JPH0441783A - Dyed artificial leather - Google Patents
Dyed artificial leatherInfo
- Publication number
- JPH0441783A JPH0441783A JP14401490A JP14401490A JPH0441783A JP H0441783 A JPH0441783 A JP H0441783A JP 14401490 A JP14401490 A JP 14401490A JP 14401490 A JP14401490 A JP 14401490A JP H0441783 A JPH0441783 A JP H0441783A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic leather
- dyed
- dyeing
- powder
- dye
- 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
Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 58
- 239000004744 fabric Substances 0.000 claims abstract description 65
- 238000004043 dyeing Methods 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000000985 reactive dye Substances 0.000 claims abstract description 39
- 229920000620 organic polymer Polymers 0.000 claims abstract description 21
- 239000010985 leather Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229920002635 polyurethane Polymers 0.000 claims abstract description 7
- 239000004814 polyurethane Substances 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 abstract description 66
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 37
- 238000000034 method Methods 0.000 abstract description 18
- 238000012546 transfer Methods 0.000 abstract description 11
- 210000002268 wool Anatomy 0.000 abstract description 5
- 229920000742 Cotton Polymers 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 description 36
- 210000003491 skin Anatomy 0.000 description 34
- 239000000975 dye Substances 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- 239000007788 liquid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 210000002615 epidermis Anatomy 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 150000003673 urethanes Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- -1 dyeing aids Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000007730 finishing process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000012192 staining solution Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- XULFCTLQSSIMOF-UHFFFAOYSA-N 1-ethenylsulfonylethene;triazine Chemical compound C1=CN=NN=C1.C=CS(=O)(=O)C=C XULFCTLQSSIMOF-UHFFFAOYSA-N 0.000 description 1
- NFGXHKASABOEEW-UHFFFAOYSA-N 1-methylethyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate Chemical compound COC(C)(C)CCCC(C)CC=CC(C)=CC(=O)OC(C)C NFGXHKASABOEEW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IHDBZCJYSHDCKF-UHFFFAOYSA-N 4,6-dichlorotriazine Chemical compound ClC1=CC(Cl)=NN=N1 IHDBZCJYSHDCKF-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- SLYUUEOAHFJYGP-UHFFFAOYSA-L disodium 5-acetamido-4-hydroxy-3-[(3-phosphonophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].CC(=O)Nc1cc(cc2cc(c(N=Nc3cccc(c3)P(O)(O)=O)c(O)c12)S([O-])(=O)=O)S([O-])(=O)=O SLYUUEOAHFJYGP-UHFFFAOYSA-L 0.000 description 1
- HJORILXJGREZJU-UHFFFAOYSA-L disodium 7-[(5-chloro-2,6-difluoropyrimidin-4-yl)amino]-4-hydroxy-3-[(4-methoxy-2-sulfonatophenyl)diazenyl]naphthalene-2-sulfonate Chemical compound ClC=1C(=NC(=NC1F)F)NC1=CC=C2C(=C(C(=CC2=C1)S(=O)(=O)[O-])N=NC1=C(C=C(C=C1)OC)S(=O)(=O)[O-])O.[Na+].[Na+] HJORILXJGREZJU-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は染色合成皮革、特に反応染料で染色された合成
皮革に関し、衣料、靴、鞄、雑貨等、各種の用途に利用
可能である。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to dyed synthetic leather, particularly synthetic leather dyed with a reactive dye, and can be used for various uses such as clothing, shoes, bags, and miscellaneous goods.
基布上に、ポリウレタン（以下、単にウレタンという）
系表皮層を有する湿式又は乾式染色合成皮革か知られて
いる。これに使用される染料は、染色か容易、耐候性が
良い等の理由から、現在、酸性染料である１、２酸性含
金染料（染料２分子と金属１分子とからなる金属錯塩染
料）が殆どである。Polyurethane (hereinafter simply referred to as urethane) on the base fabric
Wet- or dry-dyed synthetic leathers having a skin layer are known. Currently, the dyes used for this are acidic dyes such as 1- and 2-acid metal dyes (metal complex dyes consisting of 2 molecules of dye and 1 molecule of metal) because they are easy to dye and have good weather resistance. Most of them.
一方、綿、絹、羊毛等の天然繊維の染色には、反応染料
か多用されている。この染料の特徴は、染色対象物との
共有結合、配位結合等により強固な結合するために、染
料、即ち色の移行性が少ないこと、明るく、しかも深み
のある鮮やかな色が多いこと等である。On the other hand, reactive dyes are often used to dye natural fibers such as cotton, silk, and wool. The characteristics of this dye are that it has a strong bond with the object to be dyed through covalent bonds, coordination bonds, etc., so there is little migration of the dye, that is, there are many bright, deep and vivid colors. It is.
しかしながら、１，２酸性含金染料は移行し易いという
性質があるため、従来の染色合成皮革では衣料、靴、雑
貨等の商品として製造中又は製造後、重ねて置くと、色
移りが発生する。この色移りは、特に２色以上組合せた
染色品の場合は、色違い部分での積重ねが避けられない
ため、非常に目立つ。However, because 1,2-acid metal-containing dyes tend to transfer easily, color transfer occurs when conventionally dyed synthetic leather is stacked during or after manufacturing products such as clothing, shoes, and miscellaneous goods. . This color transfer is very noticeable, especially in the case of dyed products in which two or more colors are combined, because stacking of different colored parts is unavoidable.
また１、２酸性含金染料を色の面から見ると、やや暗い
色が殆どであるから色に深みがある。しかし、明るい色
にしようとして基布や接着層（基布上に表皮層を保持す
るために、接着剤を用いることが多い。）に白色顔料を
添加すると、色の深みがなくなって安っぽいものとなる
。Furthermore, when looking at mono- and di-acidic metal-containing dyes in terms of color, most of them are slightly dark, so the colors have depth. However, if white pigment is added to the base fabric or adhesive layer (adhesive is often used to hold the skin layer on the base fabric) to make the color brighter, the color will lose its depth and look cheap. Become.
これに対し、反応染料はこれらの欠点はないが、官能基
との反応で染色を行なうため、官能基を持たないウレタ
ンでは染色できないし、また官能基を持ったウレタンで
は染色できたとしても、一般に反応染料と反応するよう
な官能基が少ないため染色濃度が不充分である上、染色
条件がＰＨ９〜１１．５と強アルカリ性なので、加水分
解され易く、実用化は困難であった。On the other hand, reactive dyes do not have these drawbacks, but because they dye by reacting with functional groups, they cannot be dyed with urethane that does not have functional groups, and even if they can be dyed with urethane that has functional groups, In general, since there are few functional groups that react with reactive dyes, the dyeing concentration is insufficient, and since the dyeing conditions are strongly alkaline at pH 9 to 11.5, they are easily hydrolyzed, making it difficult to put them into practical use.
また特に衣料用染色合成皮革のように、表皮層の下に多
孔質ウレタン層があるものでは、多孔質層まで染色され
ていないと、表皮層が染色されていても引っ掻き傷等に
よって表皮層下から白い層が出ては商品にならない。従
ってこのような染色合成皮革の場合は、多孔質層まで染
色する必要があるが、多孔質層に用いられる発泡性ウレ
タンの種類によっては反応染料によって染色できない。In addition, especially for dyed synthetic leather for clothing, which has a porous urethane layer below the epidermis layer, if the porous layer is not dyed, even if the epidermis layer is dyed, scratches may occur beneath the epidermis layer. If a white layer comes out from the surface, it will not become a product. Therefore, in the case of such dyed synthetic leather, it is necessary to dye even the porous layer, but depending on the type of foamable urethane used for the porous layer, dyeing cannot be done with a reactive dye.
本発明の目的は、本来の皮革様の感触及び性能を維持し
ながら、色移行性がなく、しかも明るい色も深みのある
色も多く、染色濃度も高い染色合成皮革を提供すること
である。An object of the present invention is to provide a dyed synthetic leather that has no color migration, has many bright colors and deep colors, and has a high dye density while maintaining the original leather-like feel and performance.
〔課題を解決するための手段及び作用〕本発明は、反応
染料が、従来の１，２−酸性含金染料における欠点を全
て除去できること及びある種の天然有機高分子粉末がウ
レタンの見掛けの染色濃度向上に役立つことに着目し、
これにより前記目的を達成しようとするものである。[Means and effects for solving the problems] The present invention provides that reactive dyes can eliminate all the drawbacks of conventional 1,2-acidic metal-containing dyes, and that certain natural organic polymer powders can improve the apparent dyeing of urethane. Focusing on its usefulness in improving concentration,
This aims to achieve the above objective.
本発明の染色合成皮革は次の２種である。The dyed synthetic leather of the present invention is of the following two types.
一つは、基布上に、各々反応染料で染色可能な、ポリウ
レタン５０〜９８ｗｔと天然有機高分子粉末５０〜２ｗ
ｔ％との混合物よりなる表皮層を設けた合成皮革原反を
、反応染料で染色して構成される。One is 50 to 98 wt of polyurethane and 50 to 2 wt of natural organic polymer powder, each of which can be dyed with a reactive dye, on a base fabric.
