JPS63222701A - Adhesive composition and production of water-repellent and oil-repellent canvas shoes - Google Patents
Adhesive composition and production of water-repellent and oil-repellent canvas shoesInfo
- Publication number
- JPS63222701A JPS63222701A JP62059130A JP5913087A JPS63222701A JP S63222701 A JPS63222701 A JP S63222701A JP 62059130 A JP62059130 A JP 62059130A JP 5913087 A JP5913087 A JP 5913087A JP S63222701 A JPS63222701 A JP S63222701A
- Authority
- JP
- Japan
- Prior art keywords
- water
- rubber
- repellent
- oil
- shoes
- 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
- 230000001070 adhesive effect Effects 0.000 title claims description 26
- 239000000853 adhesive Substances 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 title claims description 16
- 239000005871 repellent Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 27
- 239000005060 rubber Substances 0.000 claims description 27
- 239000004744 fabric Substances 0.000 claims description 26
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 22
- 239000003292 glue Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000003921 oil Substances 0.000 description 27
- 244000043261 Hevea brasiliensis Species 0.000 description 12
- 229920003052 natural elastomer Polymers 0.000 description 12
- 229920001194 natural rubber Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 239000007965 rubber solvent Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- ZUHRGSQCGNLZFH-UHFFFAOYSA-N 1,3-benzothiazole-5-thiol Chemical compound SC1=CC=C2SC=NC2=C1 ZUHRGSQCGNLZFH-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- HJEINPVZRDJRBY-UHFFFAOYSA-N Disul Chemical compound OS(=O)(=O)OCCOC1=CC=C(Cl)C=C1Cl HJEINPVZRDJRBY-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- HSYFJDYGOJKZCL-UHFFFAOYSA-L zinc;sulfite Chemical compound [Zn+2].[O-]S([O-])=O HSYFJDYGOJKZCL-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
Ｌ１１立皿ユ皇Ｉ
本発明は、接着剤組成物及びそれを使用する撥水撥油性
を有する布靴の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition and a method for producing water- and oil-repellent cloth shoes using the adhesive composition.
の技術とその
近年靴の付加価値に対する要求が高まるとともに、足の
健康に良好な機能を有する靴、特に、雨の日でも履ける
全天候型であり、泥汚れしにくく、洗濯を繰返しても当
初の撥水撥油性を維持し、且つ通気性が良好で足ムレを
起こさない靴が強く望まれるようになっている。通常、
上記のような機能を発揮するには、靴胛被材に、撥水度
１００（Ｊ ｌ５Ｋ−６３２８の規定による）及び撥油
度６ （ＡＡＴＣＣの規定による）であり、且つ洗濯５
回後（Ｊ ｌ５−ＬＯ２１７−１０３法の規定による）
も前記撥水撥油塵を維持できる基材を使用する必要があ
る。In recent years, demand for footwear technology and its added value has increased, and shoes that have good functions for foot health, especially all-weather shoes that can be worn even on rainy days, are resistant to mud stains, and retain their original value even after repeated washing. There is a strong demand for shoes that maintain water and oil repellency, have good breathability, and do not cause foot stuffiness. usually,
In order to exhibit the above functions, the shoelace covering material must have a water repellency of 100 (according to the regulations of Jl5K-6328) and an oil repellency of 6 (according to the regulations of AATCC), and must be washed 5 times.
After treatment (according to the provisions of J l5-LO217-103 law)
It is also necessary to use a base material that can maintain the water-, oil-, and dust-repellency.
