JPH1136180A - Colored synthetic resin sheet or colored synthetic resin composition, and its production - Google Patents
Colored synthetic resin sheet or colored synthetic resin composition, and its productionInfo
- Publication number
- JPH1136180A JPH1136180A JP9208484A JP20848497A JPH1136180A JP H1136180 A JPH1136180 A JP H1136180A JP 9208484 A JP9208484 A JP 9208484A JP 20848497 A JP20848497 A JP 20848497A JP H1136180 A JPH1136180 A JP H1136180A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- porous
- polyurethane
- sheet
- color
- 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
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 58
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002649 leather substitute Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 66
- 239000004814 polyurethane Substances 0.000 abstract description 66
- 238000004040 coloring Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 238000004043 dyeing Methods 0.000 abstract description 6
- 238000007639 printing Methods 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 polybutylene adipate Polymers 0.000 description 14
- 239000000976 ink Substances 0.000 description 13
- 239000004745 nonwoven fabric Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 230000000740 bleeding effect Effects 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000012463 white pigment Substances 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 210000000349 chromosome Anatomy 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Ink Jet (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Coloring (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液滴噴射手段を用
いて染色や塗装等の加色した合成樹脂シート又は、合成
樹脂組成物中でも人工皮革に関するものである。更に
は、染色や塗装等の加色可能な合成樹脂シート又は、合
成樹脂組成物中でも人工皮革の製造方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin sheet colored or dyed or painted using a droplet jetting means, or an artificial leather in a synthetic resin composition. Furthermore, the present invention relates to a synthetic resin sheet which can be colored, such as dyeing and painting, or a method for producing artificial leather even in a synthetic resin composition.
【０００２】[0002]
【従来の技術】合成樹脂シート又は、合成樹脂組成物中
でも人工皮革への加色は、従来グラビアロールプリン
ト、スクリーンプリント、転写紙等による加色方法に限
られていた。これらの方法は、いわゆる捺染であり、図
柄版と被染色体のシート状物が接触することで、加色す
るものである。この場合、色素が被染色体に転写される
ことから、被染色体がその上で色素が流動することなく
確実に染色される点がメリットである。この事から、こ
れらの染色方法では、合成樹脂を染色する色素を選択す
るだけで、着色が可能である。2. Description of the Related Art In a synthetic resin sheet or a synthetic resin composition, coloring of artificial leather has conventionally been limited to a coloring method using gravure roll printing, screen printing, transfer paper, or the like. These methods are so-called printing, in which the color is added by the contact between the design plate and the sheet-like material of the chromosome. In this case, since the dye is transferred to the chromosome, the merit is that the chromosome is reliably stained without the dye flowing thereon. For this reason, in these dyeing methods, coloring is possible only by selecting a dye for dyeing the synthetic resin.
【０００３】しかしながら、近年物品のカラフルさ、デ
ザインの変化が消費者から要求される中、これらの加色
方法では対応が困難となってきている。即ち、これらグ
ラビアロールプリント、スクリーンプリント、転写紙等
による着色方法では多色刷りの場合、色の数だけの図柄
版及び染色工程が必要となる。更には、１つのデザイン
に対しそれに必要な色の数だけの図柄版が必要であり、
デザインの変更に即座に対応できるものではない。[0003] However, in recent years, consumers have been required to change the colorfulness and design of articles, and it has become difficult to deal with these coloring methods. That is, in the case of the multicolor printing in the coloring method using gravure roll print, screen print, transfer paper, or the like, it is necessary to perform the same number of pattern plates and dyeing steps as the number of colors. Furthermore, for each design, you need as many design versions as you need.
It is not an immediate response to design changes.
【０００４】このような状況に対し、従来とは異なる新
しい、コンピュータと連動した、カラーインク噴射によ
る加色方法が開発された。例えば、布帛においては、特
公昭６２−５７７５０号、特公昭６３−３１５９４号、
特開平８−３１１７８５号等で、コンピュータによって
処理して得た情報に基いてインクジェット方式によって
加色する事が開示されている。また例えば、皮革におい
ては、特開平７−２１６４００号、特開平７−３３１５
８５号、特開平８−１１３８８１号、特開平８−２０９
５５３号で、前処理方法や後処理方法を含めてインクジ
ェット方式によって加色する事が開示されている。[0004] In order to cope with such a situation, a new color addition method using color ink jetting, which is linked to a computer, has been developed. For example, in the case of cloth, Japanese Patent Publication No. Sho 62-57750, Japanese Patent Publication No. Sho 63-31594,
Japanese Patent Application Laid-Open No. 8-31785 discloses that color is added by an ink jet method based on information obtained by processing by a computer. Further, for example, in the case of leather, JP-A-7-216400, JP-A-7-3315
No. 85, JP-A-8-113881, JP-A-8-209
No. 553 discloses that a color is added by an ink jet method including a pre-processing method and a post-processing method.
【０００５】しかしながら、これら開示された発明は、
インクの比較的浸透しやすい布帛や天然皮革を加色対象
としており、合成樹脂の様な樹脂を対象としているもの
ではない。合成樹脂が加色対象である場合、その表面が
滑らかであるが故にそのままでは噴射されたインクは弾
かれてしまい、噴射位置にインクが残留しにくいととも
に、にじみや混色の発生源となり易く、またそれが滑ら
かであるが故にインクが残留したとしても染色されにく
く、繊細な図柄を色とりどりに加色できるものでは無い
のである。[0005] However, these disclosed inventions are:
Fabrics and natural leathers to which ink is relatively easy to permeate are targeted for color addition, and are not intended for resins such as synthetic resins. If the synthetic resin is to be colored, the ejected ink is repelled as it is because the surface is smooth, and it is difficult for the ink to remain at the ejection position, and it is easy to become a source of bleeding and color mixing, and Because of its smoothness, even if the ink remains, it is hardly dyed, and it is not possible to add a delicate pattern in a multicolored manner.