It is constructed by dyeing a synthetic leather material with a skin layer made of a mixture of t% and t% with a reactive dye.
他の一つは、前記表皮層下に更に、反応染料で染色可能
な多孔質ポリウレタン層を設けた合成皮革原反を、反応
染料で染色して構成される。The other type is constructed by dyeing a raw synthetic leather fabric with a porous polyurethane layer that can be dyed with a reactive dye, which is further provided under the skin layer with a reactive dye.
本発明の染色合成皮革に使用される材料について説明す
る。The materials used for the dyed synthetic leather of the present invention will be explained.
合成皮革原反用織布としては、織物、編物、不織布、ウ
レタン含浸不織布、及びそれらの混紡品；各々着色繊維
からなる織物、編物、不織布、ウレタン含浸不織布、及
びそれらの混紡品が使用される。中でも反応染料で染色
され易い基布、例えば綿、絹、羊毛、キュプラ、ナイロ
ン等が好ましい。As the woven fabric for synthetic leather material, woven fabrics, knitted fabrics, nonwoven fabrics, urethane-impregnated nonwoven fabrics, and blends thereof; woven fabrics, knitted fabrics, nonwoven fabrics, urethane-impregnated nonwoven fabrics, and blends thereof each made of colored fibers are used. . Among these, base fabrics that are easily dyed with reactive dyes, such as cotton, silk, wool, cupro, and nylon, are preferred.
合成皮革原反の表皮層に用いられるウレタンとしては、
反応染料で染色可能なもの、即ち反応染料と反応するよ
うな官能基を持つものであればいずれも使用可能である
。勿論、反応染料の染色条件（ＰＨ９〜１１．５）下で
分解したり、変性するものは使用できない。ここで注意
すべきことはウレタンの種類は非常に多く、たとえ反応
染料と反応するような官能基を持っていても、染色条件
、即ち高ＰＨ域では加水分解されるものも多いことであ
る。従って本発明で使用される表皮用ウレタンは染色条
件下で変性又は分解せずに、反応染料で染色できるもの
でなければならない。このようなウレタンとしては、例
えばポリエーテル系、ポリカーボネート系（以上は有機
溶剤又は水の溶液又は分散液としてし使用される。）、
ポリエステル系（水溶液又は水性分散液として使用され
る）、及びそれらの混合ジオール系、等のウレタンか挙
げられる。Urethane used in the skin layer of raw synthetic leather includes:
Any material can be used as long as it can be dyed with a reactive dye, that is, it has a functional group that reacts with the reactive dye. Of course, it is not possible to use reactive dyes that decompose or denature under the dyeing conditions (PH9 to 11.5). It should be noted here that there are many types of urethane, and even if they have functional groups that react with reactive dyes, many of them are hydrolyzed under dyeing conditions, that is, in the high pH range. Therefore, the urethane for skin used in the present invention must be able to be dyed with reactive dyes without being denatured or decomposed under the dyeing conditions. Such urethanes include, for example, polyether-based, polycarbonate-based (the above are used as a solution or dispersion in an organic solvent or water),
Urethanes such as polyesters (used as aqueous solutions or dispersions) and mixed diols thereof may be mentioned.
これら染色性ウレタンの市販品としては下記のものかあ
る。Commercially available dyeable urethanes include the following.
有機溶剤性製品；
大日精化社製 レザミンＭＥ−８１０５ＬＰ（ポリエー
テル系）
三洋化成工業社製 サンブレン５Ｐ２００Ｄ（ポリエー
テル系、ポリエステル
系等の混合系）
ＤＩＣ社製 クリスボン３１１６Ｓ
（ポリカーボネート系）
東洋ポリマー社製 ペタル９０６０．７１１６（ポリカ
ーボネート系）
水性製品；
第一工業製薬社製 スーパーフレックスＥ４０００（ポ
リエーテル系）
スーパーフレックスＥ２０００
（ポリエステル系）
なお、反応染料で染色可能なウレタンでも、般に反応性
官能基は少ないので、染色性は不充分である。Organic solvent-based products: Rezamin ME-8105LP (polyether type) manufactured by Dainichiseika Co., Ltd. Sunblen 5P200D (mixed type of polyether type, polyester type, etc.) manufactured by Sanyo Chemical Co., Ltd. Crisbon 3116S manufactured by DIC Corporation (polycarbonate type) Toyo Polymer Co., Ltd. Made by Petal 9060.7116 (polycarbonate-based) Water-based products; Dai-ichi Kogyo Seiyaku Co., Ltd. Superflex E4000 (polyether-based) Superflex E2000 (polyester-based) Even urethane that can be dyed with reactive dyes generally has reactive functional groups. Since the amount is small, the stainability is insufficient.
一方、多孔質層用多孔質ウレタンの原料ウレタンも表皮
層用と同様に、反応染料で染色可能なものであればよい
。勿論、染色染料の染色条件下で分解したり、変性する
ものは使用できない。多孔質層用として適したウレタン
としてはポリエーテル系、ポリカーボネート系、ポリエ
ステル系（好ましくは、へたり防止の点から架橋剤併用
型ポリエステル系）、及びそれらの混合ジオール系のウ
レタンが挙げられる。これらは水性エマルジョンで使用
することが好ましい。このような水性の市販品としては
第一工業製薬社製スーパーフレックスＥ４０００ （
ポリエーテル系） 、 Ｅ２０００ （ポリエステル
系）、大日精化社製しザミンＵＦ１３８ Ｃ改）（ポ
リエステル系）等がある。On the other hand, the raw material urethane for the porous urethane for the porous layer may be any urethane as long as it can be dyed with a reactive dye, similar to that for the skin layer. Of course, dyes that decompose or denature under the dyeing conditions cannot be used. Urethanes suitable for the porous layer include polyether-based, polycarbonate-based, polyester-based (preferably polyester-based in combination with a crosslinking agent to prevent settling), and mixed diol-based urethanes thereof. Preferably they are used in aqueous emulsions. As such a water-based commercially available product, Daiichi Kogyo Seiyaku Co., Ltd.'s Superflex E4000 (
Examples include polyether type), E2000 (polyester type), and Zamin UF138 C modified) manufactured by Dainichiseika Kaisha, Ltd. (polyester type).
反応染料で染色するのに適しているウレタンとしては、
表皮層用ウレタンも多孔質層用ウレタンも、フィルムと
して染色前後の伸び率を見た場合に、変化が少ないもの
が風合いの変化がなく、また劣化が少ないので好ましい
。この伸び率はウレタンフィルムをＰＨ１１、温度９０
℃の反応染料水溶液中１時間の染色後、伸び率が染色工
程前のものと比較して１００％±２０％以内（ＪＩＳ−
２１７０２による）であり、前記例示した染色性ウレタ
ンは全てこの伸び率の範囲内である。Urethane suitable for dyeing with reactive dyes includes:
For both the urethane for the skin layer and the urethane for the porous layer, when looking at the elongation rate of the film before and after dyeing, it is preferable to use one that shows little change in elongation rate because there is no change in texture and less deterioration. This elongation rate is urethane film at pH 11 and temperature 90.
After dyeing in a reactive dye aqueous solution at ℃ for 1 hour, the elongation rate is within 100% ± 20% compared to that before the dyeing process (JIS-
21702), and all of the above-mentioned dyeable urethanes fall within this elongation range.
合成皮革原反の表皮層に用いられる天然有機高分子粉末
としては、ウレタンや多孔質ウレタンと同様、反応染料
で染色可能なものであればよい。The natural organic polymer powder used for the skin layer of the synthetic leather material may be any powder that can be dyed with a reactive dye, similar to urethane or porous urethane.
勿論、反応染料の染色条件下で分解したり、変性するも
のは使用できない。この天然有機高分子粉末は、主とし
て表皮層におけるウレタンの染色性を向上するために使
用される。このような天然有機高分子粉末としては皮革
粉、キチン粉、シルク粉、ゼラチン粉、カゼイン粉、羊
毛粉、コラーゲン粉、セルロース粉等、好ましくは皮革
粉が挙げられる。これら粉末は表皮層に添加すると、染
色性の向上ばかりでなく、タック感の減少、吸放湿性の
付与、適度なざらつき等により表皮層に良好な感触を与
える。これら天然有機高分子粉末の表皮層への添加量は
ウレタン５０〜９８ｗｔ％に対し５０〜２ｗｔ％の範囲
である。２％よりも少ないと、添加効果が充分期待でき
ず、５０％よりも多いと、脆くなり、使用に耐えない。Of course, reactive dyes that decompose or denature under the dyeing conditions cannot be used. This natural organic polymer powder is mainly used to improve the dyeability of urethane in the epidermal layer. Examples of such natural organic polymer powder include leather powder, chitin powder, silk powder, gelatin powder, casein powder, wool powder, collagen powder, cellulose powder, etc., preferably leather powder. When these powders are added to the epidermis layer, they not only improve the dyeability, but also give the epidermis a good feel by reducing the tackiness, imparting moisture absorbing and releasing properties, and providing appropriate roughness. The amount of these natural organic polymer powders added to the skin layer is in the range of 50 to 2 wt% relative to 50 to 98 wt% of urethane. If it is less than 2%, the addition effect cannot be expected to be sufficient, and if it is more than 50%, it becomes brittle and cannot be used.