上記要望を満足させるために、例えば、１）綿布等の胛
被材を、予めフッ素系撥水撥浦剤で処理し、これを成形
して靴とする方法、２）スプレー等の機器を使用して、
成形された布靴に溶剤型の撥水間油剤を噴霧して処理す
る方法、３）綿布等の基材に予めウレタン樹脂をコーテ
ィングして極薄塗膜とし、この基材を成形して防水性を
備える靴とする方法等が提案されている。しかしながら
、上記方法には、夫々以下のような欠点があり好ましく
ない。即ち、１）の方法において、高度の撥水撥油性（
撥水度１００．撥油塵６．洗濯５回以後も前記撥水撥油
度を維持する）を施した胛被材を使用した場合、該牧師
被材と靴ゴム底、ゴムテープ等とを貼り合せ糊によって
貼着することが極めて困難である。そのため、牧師被材
として、撥水撥油性能を撥水度８０〜９０．撥油度４．
且つ洗濯１回で撥水度６０〜７０にまで下げた綿布等を
使用し、並びに貼り合せ糊として、例えば、天然ゴム糊
等に、商品名［デスモジュールＲＦＪ〔***バイエル社
製〕の下に市販されているトリス−４−フェニルイソシ
アネートチオフォスフェートを添加したもの、ラテック
ス系接着剤にフッ素系浸透剤を添加したもの等を使用し
て接着性を高める試みがなされている。しかしながら、
その接着性はやはり満足のゆくものではなく、しかも当
然のことなから撥水撥油性も充分ではない。２）の方法
は、塗布ムラが生じる、撥水効果が低下する、製造工程
が複雑である等の欠点を有している。In order to satisfy the above requirements, for example, 1) a method of pre-treating a cover material such as cotton cloth with a fluorine-based water-repellent agent and molding it into shoes; 2) the use of equipment such as a sprayer; do,
A method in which molded cloth shoes are treated by spraying a solvent-based water-repellent oil agent; 3) A base material such as cotton cloth is coated with urethane resin in advance to form an ultra-thin film, and this base material is molded to make it waterproof. There have been proposals for methods of making shoes with characteristics. However, each of the above methods has the following disadvantages and is not preferable. That is, in method 1), high water and oil repellency (
Water repellency 100. Oil-repellent dust6. When using a jacket material that has been treated with water and oil repellency that maintains the above-mentioned water and oil repellency even after 5 washes, it is extremely difficult to attach the pastor jacket material to shoe rubber soles, rubber tape, etc. using glue. It is. Therefore, it can be used as a covering material for pastors, and has a water and oil repellency of 80 to 90. Oil repellency 4.
In addition, use cotton cloth whose water repellency has been lowered to 60 to 70 after washing once, and as a bonding glue, such as natural rubber glue, under the product name [Desmodule RFJ [manufactured by Bayer AG]]. Attempts have been made to improve adhesion using commercially available adhesives, such as those to which tris-4-phenylisocyanate thiophosphate is added, and latex adhesives to which a fluorine-based penetrant is added. however,
Its adhesive properties are still unsatisfactory, and as a matter of course, its water and oil repellency are also not sufficient. Method 2) has drawbacks such as uneven coating, decreased water repellency, and complicated manufacturing process.
３）の方法では、得られる布靴の撥水撥油効果及び通気
性が不充分であり、しかも、風合が硬くなり好ましくな
い。In method 3), the water and oil repellency and breathability of the cloth shoes obtained are insufficient, and the texture becomes hard, which is not preferable.
問題１、を解決するための手段
本発明者は、上記従来技術の問題点に鑑みて鋭意研究を
中ねた結果、特定のポリイソシアネート化合物とゴム系
溶剤糊とを含む接着剤を使用した場合には、高度の撥水
撥油性（撥水度１００．撥油塵６．洗濯５回以後も前記
撥水溌油度を維持する）を施した胛被材と靴ゴム底、ゴ
ムテープ等とを極めて強力に接着できることを見い出し
、本発明を完成した。Means for Solving Problem 1 The present inventor has conducted extensive research in view of the problems of the prior art described above, and has found that when an adhesive containing a specific polyisocyanate compound and a rubber-based solvent glue is used. For this purpose, a shoe cover material with a high degree of water and oil repellency (water repellency of 100, oil and dust repellency of 6. maintains the water and oil repellency even after 5 washes), rubber soles of shoes, rubber tape, etc. They discovered that extremely strong adhesion can be achieved and completed the present invention.
