、高周波ウェルダ
ー性、柔軟性、縫い目の広がり状態、ロール加工性、耐
熱性、耐光性を調べた。その結果を併せて表1に示す。
EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Examples 1-5, Comparative Examples 1-2 As Examples 1-5, thermoplastic polyurethane (UHE-
75A: Mitsubishi Chemical Co., polyurethane using special ether-based polyol, Shore A hardness 77), thermoplastic polyurethane (UE-80: Mitsubishi Chemical Co., using ether-based polyol, Shore A hardness 80), acrylic soft Resin (SA-1000P: manufactured by Kuraray Co., Ltd., Shore hardness 70), methyl methacrylate-alkyl acrylate copolymer (Metabrene P-530A: manufactured by Mitsubishi Rayon Co., Ltd.), calcium carbonate (NS-A: Nitto Koka Kogyo) Company), antioxidant (PEP-36: Asahi Denka Kogyo Co., Ltd.), plasticizer (# 124: Kao Corporation, phthalate ester), lubricant (polyethylene wax), ultraviolet absorber (benzotriazole type). The proportions of the light stabilizer (HALS) and the pigment shown in Examples 1 to 5 and Comparative Examples 1 and 2 in Table 1 (the numbers are parts by weight). (Shown) and were calendered to form a sheet having a thickness of 0.25 mm. An ethylene-vinyl acetate emulsion adhesive was applied to a plain knitted fabric of 7: 3 mixed yarn of rayon and polyester fibers. The above-mentioned sheet was placed on this adhesive-coated surface, heated and pressed to some extent, and bonded so as not to shift. After that, the sheet was heated to 180 ° C. and pressed with a squeeze roll and a rubber roll at room temperature. The synthetic knitted fabric and the mixed resin sheet were integrated, and synthetic resin leather with a tie pattern was obtained. The leather produced in this example and the comparative example were examined for surface scratch resistance, cold resistance, high frequency welder property, flexibility, seam spread state, roll processability, heat resistance, and light resistance. The results are also shown in Table 1.

【0027】[0027]

【表1】 [Table 1]

【0028】表1において、表面傷付き性は、JIS
K 7204に準拠して測定した。但し、摩耗輪はCS
−10、荷重は1kgf×2000回にした。耐寒性
は、JIS K 6772に準拠して合格する最も低い温
度を示した。高周波ウェルダー性は、市販の機械を用い
て実際に溶着加工し、混合樹脂同士の接着性を剥離試験
によって評価した。○は剥離時に材料破壊、×は剥離時
に界面剥離を表す。柔軟性は、製造した各レザーを手で
触り、その感触を軟質ポリ塩化ビニルレザー(合成樹脂
層がポリ塩化ビニル100重量部に可塑剤フタル酸ジエ
チルヘキシル100重量部配合したポリ塩化ビニル組成
物であるレザー)と対比して評価した。○は軟質ポリ塩
化ビニルレザーと同等の感触を有する、△は軟質ポリ塩
化ビニルレザーよりやや硬い感触を有する、×は感触が
硬く、軟質ポリ塩化ビニルレザーの代替不可、を表す。
In Table 1, the surface scratch resistance is JIS
It measured based on K7204. However, wear wheels are CS
-10, the load was 1 kgf x 2000 times. Cold resistance showed the lowest temperature which passed according to JIS K 6772. The high-frequency welder property was evaluated by performing a welding process using a commercially available machine and adhering the mixed resins to each other by a peeling test. ◯ indicates material destruction during peeling, and x indicates interfacial peeling during peeling. As for flexibility, each produced leather is touched by hand, and the feel is soft polyvinyl chloride leather (a polyvinyl chloride composition in which 100 parts by weight of a synthetic resin layer is mixed with 100 parts by weight of plasticizer diethylhexyl phthalate as a plasticizer). It was evaluated in comparison with a certain leather). ◯ means that the feel is equivalent to that of soft polyvinyl chloride leather, Δ means that the feel is slightly harder than that of soft polyvinyl chloride leather, and that x means that the feel is hard and the soft polyvinyl chloride leather cannot be replaced.