粉末の粒径は、コーティングによる表皮層の形成、即ち
フィルムまたはシート化を考慮すると、コーティング時
の湿潤塗膜の厚さと同等以下が適当であるが、好ましく
は、表皮層となる乾燥塗膜の厚さと同等以下、更に好ま
しくは１７３以下である。一般には衣料用で表皮層の厚
さは２０〜５０μｍ、靴用、家具用、又は自動車シート
用で２０〜２００μｍであるから、粒径は２００！１ｍ
以下、好ましくは７０μｍ以下、更に好ましくは１０μ
ｍ以下である。Considering the formation of a skin layer by coating, that is, the formation of a film or sheet, the particle size of the powder is suitably equal to or smaller than the thickness of the wet paint film during coating, but preferably it is equal to or smaller than the thickness of the dry paint film that will become the skin layer. It is equal to or less than the thickness, more preferably 173 or less. Generally, the thickness of the skin layer is 20 to 50 μm for clothing, and 20 to 200 μm for shoes, furniture, or car seats, so the particle size is 200!1 m.
Below, preferably 70μm or less, more preferably 10μm
m or less.
以上の天然有機高分子粉末のうち、皮革粉の具体例とし
しては、微細皮革粉（例えば特開昭６３−１５６５５２
号に記載の方法で得られる。）を更にジェットミルで平
均粒径Ｄｓｏ＝７μｍ以下に再微粉砕したものが、シル
ク粉としてはＫＡＮＥＢＯ５ＰＡＮ ５ＩＬＫＬＴＤ製
シルクパウダ−ＩＭ又はＰ２Ｏ等でＤ５゜が８μｍ以下
のものが、ゼラチン粉としては特開平１−２９４７４０
号に記載のＤｌ！＝６μｍ以下のものが、またセルロー
ス粉としては重陽国策バルブ社製ＫＣフロック Ｗ２Ｏ
３，Ｗ２Ｏ３が挙げられる。Among the above natural organic polymer powders, specific examples of leather powder include fine leather powder (for example, Japanese Patent Application Laid-Open No. 63-156552
Obtained by the method described in No. ) is further pulverized with a jet mill to an average particle size Dso = 7 μm or less. Silk powder is KANEBO5PAN 5ILK LTD Silk Powder-IM or P2O with D5° of 8 μm or less, and gelatin powder is JP-A No. 1-294740
Dl listed in the issue! = 6 μm or less, and as a cellulose powder, KC Flock W2O manufactured by Choyo Kokusaku Valve Co., Ltd.
3, W2O3.
多孔質層には、必要に応じて、表皮層に用いられるよう
な天然有機高分子粉末やフィラーを添加することができ
る。本発明では多孔質層にも天然有機高分子粉末を添加
することが好ましく、この場合は多孔質層に染色性の向
上、吸放湿性の向上、へたり難さ等の効果を与えること
ができる。またフィラーを添加した場合は、多孔質層に
へたり防止等の効果を与えることができる。フィラーと
してはタルク、炭酸カルシウム、金属酸化物粉等の無機
フィラー等が例示できる。天然有機高分子粉末又はフィ
ラーの添加量は３０％以下が適当で、多いと固くなって
脆く伸び難くなる。また、コーティングにより層を形成
する時にコーテイング液の粘度が上がりすぎて均一なコ
ーティングが困難となり、商品価値の低下を招く。天然
有機高分子粉末又はフィラーの粒径は、表皮層の場合と
同程度が好ましいが、異なってもよいし、或いは異種の
組み合わせや、混合系でもよい。Natural organic polymer powder or filler, such as those used for the skin layer, can be added to the porous layer, if necessary. In the present invention, it is preferable to add natural organic polymer powder to the porous layer, and in this case, the porous layer can have effects such as improved dyeability, improved moisture absorption and desorption properties, and resistance to settling. . Further, when a filler is added, effects such as prevention of settling can be imparted to the porous layer. Examples of the filler include inorganic fillers such as talc, calcium carbonate, and metal oxide powder. The amount of natural organic polymer powder or filler added is suitably 30% or less; if it is too large, it becomes hard, brittle, and difficult to stretch. Furthermore, when forming a layer by coating, the viscosity of the coating liquid increases too much, making it difficult to coat uniformly, resulting in a decrease in commercial value. The particle size of the natural organic polymer powder or filler is preferably the same as that of the skin layer, but may be different, or may be a combination of different types or a mixed system.
以上のような材料で構成される合成皮革原反を染色する
ための反応染料は中温用及び高温用のいずれでもよいが
、用途別ではセルロース用及び羊毛用が好ましい。この
ような反応染料としては、ピリミジン系、トリアジン系
、ビニルスルホン系、キノキサリン系、モノアゾ系、ジ
スアゾ系等の単独型や、ビニルスルホン−トリアジン系
、モノアゾ−ビニルスルホン系、フタロシアニン−ビニ
ルスルホン系等の複合型が挙げられる。これら反応染料
の市販品の一例を表−１に示す。The reactive dye for dyeing the synthetic leather material made of the above-mentioned materials may be either medium-temperature dye or high-temperature dye, but depending on the purpose, cellulose dye and wool dye are preferable. Such reactive dyes include single types such as pyrimidine, triazine, vinylsulfone, quinoxaline, monoazo, and disazo, vinylsulfone-triazine, monoazo-vinylsulfone, and phthalocyanine-vinylsulfone. Examples include complex types. Table 1 shows examples of commercially available reactive dyes.
表−１（続） 表＝１ また、 各種反応染料の代表的な構造例を下記に示す。Table-1 (continued) Table=1 Also, Typical structural examples of various reactive dyes are shown below.
ビニルスルホン系 （反応基としてビニルスルホン 基−３Ｏ，ＣＨ＝ＣＨ。Vinyl sulfone type (vinyl sulfone as a reactive group) Group -3O, CH=CH.
またはスルファ
トエチルスルホニ
ル基−３ＯｚＣＨ２ＣＨｚＯ３ＯＪを持つ）：Ｉ
Ｒｅａｃｔｉｖｅ
ｌｕｅ
Ｉ
Ｒｅａｃｔｉｖｅ
１ａｃｋ
０ｓＮａ
ＳＯ，Ｎａ
・その他の
ト
リアジン系反応染料の例
トリアジン系
〔反応性
トリアジン環
・ジクロルトリアジン系の例
ＯＯＣ
Ｉ
Ｒｅａｃｔｉｖｅ
ｒａｎｇｅ
Ｄｙｅ＝Ｐ（ＯＨ）ｚや、９，２
ＣＩ Ｒｅａｃｔｉｖｅ Ｒｅｄ １７７ピリミ
ジン系
〔反応性ピリミ
ジン環
アクリル酸系
（反応基として
べてかＣＩ、 Ｆ等の反応基）を持つ〕 ：Ｄｙｅ−Ｎ
ＨＣ
Ｃ”ＣＨ２
Ｉ
を持つ）
代表例としては、
トリアジン系でトリアジン環
Ｉ
ＲｅａＣｔｌＶｅ
Ｒｅｄ
をピリミ
ジン環に変えたものが挙げられる。or sulfatoethylsulfonyl group -3OzCH2CHzO3OJ): I Reactive lue I Reactive 1ack 0sNa SO, Na ・Examples of other triazine-based reactive dyes Triazine-based [Examples of reactive triazine ring/dichlorotriazine-based OOC I Reactive range Dye =P(OH)z, 9,2 CI Reactive Red 177 pyrimidine system [having a reactive pyrimidine ring acrylic acid system (reactive group such as CI or F as a reactive group)]: Dye-N
Typical examples include triazine-based compounds in which the triazine ring I ReaCtlVe Red is replaced with a pyrimidine ring.
キノキサリン系
（反応基として
Ｉ
Ｒｅａｃｔｉｖｅ
Ｒｅｄ
複合型
（２種の異なる反応基を持つ）
Ｉ
Ｒｅａｃｔ＋ｖｅ
Ｒｅｄ
ホスホン酸系
（反応基として
Ｏ３Ｈ
Ｏ３Ｈ
次に本発明に係る染色合成皮革の製造方法について説明
する。Quinoxaline type (reactive group: I Reactive Red Complex type (having two different reactive groups) I React+ve Red Phosphonic acid type (reactive group: O3H O3H Next, the method for producing dyed synthetic leather according to the present invention will be described.