即ち本発明は、以下に示す接着剤組成物及びそれを使用
する撥水撥油性を有する布靴の製造法を提供するもので
ある。That is, the present invention provides the following adhesive composition and a method for producing cloth shoes having water and oil repellency using the adhesive composition.
■イソホロンジイソシアヌレートプレポリマーとゴム系
溶剤糊とを含む接着剤組成物。■Adhesive composition containing isophorone diisocyanurate prepolymer and rubber-based solvent glue.
■基材として撥水撥油性を有する繊維布を使用した牧師
被と靴ゴム底或いは該牧師被と靴ゴム底及びゴムテープ
とを、貼り合せ糊によって貼着して成形組合する撥水撥
油性を有する布靴の製造法において、該貼り合せ糊とし
て、イソホロンジイソシアヌレートプレポリマーとゴム
系溶剤糊とを含む接着剤組成物を用いることを特徴とす
る撥水撥油性を有する布靴の製造法。■Water and oil repellency achieved by bonding and molding a pastor's jacket made of water- and oil-repellent fiber cloth as a base material and a shoe rubber sole, or by bonding and molding the pastor's jacket, shoe rubber sole, and rubber tape using adhesive. A method for producing cloth shoes having water and oil repellency, characterized in that an adhesive composition containing an isophorone diisocyanurate prepolymer and a rubber solvent glue is used as the bonding glue. .
本発明接着剤組成物においては、ポリイソシアネート化
合物としてイソホロンジイソシアヌレートプレポリマー
を使用した場合にのみ、初めて本発明の所期の効果が達
成される。他のポリイソシアネート化合物を使用しても
同様な効果が奏されることはない。In the adhesive composition of the present invention, the desired effects of the present invention are achieved only when isophorone diisocyanurate prepolymer is used as the polyisocyanate compound. Similar effects will not be achieved using other polyisocyanate compounds.
イソホロンジイソシアヌレートプレポリマーは公知のポ
リイソシアネート化合物である。本発明では、該ポリマ
ーとして、通常ＮＧＯ含有含有率１０〜亢６
のを何れも使用できる。イソボロンジイソシアヌレート
プレポリマーを適当な溶剤で希釈して使用してもよい。Isophorone diisocyanurate prepolymer is a known polyisocyanate compound. In the present invention, any polymer having an NGO content of 10 to over 6 can be used as the polymer. The isoborone diisocyanurate prepolymer may be used after being diluted with a suitable solvent.
適当な溶剤としては、例えば、酢酸セロソルブ、キシレ
ン、ツルペッツ等を挙げることができる。Suitable solvents include, for example, cellosolve acetate, xylene, Tsurpetz, and the like.
、ゴム系溶剤糊としては、公知のものが何れも使用でき
、例えば、天然ゴム配合物、天然ゴム・ＭＭＡ共重合体
、合成ゴム配合物、天然ゴム・合成ゴム配合物等を挙げ
ることができる。その具体例としては、例えば、天然ゴ
ム、天然ゴムＭＭＡ共重合体（ＭＧ２５）、ＳＢＲ、イ
ソプレンゴム、クロロブレンゴム等の合成ゴム、天然ゴ
ムとＮＢＲ等の合成ゴムとの混合物等のゴムに、硫黄、
メルカプトベンゾチアゾール、ジベンゾチアゾールジス
ルファイド、テトラメチルチウラムモノスルファイド、
亜鉛華、ステアリン酸、ロジン樹脂、軽質炭酸カルシウ
ム、炭酸マグネシウム、老防剤、顔料等の通常ゴム系溶
剤糊に使用される添加剤を添加したもの等を挙げること
ができる。上記の添加剤の添加間は特に制限されず、通
常使用される量を添加すればよい。本発明では、ゴム系
溶剤糊を適当な溶剤に希釈して使用してもよい。溶剤と
しては、例えば、トルエン、メチルエチルケトン、ｎ−
ヘキサン、酢酸エチル、ゴム揮発油等を挙げることがで
きる。As the rubber-based solvent glue, any known one can be used, such as natural rubber compound, natural rubber/MMA copolymer, synthetic rubber compound, natural rubber/synthetic rubber compound, etc. . Specific examples include natural rubber, natural rubber MMA copolymer (MG25), synthetic rubber such as SBR, isoprene rubber, chloroprene rubber, and mixtures of natural rubber and synthetic rubber such as NBR. sulfur,
Mercaptobenzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide,
Examples include those containing additives commonly used in rubber-based solvent pastes, such as zinc white, stearic acid, rosin resin, light calcium carbonate, magnesium carbonate, antiaging agents, and pigments. The time between additions of the above additives is not particularly limited, and it is sufficient to add the additives in normally used amounts. In the present invention, the rubber-based solvent paste may be diluted with an appropriate solvent and used. Examples of the solvent include toluene, methyl ethyl ketone, n-
Examples include hexane, ethyl acetate, rubber volatile oil, and the like.