【０００６】特開平７−３３１５８５号、特開平８−１
１３８８１号、特開平８−２０９５５３号において、請
求項に加色対象を皮革としているが、詳細な説明の中で
天然皮革を特に記載していること、実施例において天然
皮革への加色例しか無いことから、これら発明は、合成
樹脂シート或は、合成樹脂組成物、中でも人工皮革を対
象にした加色では無い。JP-A-7-331585 and JP-A-8-1
In 13881 and JP-A-8-209553, the subject of coloring is leather, but natural leather is specifically described in the detailed description. Since there is no such color, these inventions are not additive colors for synthetic resin sheets or synthetic resin compositions, especially artificial leather.
【０００７】[0007]
【発明が解決しようとする課題】従来の加色方法では行
えなかった、多くの色の加色を１工程で行え且つデザイ
ンの変更にも即座に対応可能な、液滴噴射手段を用いた
加色方法で、合成樹脂シート或は、合成樹脂組成物、中
でも人工皮革を加色することが課題である。[0006] An application using a droplet jetting means, which can perform addition of many colors in one step and can immediately respond to design changes, which cannot be performed by the conventional addition method. The problem is to add a color to a synthetic resin sheet or a synthetic resin composition, especially an artificial leather, by a color method.
【０００８】[0008]
【課題を解決するための手段】本発明は、以上の課題を
解決すべく種々検討し、液滴噴射手段を用いて加色した
多孔性合成樹脂シート或は、それにて加色した多孔性合
成樹脂組成物中でも人工皮革を見出し、本課題を解決し
た。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention has been studied in various ways, and a porous synthetic resin sheet colored by using a droplet jetting means or a porous synthetic resin sheet colored therewith is provided. This problem was solved by finding artificial leather even in the resin composition.
【０００９】そして本発明は、加色した合成樹脂シート
又は合成樹脂組成物を製造する方法であって、多孔質合
成樹脂層を形成し、次いで表皮を除去し、しかる後に液
的噴射することにより加色した多孔性合成シート又は多
孔性合成組成物の製造方法であり、更には、多孔質合成
樹脂層において多孔質の平均直径が１０〜２００ミクロ
ンであり、且つ最長の直径がシート面に対し実質垂直に
配向している多孔性合成シート又は多孔性合成組成物の
表皮を除去し、しかる後に液的噴射することにより加色
した多孔性合成シート又は多孔性合成組成物の製造方法
を見出したものである。The present invention provides a method for producing a colored synthetic resin sheet or a synthetic resin composition, comprising forming a porous synthetic resin layer, removing the skin, and then subjecting it to liquid jetting. A method for producing a colored synthetic sheet or a porous synthetic composition, wherein the porous synthetic resin layer has an average porous diameter of 10 to 200 microns, and the longest diameter is relative to the sheet surface. A method for producing a porous synthetic sheet or a porous synthetic composition colored by removing the skin of a porous synthetic sheet or a porous synthetic composition that is oriented substantially vertically, and then jetting liquid. Things.
【００１０】[0010]
【発明の実施の形態】本発明に用いられる合成樹脂は、
特に限定されるものでは無いが、例えば、ポリウレタン
である場合、ポリカーボネート系ポリウレタン、ポリテ
トラメチレンエーテルグリコール系ポリウレタン、ポリ
エステルエーテル系ポリウレタン、ポリブチレンアジペ
ート系ポリウレタン、ポリメチルペンタンアジペート系
ポリウレタン、ポリノナンジオールアジペート／ポリオ
クタンアジペート系ポリウレタン、ポリメチルペンタン
アジペート系ポリウレタンが挙げられ、その他の樹脂と
しては、ポリウレア、ポリウレタンポルイウレア、スチ
レンブタジエンゴム、アクリルニトリルブタジエンゴム
等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The synthetic resin used in the present invention comprises:
Although not particularly limited, for example, in the case of polyurethane, polycarbonate polyurethane, polytetramethylene ether glycol polyurethane, polyester ether polyurethane, polybutylene adipate polyurethane, polymethylpentane adipate polyurethane, polynonanediol adipate / Polyoctane adipate polyurethane and polymethylpentane adipate polyurethane. Other resins include polyurea, polyurethane polyurea, styrene butadiene rubber, and acrylonitrile butadiene rubber.
【００１１】さらに例えば、ポリウレタン、塩化ビニル
樹脂、アクリル酸エステル−スチレン共重合体、スチレ
ンブタジエン共重合体、ウレタン−塩化ビニル共重合体
の混合物が挙げられる。Further, for example, a mixture of a polyurethane, a vinyl chloride resin, an acrylate-styrene copolymer, a styrene-butadiene copolymer, and a urethane-vinyl chloride copolymer may be used.