まず染色用合成皮革原反を作るため、基布に染色性ウレ
タン−染色性天然有機高分子粉末混合物の表皮層を形成
する。表皮層の形成方法としては直接コーティング法、
転写コーティング法、グラビアコーティング法、スプレ
ーコーティング法等、公知の方法がいずれも採用できる
が、中でも転写コーティング法が好ましい。First, in order to produce a synthetic leather material for dyeing, a skin layer of a dyeable urethane-dyeable natural organic polymer powder mixture is formed on a base fabric. Methods for forming the epidermal layer include direct coating method,
Any known method such as a transfer coating method, a gravure coating method, a spray coating method, etc. can be employed, and among them, a transfer coating method is preferable.
直接コーティング法の場合は、第１図に示すように、基
布１上に、染色性ウレタン溶液に染色性天然有機高分子
粉末を分散したコーテイング液２をドクターナイフ３等
によって所望の厚さに塗布し、乾燥機４で乾燥した後、
冷却筒６のような冷却手段で冷却して表皮層（図示せず
）を設けることにより、合成皮革原反７が得られる。な
お５は搬送用ゴムロールである。In the case of the direct coating method, as shown in Figure 1, a coating liquid 2, which is a dyeable natural organic polymer powder dispersed in a dyeable urethane solution, is applied onto the base fabric 1 to the desired thickness using a doctor knife 3 or the like. After applying and drying with dryer 4,
By cooling with a cooling means such as a cooling cylinder 6 and providing a skin layer (not shown), a synthetic leather raw fabric 7 is obtained. In addition, 5 is a rubber roll for conveyance.
転写コーティング法には、次のように種々の方法がある
。There are various transfer coating methods as follows.
■予め離型紙上に樹脂フィルムを形成し、これを接着〜
剤を用いて基布にラミネートする。■ Form a resin film on the release paper in advance and glue it ~
Laminate it on the base fabric using an adhesive.
■接着剤を用いないで樹脂フィルム表面が粘着性を持っ
ている間に、これを基布に圧着する。■Press the resin film to the base fabric without using adhesive while the surface of the resin film is sticky.
■接着剤を用いないで樹脂フィルム表面を加熱して粘着
性を与え、これを基布に圧着する。■ Heat the surface of the resin film to make it sticky without using adhesive, and then press it onto the base fabric.
このうち■の方法を第２図に従って説明すると、この転
写コーティング法の場合は、まず前述のようなコーテイ
ング液１２をナイフロール１７よって離型紙１０上に所
望の厚さに塗布し、乾燥機１３で乾燥し、冷却ロール１
４等で冷却して、離型紙上に、表皮層となる樹脂フィル
ム１５を形成する。次に、この樹脂フィルム上に、接着
剤１６をナイフロール１７等により塗布した後、その上
に、別途に供給される基布１８を、ニップロール１９に
よって積層し、乾燥機２０で乾燥した後、冷却ロール２
１等で冷却することにより、表皮層を有する合成皮革原
反２２が得られる。Of these methods, method (2) will be explained according to FIG. Dry with cooling roll 1
4 or the like to form a resin film 15 that will become a skin layer on the release paper. Next, after applying the adhesive 16 on this resin film using a knife roll 17 or the like, a separately supplied base fabric 18 is laminated thereon using a nip roll 19, and after drying with a dryer 20, cooling roll 2
By cooling with No. 1 or the like, a synthetic leather raw fabric 22 having a skin layer is obtained.
グラビアコーティング法の場合は、第３図に示すように
、基布３０上に、前述のようなコーテイング液３１をグ
ラビアコーター３２で塗布し、乾燥機３３で乾燥して表
皮層（図示せず）を形成することにより、合成皮革原反
３４が得られる。In the case of the gravure coating method, as shown in FIG. 3, a coating liquid 31 as described above is applied onto a base fabric 30 using a gravure coater 32, and is dried using a dryer 33 to form a skin layer (not shown). By forming, a synthetic leather raw fabric 34 is obtained.
またスプレーコーティング法の場合は、基布４０上に、
前述のようなコーテイング液をスプレー４２で噴霧（４
１は噴霧状態を示す。）、付着させ、乾燥機４３で乾燥
した後、冷却ロール４４等で冷却して表皮層（図示せず
）を形成することにより、合成皮革原反４５が得られる
。In addition, in the case of the spray coating method, on the base fabric 40,
Spray the coating liquid as described above with the spray 42 (4
1 indicates a spray state. ), and after drying with a dryer 43, cooling with a cooling roll 44 or the like to form a skin layer (not shown), a synthetic leather raw fabric 45 is obtained.
こうして作製された合成皮革原反は基布上に直接、又は
接着層を介して表皮層を設けたものであるが、表皮層の
下に多孔質ウレタン層を有する合成皮革原反を作製する
場合は、多孔質層用染色性ウレタン、発泡剤等を含む発
泡性ウレタン組成物を乾式発泡機で機械的に約１．２〜
５倍（容量）、好ましくは１．５〜４倍に空気発泡させ
、これを基布上に塗布し、６０〜１４０℃、好ましくは
６０〜１２０℃で乾燥する。発泡の程度が１．２倍より
小さいと発泡による柔軟性や多孔性が低下して硬く、ゴ
ムライクになり、また５より大きいと、多孔質の強度が
低下して剥離し易く使用に耐えなくなる。The synthetic leather raw fabric produced in this way has a skin layer provided directly on the base fabric or via an adhesive layer, but when producing a synthetic leather raw fabric that has a porous urethane layer below the skin layer. The foamable urethane composition containing the dyeable urethane for the porous layer, the foaming agent, etc. is mechanically heated to about 1.2~
The foam is air-foamed to 5 times (by volume), preferably 1.5 to 4 times, and then applied onto a base fabric and dried at 60 to 140°C, preferably 60 to 120°C. If the degree of foaming is less than 1.2 times, the flexibility and porosity due to foaming will decrease, making it hard and rubber-like, and if it is greater than 5, the porous strength will decrease and it will be easy to peel off, making it unusable.
乾燥温度が１４０℃を越えると、乾燥速度がコーティン
グ層内部で大きく異なり易く、その結果、安定な多孔質
層とならない。乾燥温度が６０℃未満では乾燥速度が遅
くなり、発泡層のへたつが生じたり、工業的には乾燥工
程がネックとなり高コストのものとなる。If the drying temperature exceeds 140° C., the drying rate tends to vary greatly within the coating layer, and as a result, a stable porous layer cannot be obtained. If the drying temperature is less than 60° C., the drying speed will be slow and the foamed layer will sag, and the drying process will become a bottleneck from an industrial perspective, resulting in high costs.
多孔質層形成用発泡性ウレタン組成物は一般に、多孔質
層用ウレタン６０〜９０ｗｔ％、起泡剤２〜７ｗｔ％、
発泡剤０〜１０ｗｔ％、発泡安定剤０．５〜１、５ｗｔ
％、増粘剤０〜５ｗｔ％、架橋剤θ〜１５猶・［％、前
記天然有機高分子粉末０〜２０ｗｔ％、及びフィラーθ
〜２０ｗｔ％を水に溶解又は分散したものである。ここ
で、前記天然有機高分子粉末とフィラーとの合計量は３
０ｗｔ％以下が溶液の粘度の点や均一発泡性の点から好
ましい。また、３０ｗｔ％を超えると製品か硬くて脆い
ものになり易いからである。The foamable urethane composition for forming a porous layer generally contains 60 to 90 wt% of the urethane for the porous layer, 2 to 7 wt% of a foaming agent,
Foaming agent 0-10wt%, foaming stabilizer 0.5-1.5wt
%, thickener 0 to 5 wt%, crosslinking agent θ to 15 wt%, the natural organic polymer powder 0 to 20 wt%, and filler θ
~20wt% is dissolved or dispersed in water. Here, the total amount of the natural organic polymer powder and filler is 3
A content of 0 wt % or less is preferable from the viewpoint of solution viscosity and uniform foamability. Moreover, if it exceeds 30 wt%, the product tends to be hard and brittle.
起泡剤としては第一工業製薬社製スコアミンフォーマー
ＲＦがある。As a foaming agent, there is Scoremin Former RF manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
発泡剤としては例えばフロン、水等がある。Examples of foaming agents include fluorocarbons and water.
発泡安定剤としては例えば第一工業製薬社製ファインガ
ムＧ２７０がある。Examples of the foaming stabilizer include Fine Gum G270 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
増粘剤としては例えば第一工業製薬社製スーパーフレッ
クスＶＦがある。Examples of thickeners include Superflex VF manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
架橋剤としては例えば第一工業製薬社製Ｐ８９１４があ
る。Examples of the crosslinking agent include P8914 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
フィラーとしては例えば炭酸カルシウム、タルク等があ
る。Examples of fillers include calcium carbonate and talc.