イソホロンジイソシアヌレートプレポリマーとゴム系溶
剤糊との配合割合は特に制限されず、適宜選択すればよ
いが、通常固形分換算でゴム系溶剤糊１００重量部に対
しイソホロンジイソシアヌレートプレポリマーを７〜７
０重量部重量部会すればよい。The blending ratio of isophorone diisocyanurate prepolymer and rubber solvent glue is not particularly limited and may be selected as appropriate, but usually 7 parts by weight of isophorone diisocyanurate prepolymer per 100 parts by weight of rubber solvent glue in terms of solid content. ~7
0 parts by weight should be used.
本発明接着剤組成物は、上記各成分を公知の方法によっ
て混合することによって製造される。かくして得られる
接着剤は、後述の製造法において貼り合せ糊として使用
されるだけでなく、靴の表布と裏布とを貼り合せにも用
い得ることは勿論のこと、ゴム引布その他の各種の工業
用品、カーペット材等の用途にも使用できる。The adhesive composition of the present invention is produced by mixing the above-mentioned components by a known method. The adhesive obtained in this way can be used not only as a bonding glue in the manufacturing method described below, but also for bonding the outer and lining fabrics of shoes, as well as rubberized fabrics and various other materials. It can also be used for industrial products, carpet materials, etc.
本発明製造法において、牧師被用基材としては、撥水撥
油性を有する繊維布が何れも使用できるが、撥水度１０
０．撥油度６．洗１１１５回以上後も前記撥水撥油度を
維持できる撥水撥油性能を施されたものを特に好ましく
使用できる。その具体例としては、例えば、繊維布を、
パーフルオロアルキル基を有するフッ素系樹脂を主成分
とし、バインダーとしてアクリル樹脂、シリコン樹脂等
を添加した撥水撥油剤をトリクレンで希釈した溶液に含
浸して１６０℃程度で２〜５分程度ベーキング加工した
もの等を使用すればよい。この際使用される繊維布とし
ては、公知のものが何れも使用でき、例えば、綿布、ビ
ニロン、スフ、レーヨン、麻等の天然繊維、合成繊維若
しくは人造繊維を挙げることができる。また、市販の撥
水撥油性加工基材を採用してもよく、その具体例として
、例えば、１２６Ｘ６０
加工したもの〔敷島紡績■製〕等を挙げることができる
。In the production method of the present invention, any fiber cloth having water and oil repellency can be used as the base material for pastor's clothing, but water repellency is 10
0. Oil repellency 6. It is particularly preferable to use a material that has been given water and oil repellency so that the water and oil repellency can be maintained even after washing 1115 times or more. Specific examples include, for example, fiber cloth,
A water and oil repellent mainly composed of a fluororesin having a perfluoroalkyl group and acrylic resin, silicone resin, etc. added as a binder is impregnated in a solution diluted with trichlene and baked at about 160°C for about 2 to 5 minutes. You can use the one that has been prepared. As the fiber cloth used in this case, any known fiber cloth can be used, and examples thereof include natural fibers such as cotton cloth, vinylon, cotton cloth, rayon, linen, etc., synthetic fibers, and man-made fibers. Further, a commercially available water- and oil-repellent treated base material may be used, and a specific example thereof includes a 126×60 treated base material (manufactured by Shikishima Boseki).