【００１２】該合成樹脂を合成樹脂シートや合成樹脂組
成物に用いる場合、塗工液とするが、それがポリウレタ
ンである場合、例えば下記の塗工液である２０〜３０％
ポリテトラメチレンエーテル系ポリウレタン溶液が挙げ
られる。 塗工液 ポリテトラメチレンエーテル系ポリウレタン １００部 ジメチルホルムアミド（ＤＭＦ） ３０〜５０部 アニオン（及び又はカチオン及び又はノニオン）系界面活性剤 ０．５〜２部 シリコン ０．５〜２部 白顔料 １５部When the synthetic resin is used for a synthetic resin sheet or a synthetic resin composition, it is used as a coating liquid. When the synthetic resin is polyurethane, for example, the following coating liquid is used in an amount of 20 to 30%.
A polytetramethylene ether-based polyurethane solution may be used. Coating liquid Polytetramethylene ether-based polyurethane 100 parts Dimethylformamide (DMF) 30-50 parts Anion (and / or cation and / or nonion) surfactant 0.5-2 parts Silicon 0.5-2 parts White pigment 15 parts
【００１３】多孔質合成樹脂層において多孔質の平均直
径や形状について特に限定されるものでは無いが、多孔
質の平均直径が１０〜２００ミクロンであり、且つ最長
の直径がシート面に対し実質垂直に配向している場合、
液的噴射手段を用いた加色が良好に行うことができる。
多孔質の平均直径が１０ミクロン以下である場合、色材
の浸透量が少なく鮮明に加色できない場合があり、多孔
質の平均直径が２００ミクロン以上であれば、隣接する
色材も同時に一つの孔に入る確立が増加し、繊細な加色
が困難となる場合がある。The average diameter and shape of the porous synthetic resin layer are not particularly limited, but the average diameter of the porous layer is 10 to 200 microns and the longest diameter is substantially perpendicular to the sheet surface. If oriented
Coloring using the liquid jetting means can be performed favorably.
When the average diameter of the porous material is 10 μm or less, the coloring material may have a small amount of penetration and the color may not be sharply added. The probability of entering the holes increases, and delicate coloring may be difficult.
【００１４】多孔質合成樹脂層において、多孔質の平均
直径が１０〜２００ミクロンであり、且つ最長の直径が
シート面に対し実質垂直に配向している多孔質合成樹脂
を得るには、特に限定されるものではないが、例えば前
述の塗工液をシート状あるいは基材上で表面を覆い、水
洗することで形成することができる。In order to obtain a porous synthetic resin in which the average diameter of the porous synthetic resin layer is from 10 to 200 microns and the longest diameter is oriented substantially perpendicular to the sheet surface, there is no particular limitation. Although not required, for example, it can be formed by covering the surface of the above-mentioned coating solution on a sheet or on a base material and washing with water.
【００１５】多孔性合成樹脂シートを製造する場合、湿
式法でも乾式法でも特に限定されるものでは無い。例え
ば、ポリウレタンである場合、塗工液を離型紙等の上に
フィルム状に塗布し、温水中で湿式凝固させることで多
孔性合成樹脂シートとすることができる。また、それを
含む塗工液に水や発泡剤を添加し乾燥させることで多孔
性合成樹脂シートとすることができる。When producing a porous synthetic resin sheet, there is no particular limitation on the wet method or the dry method. For example, in the case of polyurethane, a porous synthetic resin sheet can be obtained by applying a coating solution in the form of a film on release paper or the like and wet-solidifying it in warm water. In addition, a porous synthetic resin sheet can be obtained by adding water or a foaming agent to a coating liquid containing the same and drying it.
【００１６】合成樹脂組成物は、例えば人工皮革、合成
皮革、接着剤の付加されたシート等が挙げられる。その
皮膜を形成する場合、合成樹脂は一般的な合成樹脂でも
十分であり、例えば、合成樹脂がポリウレタンである場
合、前述の樹脂が挙げられる。人工皮革を製造する場
合、湿式法でも乾式法でも特に限定されるものでは無い
が、以下の様な製造方法が挙げられる。Examples of the synthetic resin composition include artificial leather, synthetic leather, and a sheet to which an adhesive is added. When forming the film, a general synthetic resin is sufficient as the synthetic resin. For example, when the synthetic resin is polyurethane, the above-mentioned resins may be used. When producing artificial leather, there is no particular limitation on the wet method or the dry method, but the following production methods are exemplified.
【００１７】即ち、不織布シートに弾性高分子の溶液又
は水性エマルジョンを含浸させ、乾燥した上にポリウレ
タン弾性体１０〜３５重量％の水混和性有機溶剤溶液を
５０〜１０００ｇ／ｍ2 程度塗布し、これを水或は水と
溶剤の混合系中に浸せきして湿式凝固させた後、水洗し
た。これを乾燥することにより得られる。或は、離型紙
上にポリウレタン弾性体の有機溶剤溶液を塗布し乾燥し
て表皮層を形成した後、該表皮層上に２液反応型の弾性
高分子の溶液又は水性エマルジョンを塗布し、次いで乾
燥した後、該塗布面に不織布シートを熱圧着して貼り合
せ、熟成後離型紙を剥離することにより形成できる。That is, a non-woven fabric sheet is impregnated with a solution or an aqueous emulsion of an elastic polymer, dried and coated with a water-miscible organic solvent solution of 10 to 35% by weight of a polyurethane elastic material in an amount of about 50 to 1000 g / m 2 . This was immersed in water or a mixed system of water and a solvent for wet coagulation and then washed with water. It is obtained by drying this. Alternatively, after applying an organic solvent solution of a polyurethane elastic material on release paper and drying to form a skin layer, a two-pack reaction type elastic polymer solution or aqueous emulsion is applied on the skin layer, and then After drying, a non-woven fabric sheet is bonded to the coated surface by thermocompression bonding, and after aging, it can be formed by peeling off the release paper.