発泡後のウレタン組成物のコーティング法としては表皮
層の場合と同様なコーティング法が採用できるが、通常
は直接コーティング法が使用される。塗布量は固形分で
５０〜２００ｇ／ｒｒｒが適当である。こうして形成さ
れる多孔質層の厚さは用途によって異なるが、一般に２
０〜１０００μｍ程度である。As a coating method for the urethane composition after foaming, a coating method similar to that for the skin layer can be adopted, but a direct coating method is usually used. The appropriate coating amount is 50 to 200 g/rrr in terms of solid content. The thickness of the porous layer formed in this way varies depending on the application, but is generally 2.
It is about 0 to 1000 μm.
以上のようにして基布上に多孔質ウレタン層を形成した
後、更にその上に前述のようなコーティング法で表皮層
を形成することにより、表皮層下に多孔質ウレタン層を
有する合成皮革原反が得られる。After forming a porous urethane layer on the base fabric as described above, a skin layer is further formed on top of it by the coating method described above, thereby producing a synthetic leather raw material having a porous urethane layer under the skin layer. The opposite is obtained.
次に合成皮革原反の染色法について説明する。Next, a method for dyeing raw synthetic leather will be explained.
染色用原反はまず精錬される。これは表面の汚れ、糊、
油脂分等を取り除き染料が浸透し易くして、むら染めに
ならないように実施する準備工程である。この工程では
、原反は界面活性剤（通常０．０５〜０．２ｗｔ％）、
浸透潤滑剤（通常０．０５〜０．５ｗｔ％）及び均染剤
（通常０．１〜０．５ｗｔ％）を溶解した水溶液中、常
温〜９５℃の温度範囲で約２０分〜６０分間洗浄される
。The raw fabric for dyeing is first refined. This is due to surface dirt, glue,
This is a preparatory process that removes fats and oils to make it easier for the dye to penetrate and prevent uneven dyeing. In this process, the original fabric contains a surfactant (usually 0.05 to 0.2 wt%),
Washing in an aqueous solution containing a penetrating lubricant (usually 0.05 to 0.5 wt%) and a leveling agent (usually 0.1 to 0.5 wt%) at a temperature range of room temperature to 95°C for about 20 to 60 minutes. be done.
精錬後の原反は水洗され、次の染色工程により染色され
る。染色工程は、まず染色用原反を入れた染色助剤水溶
液を昇温しつつ染料及び染色助剤を加えて行なわれる。After refining, the original fabric is washed with water and dyed in the next dyeing process. The dyeing process is first carried out by adding a dye and a dyeing aid while heating an aqueous solution of a dyeing aid containing an original fabric for dyeing.
この染色溶液が染料の固着温度に達したならば、この温
度に一定時間保持した後、冷却する。染色溶液は反応染
料（通常、０゜５〜１０ｗｔ％）及び染色助剤（通常、
被染色物重量に対し２．５〜ｌｏｗｔ％）を必須成分と
し、これに、必要あれば分散均染剤（通常、染色溶液に
対し０．０５〜１．０ｗｔ％）、浴中柔軟剤（通常、染
色溶液に対し０．０５〜０．１５ｗｔ％）、染料固着剤
（通常、染色溶液に対し０．１〜０．４ｗｔ％）を加え
て構成される。When the dyeing solution reaches the fixation temperature of the dye, it is maintained at this temperature for a certain period of time and then cooled. The dyeing solution contains a reactive dye (usually 0°5-10wt%) and a dyeing aid (usually
2.5~lowt% of the weight of the object to be dyed) is an essential component, and if necessary, a dispersion leveling agent (usually 0.05~1.0wt% of the dyeing solution) and a bath softener ( Usually, 0.05 to 0.15 wt% of the dyeing solution) and a dye fixing agent (usually 0.1 to 0.4 wt% of the dyeing solution) are added.
次にこうして染色された原反はソーピング（洗浄）工程
により洗浄される。ソーピング工程はソーピング剤とし
て界面活性剤（通常、０．０２〜０．０５ｗｔ％）の水
溶液中に、常温〜９５℃の温度範囲で約１０〜３０分間
、染色用原反を浸漬して、染色工程で付着した未固着の
余分な染料を取り除くことにより行なわれる。充分取り
除けない場合は再度繰り返す。Next, the original fabric dyed in this way is washed in a soaping (washing) step. The soaping process involves immersing the original fabric for dyeing in an aqueous solution of a surfactant (usually 0.02 to 0.05 wt%) as a soaping agent for about 10 to 30 minutes at a temperature range of room temperature to 95°C. This is done by removing unfixed excess dye that has adhered during the process. If it cannot be removed sufficiently, repeat again.
最後に、ソーピング後の湿潤染色原反は、必要あればテ
ンターにより一定の張りを与える仕上げ工程を経た後、
乾燥工程で乾燥される。乾燥工程は湿潤染色原反をマン
グルで絞って、余分な水分を除去した後、テンターに掛
は乾燥機中に通して乾燥することにより行なわれる。こ
の時の乾燥温度は１３０°Ｃ以下、好ましくは１２０°
Ｃ以下である。Finally, the wet dyed raw fabric after soaping goes through a finishing process to give it a certain tension using a tenter if necessary.
It is dried in the drying process. The drying process is carried out by squeezing the wet dyed fabric with a mangle to remove excess water, then hanging it on a tenter and passing it through a dryer to dry it. The drying temperature at this time is 130°C or less, preferably 120°C.
C or lower.
１３０℃以上で乾燥すると、表皮層や多孔質層のウレタ
ンが分解したり、或いは乾燥機の温度むら等が生じて局
部的に高温となり、ウレタンが溶融又は変形したりする
。なお乾燥工程の前後、どちらでもよいが、もみ工程、
及び／又は表面処理工程を経てもよい。また仕上げ工程
は接水剤、撲油剤帯電防止剤、柔軟剤、風合い調整剤、
防災剤等の存在下で行なってもよい。If dried at 130° C. or higher, the urethane in the skin layer or porous layer may decompose, or the temperature of the dryer may become uneven, resulting in locally high temperatures, which may cause the urethane to melt or deform. It may be done either before or after the drying process, but the kneading process,
and/or may undergo a surface treatment step. In addition, the finishing process includes water-wetting agents, antistatic agents, anti-static agents, fabric softeners, texture control agents,
It may be carried out in the presence of disaster prevention agents, etc.
以上の染色法で用いられる界面活性剤、浸透湿潤剤、均
染剤、染色助剤、分散均染剤、浴中柔軟剤、染料固着剤
等はいずれも通常使用されているものでよい。The surfactants, penetrating wetting agents, leveling agents, dyeing aids, dispersion leveling agents, bath softeners, dye fixing agents, etc. used in the above dyeing methods may all be those commonly used.
第５図に本発明に係る染色合成皮革の代表的な製造工程
を示した。FIG. 5 shows a typical manufacturing process for the dyed synthetic leather according to the present invention.
以下に本発明を実施例によって説明する。 The present invention will be explained below by way of examples.
表−１に示す各コーテイング液を５０Ｏｒｐｍで１時間
攪拌、混合した後、アスピレータ−で吸引、脱気した。Each coating solution shown in Table 1 was stirred and mixed at 50 rpm for 1 hour, and then suctioned and degassed using an aspirator.
なおコーテイング液Ａ、Ｂ、Ｃ，Ｄ、Ｅの各皮革粉含有
量は夫々、ウレタンとの固形分換算で１０ｗｔ％、２０
ｗｔ％、１ｗｔ％、６０ｗｔ％、０ｗｔ％である。The leather powder content of coating liquids A, B, C, D, and E is 10 wt% and 20 wt%, respectively, in terms of solid content with urethane.
wt%, 1wt%, 60wt%, and 0wt%.
表−１
（至）混合ジオール系ウレタン：三洋化成工業社製５Ｐ
２００Ｄ ｆ分３０ｗｔ％）皮革粉：出光石油化学社製
ＤＭＦニジメチルホルムアミド
ＩＰＡ：イソプロビルアルコール
各コーテイング液を第２図の転写コーティング装置を用
いて離型紙（大日本印刷社製ＤＮ−ＴＰシリーズのセミ
マット調を使用）上に１２０ｇ／ｒｒｒ塗布し、１１０
℃で約９０秒間乾燥して、表皮層となる２０μｍ厚のウ
レタンフィルムを形成し、その上に接着剤（三洋化成工
業社製サンブレンＬＱＸ５：５０ｇとサンブレンＬＯ３
−Ａ：５０ｇとを混合、攪拌後、脱気して調製）を１０
０ｇ／ｒｒ？塗布し、更にその上に、ニップロールによ
り無地のナイロンタフタ基布（２１Ｏデニールの繊維に
よる手織）を重ねて接着し、１００℃で約９０秒間乾燥
して５種の染色用合成皮革原反（これら原反は、コーテ
イング液Ａ、Ｂ、Ｃ，Ｄ及びＥに対応してそれぞれ、Ｇ
−Ａ、 Ｇ−Ｂ、 Ｇ−Ｃ，Ｇ−Ｄ及びＧ−εとする。Table-1 (To) Mixed diol urethane: 5P manufactured by Sanyo Chemical Industries, Ltd.