本発明接着剤組成物を使用して撥水撥油性を有する布靴
を製造するに当っては、例えば、以下のようにして行え
ばよい。即ち、基材として撥水撥油性を有する繊維布を
使用した牧師被と、靴ゴム底或いは靴ゴム底及びゴムテ
ープとを、本発明接着剤を介して貼着し、次いで常法に
従って成形組合した後、これに、必要に応じて加硫缶に
おいて熱空気加硫処理することによって、高度の撥水撥
油性を有する布靴を製造することができる。本発明接着
剤の塗布量は特に制限されないが、通常１足につきｗｅ
ｔｍで３〜６ｇ程度（固形分換算的１．５ｇ）とすれば
よい。接Ｍ斉ｒの塗布は、常法に従って行えばよい。ま
た、熱空気加硫処理は、通常１２０〜１３０℃程度、２
Ｋｙ／ａｌの加圧雰囲気下、４０〜９０分程度行えばよ
い。In manufacturing water- and oil-repellent cloth shoes using the adhesive composition of the present invention, it may be carried out, for example, as follows. That is, a pastor's jacket made of a water- and oil-repellent fiber cloth as a base material, a shoe rubber sole or a shoe rubber sole, and a rubber tape were attached via the adhesive of the present invention, and then molded and assembled according to a conventional method. Thereafter, if necessary, this is subjected to hot air vulcanization treatment in a vulcanizer to produce cloth shoes having a high degree of water and oil repellency. The amount of the adhesive of the present invention applied is not particularly limited, but usually we
The amount may be about 3 to 6 g (1.5 g in terms of solid content) in terms of tm. The application of the tangent may be carried out according to a conventional method. In addition, hot air vulcanization treatment is usually performed at a temperature of about 120 to 130°C, 2
It may be carried out for about 40 to 90 minutes under a pressurized atmosphere of Ky/al.
かくして得られる末完羽化は、あらゆる用途の靴として
使用できるが、特に、全天候型の通学靴、カジュアル靴
等に好適である。The finished product thus obtained can be used as shoes for all kinds of purposes, but is particularly suitable for all-weather school shoes, casual shoes, and the like.
ＲＦＩＪｆ）丸里
本発明によれば、以下のような優れた効果が達成される
。RFIJf) Marusato According to the present invention, the following excellent effects are achieved.
（１）本発明方法によれば、イソホロンジイソシアヌレ
ートプレポリマーとゴム系溶剤糊とを含む接着剤を使用
することによって、高度の撥水撥油性を有する牧師被材
と靴ゴム底、ゴムテープ等を極めて強力に接着できる。(1) According to the method of the present invention, by using an adhesive containing an isophorone diisocyanurate prepolymer and a rubber-based solvent glue, pastor covering materials, shoe rubber soles, rubber tapes, etc., which have a high degree of water and oil repellency are produced. can be bonded extremely strongly.
尚、この場合化胛被材としては、必ずしも繊維布を用い
たもののみでなく、天然皮革、合成皮革製胛被等広く一
般の胛被材にも適用できることは言うまでもない。In this case, it goes without saying that the synthetic covering material is not necessarily limited to those using fiber cloth, but can also be applied to a wide variety of general covering materials such as natural leather and synthetic leather.
（２）本発明方法によれば、高度の撥水撥油性、耐洗濯
性及び通気性を備え、しかも耐久性に優れた布靴を、安
価に且つ簡便に製造することができる。また、溶剤系撥
水撥油剤をスプレー塗布する場合に見られるような塗布
ムラ、耐久性の低下等がない。(2) According to the method of the present invention, cloth shoes having high water and oil repellency, wash resistance, and breathability and excellent durability can be manufactured easily and inexpensively. Furthermore, there is no uneven coating, no decrease in durability, etc. that occurs when spray coating a solvent-based water and oil repellent.