【００１８】人工皮革の基材としては、一般的な繊維質
及び合成樹脂（高分子弾性体）からなる構造物を示す
が、該繊維質としては、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、ポリアクリロ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、織成あるいは、交絡
させた編布、織布、不織布等が用いられる。As a base material of artificial leather, a structure made of general fibers and synthetic resin (polymer elastic body) is shown. Examples of the fibers include natural fibers such as cotton and hemp,
Knitted fabrics, woven fabrics, nonwoven fabrics, etc. obtained by knitting, weaving, or entangled various recycled fibers, such as regenerated fibers such as rayon, swoof, and acetate, and synthetic fibers such as polyester, polyamide, and polyacrylonitrile, alone or in combination.
【００１９】基材と皮膜を結合するには、前述の如く基
材を皮膜溶液に含浸させる方法や、互いに接着させる方
法、双方を組み合わせる方法がある。As described above, the method of bonding the substrate and the film includes a method of impregnating the substrate with the film solution, a method of bonding the substrates to each other, and a method of combining both.
【００２０】接着させる方法においては接着剤として、
基材と表皮層を接着しうるものであればいかなる接着剤
でもよいが、通常ウレタン系接着剤を用いる。ウレタン
系接着剤としては、１００％モジュラスが、１０〜１０
０ｋｇ／ｃｍ2 のものが好ましく、このウレタン系接着
剤におけるポリウレタンとしては、ポリカーボネート系
ポリウレタン、ポリテトラメチレンエーテル系ウレタ
ン、ポリプロピレンエーテル系ポリウレタン、ポリエス
テルエーテル系ポリウレタンが挙げられる。In the method of bonding, as an adhesive,
Any adhesive may be used as long as it can bond the base material and the skin layer, but a urethane-based adhesive is usually used. As a urethane-based adhesive, 100% modulus is 10 to 10%.
Preferably having from 0 kg / cm 2, as the polyurethane of the urethane-based adhesive, a polycarbonate-based polyurethane, polytetramethylene ether urethane, polypropylene ether polyurethane, polyester ether polyurethane.
【００２１】得られた多孔性合成樹脂シート又は、多孔
性合成樹脂組成物は、例えばサンドペーパー等の研削機
によってその表皮を除去する。このことによって、樹脂
内部の多孔性を表面に露出させるのである。この時、例
えば１００〜３００メッシュのサンドペーパーをロール
に巻き付けた研削機で多孔質ポリウレタン層の表皮を削
除する。The skin of the obtained porous synthetic resin sheet or porous synthetic resin composition is removed by a grinder such as sandpaper. This exposes the porosity inside the resin to the surface. At this time, for example, the skin of the porous polyurethane layer is removed by a grinder in which sandpaper of 100 to 300 mesh is wound around a roll.
【００２２】該色多孔性合成樹脂シート又は、多孔性合
成樹脂組成物は、液的噴射手段を用いた加色が可能とな
る。この場合、液的噴射手段として特に限定するもので
無く、各色材が噴射されて該色多孔性合成樹脂シート又
は、多孔性合成樹脂組成物の目的位置に加色されればよ
い。液的噴射手段としては例えば、The color porous synthetic resin sheet or the porous synthetic resin composition can be colored by using a liquid jetting means. In this case, the liquid jetting means is not particularly limited, and it is sufficient that each color material is jetted and colored at a target position of the color porous synthetic resin sheet or the porous synthetic resin composition. As the liquid jetting means, for example,
【００２３】この時、加色に用いられる色材としては、
従来からある染料や顔料を用いる事ができるが、インク
ジェット加色を行う場合でも染料、顔料のいずれかに限
定する必要は無い。顔料は、溶剤に不溶のため合成樹脂
によるエマルジョン形態で分散状態にして使用すること
が望ましい。一方、染料の場合は、水やアルコールに溶
け易いものが多く、使用方法も簡単である。本発明の加
色に使用する染料としては直接染料、反応染料、酸性染
料、カチオン染料、分散染料等を用いる事ができる。At this time, the coloring materials used for adding colors include:
Conventional dyes and pigments can be used, but it is not necessary to limit to either dyes or pigments when performing ink-jet coloring. Since the pigment is insoluble in a solvent, it is desirable to use the pigment in a dispersed state in the form of an emulsion of a synthetic resin. On the other hand, in the case of dyes, many of them are easily soluble in water or alcohol, and the method of use is simple. As the dye used for the coloring of the present invention, a direct dye, a reactive dye, an acid dye, a cationic dye, a disperse dye, or the like can be used.
【００２４】加色した多孔性合成樹脂シートは、表面を
覆ったり、保護するためのシート、例えば壁紙、カバ
ー、床材等のインテリア材に用いられる。また、加色し
た多孔性合成樹脂組成物中でも多孔性合成皮革は、天然
皮革の代替として用いられるもの、例えば靴、鞄、袋
物、衣服、家具、インテリア材等、多方面で使用でき
る。The colored porous synthetic resin sheet is used as a sheet for covering or protecting the surface, for example, an interior material such as a wallpaper, a cover, and a floor material. In addition, among the colored porous synthetic resin compositions, porous synthetic leather can be used in various fields such as those used as substitutes for natural leather, such as shoes, bags, bags, clothes, furniture, and interior materials.