200D f content 30 wt%) Leather powder: DMF Nidimethylformamide manufactured by Idemitsu Petrochemical Co., Ltd. IPA: Isopropyl alcohol Each coating solution was coated with release paper (DN-TP series manufactured by Dai Nippon Printing Co., Ltd.) using the transfer coating device shown in Figure 2. Apply 120g/rrr on top (using semi-matte tone), 110
℃ for about 90 seconds to form a 20 μm thick urethane film that will become the skin layer, and adhesives (Sanyo Chemical Industries, Ltd. Sunbren LQX5: 50 g and Sunbren LO3
-A: Prepared by mixing 50g, stirring, and degassing) 10
0g/rr? On top of that, a plain nylon taffeta base fabric (hand-woven from 21O denier fibers) was layered and adhered using nip rolls, and dried at 100°C for about 90 seconds to obtain five types of dyed synthetic leather raw fabrics (these The original fabric was coated with G corresponding to coating liquids A, B, C, D and E, respectively.
-A, G-B, G-C, G-D and G-ε.
）を作製した。) was created.
合成皮革原反の染色
まず染色用各原反に対し、非イオン系界面活性剤（開成
化学工業社製ゾルゲＡＨ）２ｇ、非イオン系界面活性剤
（明成化学工業社製浸透潤滑剤メイセリン旧００） ０
．５ｇ及び非イオン系界面活性剤（明成化学工業社製脱
気浸透剤マイネックスＴｆ（） ０．５ｇを水１ｊ７に
溶解した水溶液中、６０°Ｃで２０分間精錬処理し、更
に、簡単に脱水処理した。Dyeing of synthetic leather raw fabric First, for each raw fabric for dyeing, 2 g of nonionic surfactant (Solge AH manufactured by Kaisei Chemical Industry Co., Ltd.), 2 g of nonionic surfactant (penetrating lubricant Meiselin Old 00 manufactured by Meisei Chemical Industry Co., Ltd.) ) 0
．． 5 g of nonionic surfactant (Deaeration Penetrant Minex Tf (manufactured by Meisei Chemical Industry Co., Ltd.) in an aqueous solution of 0.5 g dissolved in water 1j7 at 60°C for 20 minutes, and then easily dehydrated. Processed.
次に精錬後の各原反を、ピリミジン系反応染料（５ａｎ
ｄｏｚ社製Ｄｒｉｍａｒｅｎｅ Ｔｕｒｑｕｏｉｓｅ
Ｘ−Ｂ） ３０ ｇ 。Next, each raw fabric after refining was treated with pyrimidine-based reactive dye (5an
Drimarene Turquoise manufactured by doz
X-B) 30 g.
無水芒硝６０ｇおよび染色助剤（５ａｎｄｏｚ社製Ｒｅ
ｖａｔｏｌ ＳＨｇを水ＩＡに溶解した染色溶液中、４
０℃で１０分間染色処理し、更にソーダ灰１５ｇを加え
て１０分間放置後、昇温し、８５〜９０℃で６０分間固
着処理した。引き続きこの染色原反を、トリポリりん酸
ソーダ１ｇを１１の水に溶解した沸騰ソーピンダ液（Ｃ
ｉｂａ−ＧｅｉｇＹ社製５ａｎｄｏｐｕｒ Ｒ３ＫＬｉ
ｑｕｉｄ）中で２０分間ソーピング処理し、２回水洗し
、マングルで絞って余分な水分を除去した後、１００℃
で乾燥した。得られた５種の染色合成皮革は、使用した
染色用合成皮革原反Ｇ−Ａ、 Ｇ−Ｂ、 Ｇ−Ｃ。60g of anhydrous sodium sulfate and dyeing aid (Re manufactured by 5andoz)
In a staining solution of vator SHg dissolved in water IA, 4
After dyeing at 0°C for 10 minutes, 15 g of soda ash was added and left to stand for 10 minutes, the temperature was raised and fixation was carried out at 85 to 90°C for 60 minutes. Subsequently, this dyed raw fabric was treated with a boiling soapinda solution (C
5andopur R3KLi manufactured by iba-GeigY
(quid) for 20 minutes, rinsed with water twice, squeezed with a mangle to remove excess moisture, and then heated to 100°C.
It was dried. The five types of dyed synthetic leather obtained were the dyed synthetic leather raw fabrics G-A, G-B, and G-C.
Ｇ−Ｄ及びＧ−Ｅに対応して夫々、実施例】、実施例２
、比較例１、比較例２及び比較例３とする。Example] and Example 2 corresponding to G-D and G-E, respectively.
, Comparative Example 1, Comparative Example 2, and Comparative Example 3.
比Ｕ土：」一
実施例１、実施例２及び比較例３で作製した各染色用合
成皮革原反Ｇ−Ａ、 Ｇ−Ｂ、 Ｇ−Ｅを硫酸アンモニ
ウム２０ｇ及び染色助剤（Ｃｉｂａ−Ｇｅｉｇｙ社製Ａ
ｌｂｅｇａｆ ＳＷ） ２０ ｇを水１１に溶解した溶
液中、３０°Ｃで１０分間予備処理した後、 １．２酸
性含金染料（Ｃ１ｂａ−Ｇｅ ｉｇＹ社製Ｌａｎａｃｒ
ｏｎ ＢｌａｃｋＳ−Ｒ）３０ ｇ及び酢酸５ｇを加え
て染色溶液とし、この溶液中で３０℃で１０分間染色処
理し、引き続き９５℃で４５分間固着処理した。得られ
た３種の染色合成皮革は、使用した染色用合成皮革原反
Ｇ−Ａ、 Ｇ−Ｂ、及びＧ−Ｈに対応して夫々、比較例
４、比較例５及び比較例６とする。Philippine Soil: Each of the raw synthetic leather fabrics G-A, G-B, and G-E for dyeing prepared in Example 1, Example 2, and Comparative Example 3 was mixed with 20 g of ammonium sulfate and a dyeing aid (Ciba-Geigy Co., Ltd.). Made by A
After pretreatment at 30°C for 10 minutes in a solution of 20 g of lbegaf SW) dissolved in 11 parts of water, 1.2 acidic metal-containing dye (C1ba-GeigY Lanacr)
On BlackS-R) 30 g and acetic acid 5 g were added to prepare a staining solution, dyeing was carried out in this solution at 30°C for 10 minutes, and then fixation was carried out at 95°C for 45 minutes. The three types of dyed synthetic leather obtained were designated as Comparative Example 4, Comparative Example 5, and Comparative Example 6, respectively, corresponding to the dyed synthetic leather originals G-A, G-B, and G-H used. .
以上の実施例１〜２及び比較例１〜６で製造した染色合
成皮革と、使用したコーテイング液及び使用した染料と
の関係を表−２に、またこれら染色合成皮革の性能を試
験した結果を表−３に示す。Table 2 shows the relationship between the dyed synthetic leathers produced in Examples 1 to 2 and Comparative Examples 1 to 6, the coating liquid used, and the dye used, and the results of testing the performance of these dyed synthetic leathers. It is shown in Table-3.
表−２
表＝３
ゑく日」四９１２ｃはルａ＜ 鼻”／こν入ｔ口ろ→こ
弓弓く、会呼月１爾１わ（た１〜試験方法は次の通りで
ある。Table 2 Table = 3 4912c is rua<nose''/koν 入口ro→koyumi yuku, meeting month 1 er 1 wa (ta 1 ~ The test method is as follows. .
染色性：比較例５の染色の程度を基準に評価した。Dyeability: Evaluated based on the degree of staining in Comparative Example 5.
○は良好、△はやや薄い、×はほとんど染まらない、を
表す。○ means good, △ means slightly dyed, and × means almost no staining.
色移行性：
各合成皮革原反の染色前のものと染色後のものを表皮層
同士で接触するように直径３〜５■のガラス管に輪ゴム
で固定し７０°Ｃ〜９５％ＲＨの恒温槽中で３日間放置
する。Color transferability: Each raw material of synthetic leather before and after dyeing was fixed with a rubber band in a glass tube with a diameter of 3 to 5 cm so that the skin layers were in contact with each other, and kept at a constant temperature of 70°C to 95% RH. Leave it in the tank for 3 days.
冷却後表皮を観察し、色の移行の有無を調べる。After cooling, observe the epidermis to check for color migration.
○は良好、△は薄く着色、×ははっきりと全面移行する
、を表す。○ means good, △ means light coloring, and × means clear transfer over the entire surface.
タック感：
手で触った感じ、及び各染色合成皮革の表皮層同士を接
触させて表皮層の滑り易さを評価した。Tackiness: The slipperiness of the skin layers of each dyed synthetic leather was evaluated by touching it with the hand and by bringing the skin layers of each dyed synthetic leather into contact with each other.