（３）綿布等にウレタン樹脂をコーティングしたものに
比べ、風合が硬くならず、綿布等のソフトな風合を保持
することができ、バランスの良好な靴を（ｑることがで
きる。(3) Compared to cotton cloth or the like coated with urethane resin, the feel is not stiff, and the soft feel of cotton cloth can be maintained, making it possible to create well-balanced shoes.
実 施 例
以下に実施例及び比較例を挙げ、本発明をより一層明瞭
なものとする。EXAMPLES Examples and comparative examples are given below to make the present invention even clearer.
実施例１
１２６Ｘ６０
度１００．溌油度６．洗濯５回以上後も前記溌水撥油度
を維持するフッ素樹脂系加工を行ったエクスト加工基材
〔敷島紡績１１製〕を牧師被として使用した。該牧師被
と化ゴム底及びゴムテープとを、下記■の組成を有する
天然ゴム溶剤糊溶液１００重足部とイソホロンジイソシ
アヌレートプレポリマ−（商品名：デスモジュールＺ４
３７０．***バイエル社製）１０重量部を含む本発明接
着剤を塗布して貼着した。塗付量は、約６ｙ／足であっ
た。これを、成形組合した後、加硫缶にて１３０”Ｃ，
２Ｎ９／ｉの加圧下に、６０分熱空気加硫して本発明の
靴を製造した。Example 1 126 x 60 degrees 100. Oil permeability 6. An extruded base material (manufactured by Shikishima Boseki 11) treated with a fluororesin system that maintains the above-mentioned water and oil repellency even after being washed five times or more was used as a pastor coat. The rubber sole and the rubber tape were mixed with a natural rubber solvent glue solution having the following composition (1) and an isophorone diisocyanurate prepolymer (trade name: Desmodur Z4).
370. An adhesive of the present invention containing 10 parts by weight (manufactured by West German Bayer AG) was applied and adhered. The amount of coating was approximately 6y/foot. After molding and assembling this, it was heated to 130"C in a vulcanizer.
Shoes of the present invention were manufactured by hot air vulcanization for 60 minutes under a pressure of 2N9/i.
■天然ゴム溶剤糊溶液
天然ゴム １００重量部硫黄
２．５ 〃メルカプトベンゾチアゾ
ール ０．３ １！ジベンゾチアゾールジスル ０．
３ 、。■Natural rubber solvent glue solution Natural rubber 100 parts by weight sulfur
2.5 Mercaptobenzothiazole 0.3 1! Dibenzothiazole disul 0.
3.
フッイド
テトラメヂルチウラムモノ ０．１ｎスルフフイト
亜鉛華１号 ８．０ 〃ステアリン酸
１．Ｏ〃軽質炭酸カルシウム
５２ 〃スチレン化フェノール １．ｏ 。Fluid tetramedylthiuram mono 0.1n sulfite zinc white No. 1 8.0 Stearic acid 1. O〃Light calcium carbonate
52 Styrenated phenol 1. o.
（老化防止剤）
上記各成分を混練し、トルエンで溶解して１１度３０％
の天然ゴム溶剤糊溶液を作製した。(Anti-aging agent) Knead each of the above ingredients and dissolve in toluene to give 11% 30%
A natural rubber solvent glue solution was prepared.
得られた靴を、ＪＩＳＫ６３０１に規定の常態接着力試
験及び耐水接着力試験（試料を水に２４時間浸漬した後
、接着力を測定）に供した。結果を第１表に示す。The obtained shoes were subjected to a normal adhesion test and a water-resistant adhesion test (adhesion was measured after immersing the sample in water for 24 hours) as specified in JIS K6301. The results are shown in Table 1.
比較例１
イソホロンジイソシアヌレートプレポリマーを使用しな
い以外は、実施例１と同様にして靴を製造した。Comparative Example 1 Shoes were manufactured in the same manner as in Example 1, except that the isophorone diisocyanurate prepolymer was not used.