【００２５】[0025]
【実施例】以下、本発明を実施例および比較例により更
に具体的に説明する。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
【００２６】（実施例１）多孔性ポリウレタンシートを
以下の如く製造した。即ち、厚み０．２ｍｍのポリエス
テルフィルム上に固形分２６％のポリテトラメチレンエ
ーテル系ポリウレタン溶液（下記塗工液）をドクターナ
イフにて１０００ｇ／ｍ2 塗工し、３５度温水にて湿式
凝固させた。 塗工液 ポリテトラメチレンエーテル系ポリウレタン １００部 ジメチルホルムアミド（ＤＭＦ） ４０部 アニオン系界面活性剤 ２部 シリコン ２部 白顔料 １５部(Example 1) A porous polyurethane sheet was produced as follows. That is, a polytetramethylene ether-based polyurethane solution having a solid content of 26% (the following coating solution) was coated on a 0.2 mm-thick polyester film with a doctor knife at 1000 g / m 2 and wet coagulated with 35 ° C warm water. Was. Coating liquid Polytetramethylene ether polyurethane 100 parts Dimethylformamide (DMF) 40 parts Anionic surfactant 2 parts Silicon 2 parts White pigment 15 parts
【００２７】更に、５０度温水にて充分水洗後１２０度
にて乾燥させ、厚み０．７ｍｍ、密度０．３７ｇ／ｃｍ
3 の多孔質ポリウレタンシートを得た。１８０メッシュ
のサンドペーパーをロールに巻き付けた研削機（ロール
回転数７００回／分、ラインスピード５ｍ／分、切削厚
み１０ミクロン）で該多孔質ポリウレタンシートの表面
を除去した。Further, after sufficiently washing with 50 ° C warm water and drying at 120 ° C, the thickness is 0.7 mm and the density is 0.37 g / cm.
3 was obtained. The surface of the porous polyurethane sheet was removed by a grinder (roll speed: 700 times / min, line speed: 5 m / min, cut thickness: 10 μm) in which a 180-mesh sandpaper was wound around a roll.
【００２８】処理したポリウレタンシートを、液滴噴射
手段によって加色した。即ち、表１の４種類のインクを
調製し、４個のインクジェットヘッドを持つインクジェ
ットプリンターに搭載し、８ドット／ｍｍの連続プリン
ター（ブルー色及びグリーン色）を行いコンピューター
上に描かせた画像を該シート上に加色した。The treated polyurethane sheet was colored by a droplet jetting means. That is, the four types of inks shown in Table 1 were prepared, mounted on an ink jet printer having four ink jet heads, and an 8 dot / mm continuous printer (blue and green) was used to print an image drawn on a computer. Color was applied on the sheet.
【００２９】[0029]
【表１】 [Table 1]
【００３０】（比較例１）非多孔性ポリウレタンシート
を以下の如く製造した。即ち、厚み０．２ｍｍのポリエ
ステルフィルム上に固形分２６％のポリテトラメチレン
エーテル系ポリウレタン溶液（下記塗工液）をドクター
ナイフにて１０００ｇ／ｍ2 塗工し、３５度温水にて湿
式凝固させた。 塗工液 ポリテトラメチレンエーテル系ポリウレタン １００部 ジメチルホルムアミド（ＤＭＦ） ４０部 アニオン系界面活性剤 ２部 白顔料 １５部Comparative Example 1 A non-porous polyurethane sheet was produced as follows. That is, a polytetramethylene ether-based polyurethane solution having a solid content of 26% (the following coating solution) was coated on a 0.2 mm-thick polyester film with a doctor knife at 1000 g / m 2 and wet coagulated with 35 ° C warm water. Was. Coating solution Polytetramethylene ether polyurethane 100 parts Dimethylformamide (DMF) 40 parts Anionic surfactant 2 parts White pigment 15 parts
【００３１】更に、５０度温水にて充分水洗後１２０度
にて乾燥させ、厚み０．７ｍｍ、密度０．４３ｇ／ｃｍ
3 の非多孔質ポリウレタンシートを得た。Further, after sufficiently washing with 50 ° C warm water and drying at 120 ° C, the thickness is 0.7 mm and the density is 0.43 g / cm.
3 non-porous polyurethane sheets were obtained.
【００３２】該ポリウレタンシートは、研削機でポリウ
レタンシートの表面を除去することなく、実施例１と同
様に液滴噴射手段によって加色した。The polyurethane sheet was colored by the droplet jetting means in the same manner as in Example 1 without removing the surface of the polyurethane sheet with a grinder.
【００３３】（比較例２）実施例１と同じ方法にて、多
孔性ポリウレタンシートを作成し、研削機で多孔質ポリ
ウレタンシートの表面を除去することなく、実施例１と
同様に液滴噴射手段によって加色した。Comparative Example 2 A porous polyurethane sheet was prepared in the same manner as in Example 1, and the droplet jetting means was used in the same manner as in Example 1 without removing the surface of the porous polyurethane sheet with a grinder. Color.
【００３４】（比較例３）比較例１と同じ方法にて、非
多孔性ポリウレタンシートを作成し、実施例１と同様に
研削機で該ポリウレタンシートの表面を除去し、液滴噴
射手段によって加色した。(Comparative Example 3) A non-porous polyurethane sheet was prepared in the same manner as in Comparative Example 1, the surface of the polyurethane sheet was removed by a grinder in the same manner as in Example 1, and the polyurethane sheet was applied by a droplet jetting means. Colored.