○は滑りやすいドライタッチ、△は滑り難い、×は滑り
難くドライタッチでない、を示す。○ indicates slippery dry touch, △ indicates non-slip, and × indicates non-slip and not dry touch.
吸放湿性：
１３０Ｍ角のアルミ板の周縁部に１５酊幅の両面テープ
を貼り付け、これを、２３℃〜５０％ＲＨの恒温槽中で
２４時間状態調節した１ ３０ｗ角の染色合成皮革を基
布側で貼り付け、表皮層側の周縁部を１５ｍｍ幅のビニ
ルテープでシールして表皮層の露出表面を約１００肛角
とする。Moisture absorption/desorption properties: A 15 mm wide double-sided tape was pasted on the peripheral edge of a 130 m square aluminum plate, and this was conditioned for 24 hours in a constant temperature bath at 23 ° C to 50% RH. It is pasted on the base fabric side, and the peripheral edge on the skin layer side is sealed with a 15 mm wide vinyl tape, so that the exposed surface of the skin layer is approximately 100 mm wide.
次に吸湿性測定の場合は、このサンプル（アルミ板付き
）を２３°Ｃ〜３０％ＲＨの恒温槽中で２４時間状態調
節した時の重量（基準重量）Ｗｏを測定し、更にこの状
態調節した同一サンプルを２３℃〜８０％ＲＨの恒温槽
又は同等の雰囲気の硫酸アンモニア飽和水溶液を入れた
容器中に２４時間放置した時の重量ＷＩを測定する。Next, in the case of hygroscopicity measurement, measure the weight (reference weight) Wo when this sample (with aluminum plate) is conditioned for 24 hours in a constant temperature bath at 23°C to 30% RH, and then The weight WI is measured when the same sample is left for 24 hours in a constant temperature bath at 23° C. to 80% RH or in a container containing a saturated aqueous solution of ammonia sulfate in an equivalent atmosphere.
一方、放湿性測定の場合はサンプルを２３°ｃ８０％Ｒ
Ｈの恒温槽又は同等の雰囲気の硫酸アンモニア飽和溶液
を入れた容器の中で２４時間状態調節した時の重量（基
準重量）Ｗｅを測定し、更にこの状態調節した同一サン
プルを２３°Ｃ〜３ｏ％Ｒ１（の恒温槽中に２４時間放
置した時の重量を測定する。On the other hand, in the case of moisture release measurement, the sample was placed at 23°C80%R.
The weight (reference weight) We was measured after conditioned for 24 hours in a constant temperature bath of H or a container containing a saturated solution of ammonia sulfate in an equivalent atmosphere, and the same sample was then heated at 23°C to 3oC. Measure the weight when the sample is left in a constant temperature bath of %R1 for 24 hours.
なお各重量は１■の単位まで測定し、また測定は原則と
して２３℃〜５０％ＲＨの雰囲気中で行なう。It should be noted that each weight is measured to the nearest inch, and the measurement is generally carried out in an atmosphere of 23 DEG C. to 50% RH.
以上の測定値から吸湿性（１耐当たりの吸湿速度又は吸
湿量として）及び放湿性（ｌｒｒｒ当たりの放湿速度又
は放湿量として）は下記式から求められる。From the above measured values, the hygroscopicity (as the rate of moisture absorption or amount of moisture absorbed per unit resistance) and the moisture release property (as the rate or amount of moisture released per lrrr) are calculated from the following formula.
す。vinegar.
表−４に示す各発泡性コーテイング液（粘度３８０００
ｃｐｓ ）をストーク社製発泡機ＦＰ−Ｉ［−Ｃとコー
ティングヘッドＣＴ−ＩＶとを組み合わせた装置で３．
０倍に発泡させ、これを第１図の直接コーティング装置
を用いて無地のナイロンニット基布上に乾燥重量で１０
０ｇ／ｒｒｒになるよう塗布し、１２０℃で２分間乾燥
して６００μｍ厚の多孔質ウレタン層を形成した。こう
して得られた多孔質層を有する３種の基布は、使用した
発泡性コーテイング液ａ、 ｂ及びＣに対応して夫々
、Ｋａ、 Ｋｂ、 Ｋｃとする。Each foamable coating liquid shown in Table 4 (viscosity 38,000
cps) using a device combining a foaming machine FP-I[-C manufactured by Stork Co., Ltd. and a coating head CT-IV].
0x foam, and then coated on a plain nylon knit base fabric with a dry weight of 10x using the direct coating device shown in Figure 1.
It was applied at a concentration of 0 g/rrr and dried at 120° C. for 2 minutes to form a porous urethane layer with a thickness of 600 μm. The three types of base fabrics having porous layers thus obtained are named Ka, Kb, and Kc, respectively, corresponding to the foamable coating liquids a, b, and C used.
（但しＷ。・・・基準重量、Ｗｌ・・・２４時間放置時
の重量、Ｓ・・・サンプルの露出表面積）○は、吸湿性
、放湿性とも４ｇ／ｒｒｒ以上、△は、同じく３〜４ｇ
／醒、×は、同じ＜３ｇ／耐以下を示表−４
※１：天然有１１砂）Ｐ粉末として出光石ｆＦＭビ勾出
製平均粒径Ｄ５１１＝７μｍの皮革粉
白石カルシウム社製ハイシライトＨ３２第一工業製薬社
製スーパーフレックス四第−工業製薬社製スーパーフレ
ックスＥ２０００第一」」遷四Ｉ化製スーパーフレック
スＥ４０００スコアミンフォーマー朋
第−１傷−８９１４
第一］Ｊ鍾訴１十製ファインガムＧ−２７０（４％）次
に、実施例１及び２と同様な染色用合成皮革原反の製造
法に従って、（１）基布Ｋｂに対しては、前記表−１の
コーテイング液Ａ、Ｂ、Ｃ，Ｄ及びＥを夫々適用して（
多孔質層上に適用、以下同様）５種の染色用合成皮革原
反（これら原反は、使用したコーテイング液Ａ、Ｂ、Ｃ
，Ｄ及びＥに対応して夫々、Ｇｂ−Ａ、 Ｇｂ−８，Ｇ
ｂ−Ｃ，Ｇｂ−Ｄ及びＧｂ−Ｅとする。）を作製し、（
２）基布Ｋａに対しては、コーテイング液Ｂを適用して
染色用合成皮革原反Ｇａ−８を作製し、また（３）基布
Ｋｃに対しては同じくコーテイング液Ｂを適用して染色
用合成皮革原反Ｇｃ−Ｂを作製した。(However, W: Standard weight, Wl: Weight when left for 24 hours, S: Exposed surface area of sample) ○: 4g/rrr or more for both hygroscopicity and moisture release, △: 3~ 4g
Table-4 *1: Naturally available 11 sand) As P powder, Idemitsuite fFM Bikagehide leather powder with average particle diameter D511 = 7 μm, Shiraishi Calcium Co., Ltd., Hisilite H32. Dai-ichi Kogyo Seiyaku Co., Ltd. Superflex 4th - Kogyo Seiyaku Co., Ltd. Superflex E2000 1st'' ``Shenshi Ika Co., Ltd. Superflex E4000 Scoremin Former Ho No. 1 Wound-8914 1st] Made by J Zhongsue 10 Fine Gum G-270 (4%) Next, according to the same method for producing synthetic leather material for dyeing as in Examples 1 and 2, (1) For the base fabric Kb, coating liquid A in Table 1 above was applied. , B, C, D and E respectively (
5 types of synthetic leather raw fabrics for dyeing (applied on the porous layer, the same applies hereinafter) (These raw fabrics are coated with the coating liquids A, B, and C used.
, D and E, respectively, Gb-A, Gb-8, G
b-C, Gb-D and Gb-E. ) and (
2) Coating liquid B was applied to the base fabric Ka to produce synthetic leather raw fabric Ga-8 for dyeing, and (3) coating liquid B was also applied to the base fabric Kc to dye it. A raw synthetic leather fabric Gc-B was prepared.
合成皮革原反の染色
染色用原反として、以上のようにして作製した７種の原
反Ｇｂ−Ａ、 Ｇｂ−Ｂ、 Ｇｂ−Ｃ，Ｇｂ−Ｄ、 Ｇ
ｂ−Ｅ、 Ｇａ−Ｂ及びＧｃ−Ｂを用い、無水芒硝６０
ｇを８０ｇに変え、且つソーダ灰１５ｇを２０ｇに変え
た他は、実施例１及び２と同じ染色法に従って７種の染
色合成皮革を作製した。Seven types of raw fabrics Gb-A, Gb-B, Gb-C, Gb-D, and G produced as described above were used as raw fabrics for dyeing synthetic leather raw fabrics.
Using b-E, Ga-B and Gc-B, anhydrous mirabilite 60
Seven types of dyed synthetic leather were produced according to the same dyeing method as in Examples 1 and 2, except that g was changed to 80 g and 15 g of soda ash was changed to 20 g.