【0029】縫い目の広がり状態は、各レザーを使用し
て椅子の上貼りを縫製で行ない、その縫い目の状態を目
視で観察した。○は縫い目が広がらない、×は縫い目が
拡がり商品性がない、を表す。ロール加工性は、カレン
ダー加工温度(適切な溶融温度になっている)で30分
経過後の粘着性で加工性を評価した。○は適度に粘着、
△はやや粘着、×は粘着、を表す。耐熱性は、110℃
で500時間放置した後の変色を測定評価した。耐光性
は、JIS−B−7751に準拠して、ブラックパネル
温度83℃の紫外線カーボンアーク式耐光試験機で30
0時間照射後の変色を評価した。
The spread state of the seam was observed by visually observing the state of the seam by stitching the top of the chair by sewing using each leather. ○ indicates that the seam does not spread, and × indicates that the seam spreads and the product is not commercially available. The roll processability was evaluated by the adhesiveness after 30 minutes at the calendering temperature (which is an appropriate melting temperature). ○ is moderately sticky,
Δ indicates slightly tacky, and x indicates tacky. Heat resistance is 110 ° C
Discoloration after standing for 500 hours was measured and evaluated. The light resistance is 30 with an ultraviolet carbon arc type light resistance tester with a black panel temperature of 83 ° C. according to JIS-B-7751.
The discoloration after 0 hour irradiation was evaluated.

【0030】[0030]

【発明の効果】本発明の合成樹脂レザーは、従来の軟質
ポリ塩化ビニルレザーと同様な柔軟性、手触りを有し、
復元性、耐寒性、耐表面傷付き性がよく、また高周波ウ
エルダーによって溶着加工できる利点があると共に、ミ
シンなどで縫製したとき、縫い目がが広がったり、縫い
目から裂けたりすることがない。したがって、自動車の
車両内装材、袋物素材、家具の表皮材として有用であ
り、従来の軟質ポリ塩化ビニルレザーに代替できる合成
樹脂レザーである。
EFFECT OF THE INVENTION The synthetic resin leather of the present invention has the same flexibility and feel as conventional soft polyvinyl chloride leather,
It has good restoration properties, cold resistance, and resistance to surface scratches, and has the advantage that it can be welded by a high-frequency welder, and when sewing with a sewing machine etc., the seams do not spread or tear from the seams. Therefore, it is a synthetic resin leather which is useful as a vehicle interior material for automobiles, a bag material, and a skin material for furniture, and which can replace conventional soft polyvinyl chloride leather.

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4F055 AA21 BA12 DA08 DA17 EA02 EA04 EA23 FA10 FA18 FA39 FA40 GA20 GA32    ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F055 AA21 BA12 DA08 DA17 EA02                       EA04 EA23 FA10 FA18 FA39                       FA40 GA20 GA32

Claims (6)