【００３５】上記実施例１および比較例１〜３で得られ
た加色ポリウレタンシートについて、その色彩におけ
る、インクの弾き、にじみ、混色から評価した。その結
果を表２に示す。The color-added polyurethane sheets obtained in Example 1 and Comparative Examples 1 to 3 were evaluated for ink repellency, bleeding, and color mixing in their colors. Table 2 shows the results.
【００３６】[0036]
【表２】 [Table 2]
【００３７】その結果、実施例１の如く、多孔性ポリウ
レタンシートであり、且つ表面が研削されたシートにお
いて、インクの弾き、にじみ、混色に遜色の無い加色が
可能であった。これは、ポリウレタンシートの加色に
は、色素が浸透しうる様に多孔性であり、且つ表面にそ
の多孔性が現れていることが必要であることを示唆す
る。As a result, as in Example 1, in the case of a porous polyurethane sheet having a ground surface, it was possible to perform color addition comparable to ink repelling, bleeding, and color mixing. This suggests that the coloring of the polyurethane sheet needs to be porous so that the dye can penetrate, and the porosity must appear on the surface.
【００３８】（実施例２）実施例１で得られた加色した
多孔性ポリウレタンシートを、更に表面処理した。即
ち、シボ付き離型紙上にレザミンＭＥ−８１１５ＬＰ
（大日精化工業製）１００部に対し、ジメチルホルムア
ミド／メチルケチルケトン＝５／５を５０部加えたポリ
ウレタン有機溶剤溶液を乾燥厚みが３０ミクロンになる
ようにナイフコーターにて塗布し、これを１００度で３
分間熱風乾燥させポリウレタン表皮層を作製した。更
に、レザミンＵＤ−８３００ＬＰ（大日精化工業製）１
００部，レザミンＵＤ−架橋剤（大日精化工業製）８
部、レザミンＵＤ−架橋促進剤（大日精化工業製）２
部、ジメチルホルムアミド／メチルケチルケトン＝５／
５を５０部加えたポリウレタン接着剤をポリウレタン表
皮層に乾燥厚みが３０ミクロンになるようにナイフコー
ターにて塗布し、これを１００度で３分間熱風乾燥し
た。該接着剤の付いた表皮層に、加色した多孔性ポリウ
レタンシートを１２０度で熱圧着し、接着剤の硬化後離
型紙を剥離して、表面コート及び加色されたポリウレタ
ンシートを得た。この事によって、透明フィルムで色落
ちが防止され、色調がより鮮明にする事ができた。(Example 2) The colored porous polyurethane sheet obtained in Example 1 was further subjected to a surface treatment. That is, REZAMINE ME-8115LP is placed on release paper with a grain.
100 parts (Dainichi Seika Kogyo) of a polyurethane organic solvent solution obtained by adding 50 parts of dimethylformamide / methylketyl ketone = 5/5 was applied by a knife coater so as to have a dry thickness of 30 μm. 3 at 100 degrees
It was dried with hot air for minutes to produce a polyurethane skin layer. Furthermore, Rezamine UD-8300LP (manufactured by Dainichi Seika Kogyo) 1
00 parts, Rezamine UD-crosslinking agent (Dainichi Seika Kogyo) 8
Part, Rezamine UD-crosslinking accelerator (Dainichi Seika Kogyo) 2
Parts, dimethylformamide / methylketyl ketone = 5 /
5 was added to the polyurethane skin layer with a knife coater so as to have a dry thickness of 30 μm, and this was dried with hot air at 100 ° C. for 3 minutes. The colored porous polyurethane sheet was thermocompression-bonded to the skin layer with the adhesive at 120 ° C., and after the adhesive was cured, the release paper was peeled off to obtain a surface-coated and colored polyurethane sheet. By this, discoloration was prevented by the transparent film, and the color tone could be made clearer.
【００３９】（実施例３）多孔性ポリウレタン組成物で
ある人工皮革を以下の如く製造した。即ち、ポリエステ
ル短繊維をニードリングし、厚み１．８ｍｍ、密度０．
１４ｇ／ｃｍ3 の不織布を得た。次に、水溶性高分子溶
液に該不織布を含浸処理し、圧搾ロールで過剰の液を絞
り、１２０度にて乾燥し、前処理段階の不織布を得た。
該不織布を固形分濃度１０％ポリテトラメチレンエーテ
ル系ポリウレタン溶液に含浸させた。Example 3 An artificial leather as a porous polyurethane composition was produced as follows. That is, the polyester short fiber is needled, the thickness is 1.8 mm, and the density is 0.8 mm.
A non-woven fabric of 14 g / cm 3 was obtained. Next, the nonwoven fabric was impregnated with a water-soluble polymer solution, excess liquid was squeezed with a pressing roll, and dried at 120 ° C. to obtain a nonwoven fabric in a pretreatment stage.
The nonwoven fabric was impregnated with a polytetramethylene ether-based polyurethane solution having a solid content of 10%.
【００４０】含浸させた該不織布の上に、ポリテトラメ
チレンエーテル系ポリウレタン１００部に対し、ジメチ
ルホルムアミド４０部、ノニオン系界面活性剤１部、シ
リコン１部、白顔料１５部を混合した２６％ポリウレタ
ン塗工液を、ドクターナイフにて９００ｇ／ｍ2 塗工
し、３５度温水にて湿式凝固させた。更に、５０度温水
で充分水洗後１２０度にて乾燥させ、厚み１．４ｍｍ、
密度０．３６ｇ／ｃｍ3の多孔質ポリウレタン層を持つ
人工皮革を得た。A 26% polyurethane obtained by mixing 40 parts of dimethylformamide, 1 part of nonionic surfactant, 1 part of silicon, and 15 parts of white pigment with 100 parts of polytetramethylene ether-based polyurethane on the impregnated nonwoven fabric. The coating solution was applied at 900 g / m 2 with a doctor knife and wet coagulated with 35 ° C warm water. Furthermore, after thoroughly washing with 50 ° C warm water and drying at 120 ° C, the thickness is 1.4 mm.