これら染色合成皮革は、使用した原反Ｇｂ−Ａ、 Ｇｂ
−Ｂ、 Ｇｂ−Ｃ，Ｇｂ−Ｄ、 Ｇｂ−Ｄ、 Ｇｂ−Ｅ
、 Ｇａ−Ｂ及びＧｃ−Ｂに対応して夫々、実施例３、
実施例４、比較例７、比較例８、比較例９、実施例５及
び実施例６とする。These dyed synthetic leathers were made using the original fabric Gb-A, Gb
-B, Gb-C, Gb-D, Gb-D, Gb-E
, Example 3 for Ga-B and Gc-B, respectively.
Example 4, Comparative Example 7, Comparative Example 8, Comparative Example 9, Example 5, and Example 6.
板敷り土ユニ±１
染色用原反として実施例３〜６で作製した原反Ｇｂ−Ａ
、 Ｇｂ−Ｂ、 Ｇｂ−Ｅ、 Ｇａ−Ｂ及びＧｃ−Ｂを
用い、且つピッミジン系反応染料３０ｇを４０ｇに変え
た他は、比較例４〜６と同じ染色法で５種の染色合成皮
革を作製した。これら染色合成皮革は、使用した原反Ｇ
ａ−Ａ、 Ｇｂ−Ｂ、 Ｇｂ−Ｅ、 Ｇａ−Ｂ及びＧｃ
−Ｂに夫々対応して比較例１０、比較例１１、比較例１
２、比較例１３及び比較例１４とする。Itagiri soil Uni±1 Original fabric Gb-A produced in Examples 3 to 6 as an original fabric for dyeing
, Gb-B, Gb-E, Ga-B, and Gc-B, and except that 30 g of pymidine-based reactive dye was changed to 40 g, five types of dyed synthetic leather were dyed using the same dyeing method as in Comparative Examples 4 to 6. Created. These dyed synthetic leathers are
a-A, Gb-B, Gb-E, Ga-B and Gc
Comparative Example 10, Comparative Example 11, Comparative Example 1 corresponding to -B, respectively.
2. Comparative Example 13 and Comparative Example 14.
以上の実施例３〜６及び比較例７〜１４で製造した染色
合成皮革と、使用した発泡性コーテイング液、使用した
コーテイング液及び使用した染料との関係を表−５に、
またこれら染色合成皮革の性能を試験した結果を表−６
に示す。Table 5 shows the relationship between the dyed synthetic leather produced in Examples 3 to 6 and Comparative Examples 7 to 14, the foamable coating liquid used, the coating liquid used, and the dye used.
Table 6 also shows the results of testing the performance of these dyed synthetic leathers.
Shown below.
表−５
染色性：
実施例３の染色の程度を基準に評価した。○、△、×の
意味は表−３に同じ。Table-5 Stainability: Evaluation was made based on the degree of staining in Example 3. The meanings of ○, △, and × are the same as in Table-3.
吸放湿性：
試験方法は表−３に同じであるが、○は６ｇ／ ｒｄ以
上、△は４〜６ｇ／イ、×は４ｇ１ｒｄ以下、を表す。Moisture absorption and desorption properties: The test method is the same as shown in Table 3, except that ◯ indicates 6 g/rd or more, △ indicates 4 to 6 g/i, and × indicates 4 g/rd or less.
へたり、樹脂劣化：
染色製品を７０℃〜９５％ＲＨ中、３週間（３年間相当
）保存し、厚さ変化を調べる。厚さ変化量が初期厚さの
１０％以内は○、２０％以内は△、２０％以上は×とし
た。同様の試験後、樹脂劣化がないときは○、あるとき
は×とした。Settling, resin deterioration: Store the dyed product at 70°C to 95% RH for 3 weeks (equivalent to 3 years) and examine changes in thickness. If the thickness change was within 10% of the initial thickness, it was rated ◯, if it was within 20%, it was △, and if it was 20% or more, it was rated ×. After the same test, if there was no resin deterioration, it was marked as ○, and if there was, it was marked as ×.
以上のような本発明によれば、多孔質層を持つものも、
持たないものも、本来の皮革様の感触及び性能を維持し
ながら、色移行性がなく、しかも明るい色も深みのある
色も多く、染色濃度も高い染色合成皮革を提供すること
ができる。According to the present invention as described above, even those having a porous layer,
Even if it does not have this, it is possible to provide dyed synthetic leather which has no color migration, has many bright colors and deep colors, and has a high dye density while maintaining the feel and performance of original leather.
第１〜４図は夫々、本発明に係る染色合成皮革用合成皮
革の原反の製造に使用できる直接コーティング装置、転
写コーティング装置、グラビアコーティング装置及びス
プレーコーティング装置の概略図、第５図は本発明に係
る染色合成皮革の代表的な製造工程図である。
１．１８，３４．４０・・・基布、２． １２． ３１
゜４１・・・コーテイング液（但し４１は噴霧状態）、
３・・・ドクターナイフ、４，１３，２０，３３．４３
・・・乾燥機、６，１４，２１．４４・・・冷却筒又は
冷却ロール、７，２０，３０．４５・・・合成皮革原反
、１０・・・離型紙、１１．１７・・・ナイフロール、
１５・・・離型紙上の表皮層用樹脂フィルム、１６・・
・接着剤、１９・・・ニップロール、３２・・・グラビ
アコーター ４２・・・スプレー。Figures 1 to 4 are schematic diagrams of a direct coating device, a transfer coating device, a gravure coating device, and a spray coating device that can be used for producing raw material for dyed synthetic leather according to the present invention, and Figure 5 is a schematic diagram of the present invention. 1 is a typical manufacturing process diagram of dyed synthetic leather according to the invention. 1.18, 34.40... base fabric, 2. 12. 31
゜41...Coating liquid (however, 41 is in a spray state),
3...Doctor knife, 4,13,20,33.43
...Dryer, 6,14,21.44...Cooling cylinder or cooling roll, 7,20,30.45...Synthetic leather raw material, 10...Release paper, 11.17... knife roll,
15...Resin film for skin layer on release paper, 16...
・Adhesive, 19... Nip roll, 32... Gravure coater 42... Spray.
Claims (4)
タン５０〜９８ｗｔ％と天然有機高分子粉末５０〜２ｗ
ｔ％との混合物よりなる表皮層を設けた合成皮革原反を
、反応染料で染色してなることを特徴とする染色合成皮
革。(1) 50 to 98 wt% polyurethane and 50 to 2 wt% natural organic polymer powder, each dyeable with a reactive dye, on the base fabric
A dyed synthetic leather characterized in that it is made by dyeing a raw synthetic leather fabric with a skin layer made of a mixture of t% and t% with a reactive dye.
１）の染色合成皮革。(2) Claim (2) wherein the natural organic polymer powder is leather powder.
1) Dyed synthetic leather.
タン層とその上に、各々反応染料で染色可能な、ポリウ
レタン５０〜９８ｗｔ％と天然有機高分子粉末５０〜２
ｗｔ％との混合物よりなる表皮層とを設けた合成皮革原
反を、反応染料で染色してなることを特徴とする染色合
成皮革。(3) On the base fabric, a porous polyurethane layer that can be dyed with a reactive dye, and on top of that, 50-98 wt% polyurethane and 50-2% natural organic polymer powder, each dyeable with a reactive dye.
A dyed synthetic leather characterized in that it is obtained by dyeing a raw synthetic leather fabric with a skin layer made of a mixture of % and % by weight with a reactive dye.
２）の染色合成皮革。(4) Claim (4) wherein the natural organic polymer powder is leather powder.
2) Dyed synthetic leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14401490A JPH0791785B2 (en) | 1990-05-31 | 1990-05-31 | Dyed synthetic leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14401490A JPH0791785B2 (en) | 1990-05-31 | 1990-05-31 | Dyed synthetic leather |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0441783A true JPH0441783A (en) | 1992-02-12 |
| JPH0791785B2 JPH0791785B2 (en) | 1995-10-04 |
Family
ID=15352319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14401490A Expired - Lifetime JPH0791785B2 (en) | 1990-05-31 | 1990-05-31 | Dyed synthetic leather |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791785B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021157351A1 (en) | 2020-02-07 | 2021-08-12 | 第一化成株式会社 | Method for manufacturing synthetic leather |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5090319B2 (en) * | 2007-11-22 | 2012-12-05 | 東レコーテックス株式会社 | Synthetic leather consisting of plant-derived components |
| JP5090320B2 (en) * | 2007-11-30 | 2012-12-05 | 東レコーテックス株式会社 | Synthetic leather consisting of plant-derived components |
-
1990
- 1990-05-31 JP JP14401490A patent/JPH0791785B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021157351A1 (en) | 2020-02-07 | 2021-08-12 | 第一化成株式会社 | Method for manufacturing synthetic leather |
| US11913167B2 (en) | 2020-02-07 | 2024-02-27 | Daiichi Kasei Co., Ltd | Method for manufacturing synthetic leather |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791785B2 (en) | 1995-10-04 |
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