比較例２
イソホロンジイソシアヌレートプレポリマーに代えてヘ
キサメチレンジイソシアネートポリマー〔商品名：デュ
ラネートＡＤ−７０．旭化成■製〕を使用する以外は、
実施例１と同様にして靴を製造した。Comparative Example 2 Hexamethylene diisocyanate polymer [trade name: Duranate AD-70. Except for using [manufactured by Asahi Kasei],
Shoes were manufactured in the same manner as in Example 1.
比較例３
イソホロンジイソシアヌレートプレポリマーに代えてジ
フェニルメタンジインシアネートポリマー〔商品名：ニ
ツボラン３０３０．日本つレタン曲製〕を使用する以外
は、実施例１と同様にして靴を製造した。Comparative Example 3 Diphenylmethane diincyanate polymer [trade name: Nituboran 3030. Shoes were manufactured in the same manner as in Example 1, except that Nippon Tsuretan Kyusei was used.
比較例４
イソホロンジイソシアヌレートプレポリマーに代えてト
リレンジイソシアネートポリマー〔商品名：デスモジュ
ールＥ−１４．***バイエル社製〕を使用する以外は、
実施例１と同様にして靴を製造した。Comparative Example 4 Tolylene diisocyanate polymer [trade name: Desmodur E-14. Manufactured by West German Bayer AG]
Shoes were manufactured in the same manner as in Example 1.
比較例５
イソホロンジインシアヌレートプレポリマーに代えてト
リス−４−フェニルジイソシアネートポリマー〔商品名
：デスモジュールＲＦ、***バイエル社製〕を使用する
以外は、実施例１と同様にして靴を製造した。Comparative Example 5 Shoes were manufactured in the same manner as in Example 1, except that tris-4-phenyl diisocyanate polymer [trade name: Desmodur RF, manufactured by Bayer AG, West Germany] was used in place of the isophorone diyne cyanurate prepolymer.
上記比較例１〜５で得られた靴を、実施例１と同様の性
能試験に供した。結果を第１表に示す。The shoes obtained in Comparative Examples 1 to 5 above were subjected to the same performance test as in Example 1. The results are shown in Table 1.
第 １ 表
第１表から、本発明接着剤を使用した場合には優れた接
着強度が発揮されること、並びに本発明で使用するイソ
ホロンジイソシアヌレートプレポリマー以外のポリイソ
シアネート化合物を使用しても、接着強度が充分ではな
いことが判る。Table 1 From Table 1, it can be seen that when the adhesive of the present invention is used, excellent adhesive strength is exhibited, and even when polyisocyanate compounds other than the isophorone diisocyanurate prepolymer used in the present invention are used. , it can be seen that the adhesive strength is not sufficient.
実施例１で得られた靴（以下本発明品とする）及び比較
例１〜５で得られた靴（以下比較量とする）の耐久性を
試験するために、世界長■徳山工場精錬課ゴム練り作業
員（立ら作業及び運搬・歩行作業、１日当り７〜９時間
作業）が２か月試験履きを行った（試験履き実施中の洗
濯回数は１〜３回程度）。試験後、靴の状態を観察した
ところ、本発明品の靴の屈曲部及び周囲接着部は完全に
接着し、良好な撥水性及び通気性を示し、泥汚れしにく
かった。一方、比較量は、１日月に屈曲部が剥離し、７
日後に周囲が拡大剥離した。In order to test the durability of the shoes obtained in Example 1 (hereinafter referred to as the products of the present invention) and the shoes obtained in Comparative Examples 1 to 5 (hereinafter referred to as comparative quantities), Sekaicho Tokuyama Factory Refining Division Rubber kneading workers (standing, transporting, walking, working 7 to 9 hours per day) wore the test shoes for 2 months (the number of washes during the test was about 1 to 3 times). After the test, the condition of the shoe was observed, and it was found that the bent part and surrounding bonded part of the shoe of the present invention were completely adhered, had good water repellency and breathability, and was resistant to dirt. On the other hand, the comparative amount is such that the bent part peels off in 1 day and 7 months.
Days later, the surrounding area expanded and peeled.