An artificial leather having a porous polyurethane layer having a density of 0.36 g / cm 3 was obtained.
【００４１】更に、実施例１と同様に研削機で該人工皮
革の表面を除去した。その上、実施例１と同様に液滴噴
射手段によって加色した。Further, the surface of the artificial leather was removed by a grinder in the same manner as in Example 1. In addition, as in the case of Example 1, the color was added by the droplet ejecting means.
【００４２】（比較例４）非多孔性ポリウレタン組成物
である人工皮革を以下の如く製造した。即ち、ポリエス
テル短繊維をニードリングし、厚み１．８ｍｍ、密度
０．１４ｇ／ｃｍ3の不織布を得た。次に、水溶性高分
子溶液に前記不織布を含浸処理し、圧搾ロールで過剰の
液を絞り、１２０度にて乾燥し、前処理不織布を得た。
次いで固形分濃度１０％のポリテトラメチレンエーテル
系ポリウレタン溶液に該基材を含浸させた。Comparative Example 4 An artificial leather as a non-porous polyurethane composition was produced as follows. That is, polyester short fibers were needled to obtain a nonwoven fabric having a thickness of 1.8 mm and a density of 0.14 g / cm 3 . Next, the nonwoven fabric was impregnated with a water-soluble polymer solution, excess liquid was squeezed with a pressing roll, and dried at 120 ° C. to obtain a pretreated nonwoven fabric.
Next, the substrate was impregnated with a polytetramethylene ether-based polyurethane solution having a solid concentration of 10%.
【００４３】含浸させた該不織布の上に、ポリテトラメ
チレンエーテル系ポリウレタン１００部に対し、ジメチ
ルホルムアミド４０部、ノニオン系界面活性剤１部、白
顔料１５部を混合した２６％ポリウレタン塗工液を、ド
クターナイフにて９００ｇ／ｍ2 塗工し、３５度温水に
て湿式凝固させた。更に、５０度温水で充分水洗後１２
０度にて乾燥させ、厚み１．４ｍｍ、密度０．４３ｇ／
ｃｍ3 の非多孔質ポリウレタン層を持つ人工皮革を得
た。On the impregnated nonwoven fabric, a 26% polyurethane coating liquid obtained by mixing 40 parts of dimethylformamide, 1 part of nonionic surfactant, and 15 parts of white pigment was mixed with 100 parts of polytetramethylene ether-based polyurethane. 900 g / m 2 was applied with a doctor knife and wet coagulated with 35 ° C warm water. In addition, after thoroughly washing with 50 ° C warm water, 12
Dry at 0 degree, thickness 1.4mm, density 0.43g /
An artificial leather having a non-porous polyurethane layer of cm 3 was obtained.
【００４４】該人工皮革は、研削機で非多孔質ポリウレ
タンシートの表面を除去することなく、実施例１と同様
に液滴噴射手段によって加色した。The artificial leather was colored by the droplet jetting means in the same manner as in Example 1 without removing the surface of the non-porous polyurethane sheet with a grinder.
【００４５】（比較例５）実施例３と同じ方法にて、多
孔性ポリウレタン組成物である人工皮革を作成し、研削
機で該人工皮革の表面を除去することなく、実施例１と
同様に液滴噴射手段によって加色した。(Comparative Example 5) In the same manner as in Example 3, an artificial leather as a porous polyurethane composition was prepared, and the artificial leather was removed in the same manner as in Example 1 without removing the surface of the artificial leather with a grinder. The color was applied by the droplet ejecting means.
【００４６】（比較例６）比較例４と同じ方法にて、非
多孔性ポリウレタン組成物である人工皮革を作成し、実
施例１と同様に研削機で該人工皮革の表面を除去し、液
滴噴射手段によって加色した。Comparative Example 6 An artificial leather as a non-porous polyurethane composition was prepared in the same manner as in Comparative Example 4, and the surface of the artificial leather was removed with a grinder in the same manner as in Example 1 to obtain a liquid. The color was applied by the drop ejecting means.
【００４７】上記実施例３および比較例４〜６で得られ
た加色ポリウレタン組成物である人工皮革について、そ
の色彩における、インクの弾き、にじみ、混色から評価
した。その結果を表３に示す。The artificial leather, which is the colored polyurethane composition obtained in Example 3 and Comparative Examples 4 to 6, was evaluated based on ink repellency, bleeding, and color mixing in its color. Table 3 shows the results.
【００４８】[0048]
【表３】 [Table 3]
【００４９】その結果、実施例３の如く、多孔性ポリウ
レタン組成物であり、且つ表面が研削された組成物にお
いて、インクの弾き、にじみ、混色に遜色の無い加色が
可能であった。As a result, as in Example 3, in the case of the porous polyurethane composition and the composition whose surface was ground, it was possible to add color comparable to ink repellency, bleeding, and color mixing.