【特許請求の範囲】[Claims] 【請求項1】基材の少なくとも片面に、ショアA硬度6
5〜90の熱可塑性ポリウレタン50〜95重量%とシ
ョアA硬度50〜80のアクリル系軟質樹脂50〜5重
量%との混合樹脂層を設けてなり、且つ混合樹脂層のシ
ョアA硬度が60〜80であることを特徴とする合成樹
脂レザー。
1. A Shore A hardness of 6 on at least one side of a substrate.
A mixed resin layer of 50 to 95 wt% of thermoplastic polyurethane of 5 to 90 and 50 to 5 wt% of acrylic soft resin of Shore A hardness of 50 to 80 is provided, and the Shore A hardness of the mixed resin layer is 60 to. 80 synthetic resin leather.
【請求項2】混合樹脂層が可塑剤を含む請求項1記載の
合成樹脂レザー。
2. The synthetic resin leather according to claim 1, wherein the mixed resin layer contains a plasticizer.
【請求項3】基材が織物、編物又は不織布或は軟質発泡
体シートである請求項1又は2記載の合成樹脂レザー。
3. The synthetic resin leather according to claim 1, wherein the base material is a woven fabric, a knitted fabric, a non-woven fabric or a soft foam sheet.
【請求項4】ショアA硬度65〜90の熱可塑性ポリウ
レタン50〜95重量%とショアA硬度50〜80のア
クリル系軟質樹脂50〜5重量%との混合樹脂をカレン
ダー加工してシートに成形し、該シートと基材とを積層
一体化することを特徴とする請求項1記載の合成樹脂レ
ザーの製造方法。
4. A sheet is formed by calendering a mixed resin of 50 to 95% by weight of a thermoplastic polyurethane having a Shore A hardness of 65 to 90 and 50 to 5% by weight of an acrylic soft resin having a Shore A hardness of 50 to 80. The synthetic resin leather manufacturing method according to claim 1, wherein the sheet and the base material are laminated and integrated.
【請求項5】混合樹脂に(メタ)アクリル系重合体を配
合することを特徴とする請求項4記載の合成樹脂レザー
の製造方法。
5. The method for producing synthetic resin leather according to claim 4, wherein a (meth) acrylic polymer is blended with the mixed resin.
【請求項6】混合樹脂に炭酸カルシウムを配合すること
を特徴とする請求項4又は5記載の合成樹脂レザーの製
造方法。
6. The method for producing a synthetic resin leather according to claim 4, wherein calcium carbonate is mixed with the mixed resin.
JP2002263598A 2001-09-13 2002-09-10 Synthetic resin leather Expired - Lifetime JP4190236B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002263598A JP4190236B2 (en) 2001-09-13 2002-09-10 Synthetic resin leather

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2001278041 2001-09-13
JP2001-278041 2001-09-13
JP2002263598A JP4190236B2 (en) 2001-09-13 2002-09-10 Synthetic resin leather

Publications (2)

Publication Number Publication Date
JP2003166181A true JP2003166181A (en) 2003-06-13
JP4190236B2 JP4190236B2 (en) 2008-12-03

Family

ID=26622147

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2002263598A Expired - Lifetime JP4190236B2 (en) 2001-09-13 2002-09-10 Synthetic resin leather

Country Status (1)

Country Link
JP (1) JP4190236B2 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015942A (en) * 2003-06-25 2005-01-20 Okamoto Ind Inc Flame-retardant synthetic resin leather
JP2005023448A (en) * 2003-06-30 2005-01-27 Okamoto Ind Inc Synthetic resin leather
JP2009109399A (en) * 2007-10-31 2009-05-21 Nintendo Co Ltd Weight applying unit for calibration and weight applying method for calibration
JP2011214191A (en) * 2010-03-31 2011-10-27 Honda Motor Co Ltd Synthetic resin leather and method for producing the same
JP2011214192A (en) * 2010-03-31 2011-10-27 Honda Motor Co Ltd Synthetic resin leather and manufacturing method of the same
JP2012193481A (en) * 2011-03-17 2012-10-11 Okamoto Kk Synthetic resin leather
JP2013002027A (en) * 2011-06-21 2013-01-07 Chuo Rika Kogyo Corp Artificial leather
WO2015156295A1 (en) * 2014-04-07 2015-10-15 株式会社カネカ Thermoplastic polyurethane resin composition, conductor covering material, and manufacturing method of these
CN106945355A (en) * 2017-03-20 2017-07-14 浙江亦阳新材料有限公司 A kind of environment-friendly type Compound Fabric and its preparation technology
US9993695B2 (en) 2013-10-10 2018-06-12 Bridgestone Sports Co., Ltd. Golf ball manufacturing method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04226154A (en) * 1990-06-21 1992-08-14 Bayer Ag Thermoplastic composition comprising polyurethane and partially crosslinked alkyl acrylate copolymer
JP2001114911A (en) * 1999-10-22 2001-04-24 Araco Corp Upholstery for automobile interior trim