実施例２
天然ゴム溶剤糊溶液に代えて下記■の組成を有する常温
糊溶液を使用し、且つ熱空気加硫を行わない以外は、実
施例１と同様にして本発明の靴を製造した。得られた靴
は、極めて優れた耐久性を有し、しかも、良好な撥水性
及び通気性を有し、泥汚れしにくかった。Example 2 Shoes of the present invention were manufactured in the same manner as in Example 1, except that a room-temperature glue solution having the following composition (2) was used in place of the natural rubber solvent glue solution, and hot air vulcanization was not performed. The obtained shoes had extremely excellent durability, had good water repellency and breathability, and were resistant to mud stains.
■常温糊溶液
クロロプレンＡＤ９０ ９０重量部〔商品名、電
気化学工業（４１製〕
クロロプレンＭＭＡ共重合物 １０ 〃亜鉛華
５ 〃酸化マグネシウム
４ 〃ロジン樹脂 ２
〃ジターシャリブチルパラクレゾール１ 、。■Normal temperature glue solution Chloroprene AD90 90 parts by weight [Product name, manufactured by Denki Kagaku Kogyo (41)] Chloroprene MMA copolymer 10 Zinc white
5 Magnesium oxide
4 Rosin resin 2
〃Ditert-butyl para-cresol 1.
（老化防止剤）
上記各成分の混線物２５重量部を、トルエン７５重四部
に溶解して２５％常温常温液溶液製した。(Antioxidant) 25 parts by weight of a mixture of each of the above components was dissolved in 75 parts by weight of toluene to prepare a 25% room temperature liquid solution.
（以 上）(that's all)
Claims (2)
ム系溶剤糊とを含む接着剤組成物。(1) An adhesive composition containing an isophorone diisocyanurate prepolymer and a rubber-based solvent glue.
靴胛被と靴ゴム底或いは該靴胛被と靴ゴム底及びゴムテ
ープとを、貼り合せ糊によって貼着して成形組合する撥
水撥油性を有する布靴の製造法において、該貼り合せ糊
として、イソホロンジイソシアヌレートプレポリマーと
ゴム系溶剤糊とを含む接着剤組成物を用いることを特徴
とする撥水撥油性を有する布靴の製造法。(2) A shoe cover made of a water- and oil-repellent fiber cloth as a base material and a shoe rubber sole, or a shoe cover, a shoe rubber sole, and a rubber tape are attached and molded together using adhesive. A method for manufacturing water- and oil-repellent cloth shoes, characterized in that an adhesive composition containing an isophorone diisocyanurate prepolymer and a rubber-based solvent glue is used as the bonding glue. Shoe manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62059130A JPH084524B2 (en) | 1987-03-13 | 1987-03-13 | Adhesive composition for adhering water / oil repellent material and method for producing cloth shoes having water / oil repellency using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62059130A JPH084524B2 (en) | 1987-03-13 | 1987-03-13 | Adhesive composition for adhering water / oil repellent material and method for producing cloth shoes having water / oil repellency using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63222701A true JPS63222701A (en) | 1988-09-16 |
| JPH084524B2 JPH084524B2 (en) | 1996-01-24 |
Family
ID=13104417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62059130A Expired - Lifetime JPH084524B2 (en) | 1987-03-13 | 1987-03-13 | Adhesive composition for adhering water / oil repellent material and method for producing cloth shoes having water / oil repellency using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH084524B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57195777A (en) * | 1981-05-29 | 1982-12-01 | Asahi Chem Ind Co Ltd | Adhesive composition for shoemaking |
| JPS61288802A (en) * | 1985-06-14 | 1986-12-19 | アキレス株式会社 | Production of canvas shoes |
-
1987
- 1987-03-13 JP JP62059130A patent/JPH084524B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57195777A (en) * | 1981-05-29 | 1982-12-01 | Asahi Chem Ind Co Ltd | Adhesive composition for shoemaking |
| JPS61288802A (en) * | 1985-06-14 | 1986-12-19 | アキレス株式会社 | Production of canvas shoes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH084524B2 (en) | 1996-01-24 |
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