【００５０】（実施例４）実施例３で得られた加色した
多孔性ポリウレタン組成物である人工皮革を、更に表面
処理した。即ち、実施例２と同様にレザミンＭＥ−８１
１５ＬＰ等の表皮層に、加色した人工皮革を１２０度で
熱圧着し、接着剤の硬化後離型紙を剥離して、表面コー
ト及び加色された人工皮革を得た。この事によって、透
明フィルムで色落ちが防止され、色調がより鮮明にする
事ができた。(Example 4) The artificial leather, which is the colored porous polyurethane composition obtained in Example 3, was further surface-treated. That is, as in Example 2, resamine ME-81
Colored artificial leather was thermocompression-bonded to the skin layer of 15LP or the like at 120 ° C., and after the adhesive was cured, the release paper was peeled off to obtain a surface-coated and colored artificial leather. By this, discoloration was prevented by the transparent film, and the color tone could be made clearer.
【００５１】[0051]
【発明の効果】以上詳述したように、本発明によれば、
ポリウレタンを多孔化し、且つ表面研削することで、従
来の加色方法では行えなかった、多くの色の加色を１工
程で行え且つデザインの変更にも即座に対応可能な、液
滴噴射手段を用いた加色が可能となり、そのことによっ
て、該手段により加色したポリウレタンシート或は、ポ
リウレタン組成物特に人工皮革を得ることができた。As described in detail above, according to the present invention,
By making the polyurethane porous and grinding the surface, a droplet jetting means that can add many colors in one process and can immediately respond to design changes, which could not be done by the conventional coloring method, The coloring used could be performed, and as a result, a polyurethane sheet or a polyurethane composition, particularly an artificial leather, colored by the means could be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ４１Ｊ 2/01 Ｃ０８Ｊ 9/00 Ｚ Ｃ０８Ｊ 9/00 Ｄ０６Ｎ 3/00 ＤＡＤ Ｄ０６Ｎ 3/00 ＤＡＤ Ｄ０６Ｐ 3/24 Ｚ Ｄ０６Ｐ 3/24 Ｂ４１Ｊ 3/04 １０１Ｚ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B41J 2/01 C08J 9/00 Z C08J 9/00 D06N 3/00 DAD D06N 3/00 DAD D06P 3/24 Z D06P 3/24 B41J 3/04 101Z
Claims (5)
性合成樹脂シート。1. A porous synthetic resin sheet which is colored by using a droplet jetting means.
性合成樹脂組成物。2. A porous synthetic resin composition obtained by adding color using a droplet jetting means.
求項２記載の多孔性合成樹脂組成物。3. The porous synthetic resin composition according to claim 2, wherein the porous synthetic resin composition is artificial leather.
物を製造する方法であって、多孔質合成樹脂層を形成
し、次いで表皮を除去し、しかる後に液的噴射すること
により加色した多孔性合成シート又は多孔性合成組成物
の製造方法。4. A method for producing a colored synthetic resin sheet or synthetic resin composition, comprising forming a porous synthetic resin layer, removing the skin, and then applying a liquid by jetting. A method for producing a porous synthetic sheet or a porous synthetic composition.
径が１０〜２００ミクロンであり、且つ最長の直径がシ
ート面に対し実質垂直に配向している、請求項４記載の
加色した多孔性合成シート又は多孔性合成組成物の製造
方法。5. The color-added porous material according to claim 4, wherein the porous synthetic resin layer has a porous average diameter of 10 to 200 microns and a longest diameter oriented substantially perpendicular to the sheet surface. For producing a porous synthetic sheet or a porous synthetic composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9208484A JPH1136180A (en) | 1997-07-16 | 1997-07-16 | Colored synthetic resin sheet or colored synthetic resin composition, and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9208484A JPH1136180A (en) | 1997-07-16 | 1997-07-16 | Colored synthetic resin sheet or colored synthetic resin composition, and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1136180A true JPH1136180A (en) | 1999-02-09 |
Family
ID=16556932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9208484A Pending JPH1136180A (en) | 1997-07-16 | 1997-07-16 | Colored synthetic resin sheet or colored synthetic resin composition, and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1136180A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008057062A (en) * | 2006-08-30 | 2008-03-13 | Teijin Cordley Ltd | Leathery, sheet-like product and method for producing the same |
| WO2009107246A1 (en) * | 2008-02-26 | 2009-09-03 | 帝人コードレ株式会社 | Leather-like sheet and method of producing the same |
| TWI427206B (en) * | 2008-02-27 | 2014-02-21 | Teijin Cordley Ltd | Quasi - leather sheet and its manufacturing method |
| JP2018150649A (en) * | 2017-03-14 | 2018-09-27 | 株式会社クラレ | Grained artificial leather and method for producing the same |
-
1997
- 1997-07-16 JP JP9208484A patent/JPH1136180A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008057062A (en) * | 2006-08-30 | 2008-03-13 | Teijin Cordley Ltd | Leathery, sheet-like product and method for producing the same |
| WO2009107246A1 (en) * | 2008-02-26 | 2009-09-03 | 帝人コードレ株式会社 | Leather-like sheet and method of producing the same |
| US8465800B2 (en) | 2008-02-26 | 2013-06-18 | Teijin Cordley Limited | Leather-like sheet and process for the production thereof |
| KR101426118B1 (en) * | 2008-02-26 | 2014-08-05 | 데이진 고도레 가부시키가이샤 | Leather-like sheet and method of producing the same |
| TWI427206B (en) * | 2008-02-27 | 2014-02-21 | Teijin Cordley Ltd | Quasi - leather sheet and its manufacturing method |
| JP2018150649A (en) * | 2017-03-14 | 2018-09-27 | 株式会社クラレ | Grained artificial leather and method for producing the same |
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