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04226154A (en) * 1990-06-21 1992-08-14 Bayer Ag Thermoplastic composition comprising polyurethane and partially crosslinked alkyl acrylate copolymer
JP2001114911A (en) * 1999-10-22 2001-04-24 Araco Corp Upholstery for automobile interior trim

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015942A (en) * 2003-06-25 2005-01-20 Okamoto Ind Inc Flame-retardant synthetic resin leather
JP2005023448A (en) * 2003-06-30 2005-01-27 Okamoto Ind Inc Synthetic resin leather
JP2009109399A (en) * 2007-10-31 2009-05-21 Nintendo Co Ltd Weight applying unit for calibration and weight applying method for calibration
US8617714B2 (en) 2010-03-31 2013-12-31 Okamoto Industries, Inc. Synthetic resin leather and manufacturing method of the same
JP2011214191A (en) * 2010-03-31 2011-10-27 Honda Motor Co Ltd Synthetic resin leather and method for producing the same
JP2011214192A (en) * 2010-03-31 2011-10-27 Honda Motor Co Ltd Synthetic resin leather and manufacturing method of the same
JP2012193481A (en) * 2011-03-17 2012-10-11 Okamoto Kk Synthetic resin leather
JP2013002027A (en) * 2011-06-21 2013-01-07 Chuo Rika Kogyo Corp Artificial leather
US9993695B2 (en) 2013-10-10 2018-06-12 Bridgestone Sports Co., Ltd. Golf ball manufacturing method
WO2015156295A1 (en) * 2014-04-07 2015-10-15 株式会社カネカ Thermoplastic polyurethane resin composition, conductor covering material, and manufacturing method of these
JPWO2015156295A1 (en) * 2014-04-07 2017-04-13 株式会社カネカ Thermoplastic polyurethane-based resin composition, conductor coating material, and production method thereof
US10311995B2 (en) 2014-04-07 2019-06-04 Kaneka Corporation Thermoplastic polyurethane resin composition, conductor covering material, and manufacturing method of these
CN106945355A (en) * 2017-03-20 2017-07-14 浙江亦阳新材料有限公司 A kind of environment-friendly type Compound Fabric and its preparation technology

Also Published As

Publication number Publication date
JP4190236B2 (en) 2008-12-03

Similar Documents

Publication Publication Date Title
JP5769382B2 (en) Synthetic resin leather and method for producing the same
EP1835068B1 (en) Synthetic resin leather
JP2002129482A (en) Synthetic resin leather
US6863953B2 (en) Surface material of urethane resin and a method for preparation thereof
JP2003166181A (en) Synthetic resin leather
JP4727394B2 (en) Synthetic leather
JP2003211612A (en) Urethane resin skin material
JP7396812B2 (en) synthetic resin leather
JP4230293B2 (en) Synthetic leather
JP2011214191A (en) Synthetic resin leather and method for producing the same
JP4376005B2 (en) Flame retardant synthetic resin leather
JP4489985B2 (en) Synthetic leather
JP3864330B2 (en) Method for producing sheet molding material for vacuum forming or pressure forming
KR100903772B1 (en) A surface material of urethane resin and a method for preparation thereof
JP5676209B2 (en) Synthetic leather
JP2002155477A (en) Acrylic resin leather
JP4570236B2 (en) Synthetic leather
JP2002370330A (en) Tarpaulin
JP4413640B2 (en) Thermoplastic polyurethane composition for calendering and film / sheet comprising the same
JP3031616B2 (en) Waterproof sheet that can be heat-sealed
JPH0939169A (en) Interior material for vehicle
JP2019136989A (en) Sheet for floor marking
JP2022013701A (en) Synthetic leather
JPH06155670A (en) Thermally stitch-weldable waterproof sheet and sewing method
JPS61123541A (en) Flexible polyvinyl chloride laminate for thermoforming processing

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20050905

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20080422

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20080507

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20080704

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20080902

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20080916

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110926

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Ref document number: 4190236

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110926

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120926

Year of fee payment: 4

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120926

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130926

Year of fee payment: 5

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

EXPY Cancellation because of completion of term