JPS6357002A - Production of synthetic leather shoes - Google Patents
Production of synthetic leather shoesInfo
- Publication number
- JPS6357002A JPS6357002A JP61203050A JP20305086A JPS6357002A JP S6357002 A JPS6357002 A JP S6357002A JP 61203050 A JP61203050 A JP 61203050A JP 20305086 A JP20305086 A JP 20305086A JP S6357002 A JPS6357002 A JP S6357002A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic leather
- skin layer
- sole
- adipate
- shoe
- 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 description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 29
- -1 polyethylene adipate Polymers 0.000 claims description 23
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 11
- 239000004632 polycaprolactone Substances 0.000 claims description 11
- 238000004383 yellowing Methods 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- 239000004800 polyvinyl chloride Substances 0.000 claims description 7
- 229920000921 polyethylene adipate Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 210000003491 skin Anatomy 0.000 description 20
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (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) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は合成皮革靴の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing synthetic leather shoes.
〔従来の技術及び発明が解決しようとする問題点〕合成
皮革よりなる胛被の底部にポリ塩化ビニルを主成分とす
る靴底材を射出成型して一体化された靴底を形成し、合
成皮革靴を製造するに際して、合成皮革製胛被として従
来より、ポリイソシアネートとしてジフェニルメタンジ
インシアネート（ＭＤＩ）を用い良熱軟化点１９０〜２
００℃程度のポリウレタン表皮層を有する合成皮革より
なるものが用いられているが、ポリ塩化ビニルを主成分
とする靴底材の射出温度が１９０〜２００℃程度である
ため射出された靴底材が胛被の表皮層に接触した時には
温度低下によって胛被の表皮層を確実に溶融し得るだけ
の温度になく、靴底と胛被との接着が不充分となる。こ
のため従来は胛被と靴底との接合部（胛被下端部外周）
に、靴底との接着性向上のためのプライマーを予め塗布
した後、射出成型を行なっていた。しかしながら、この
プライマーの塗布は刷毛等による手作業で行なわれてお
り、生産能率が低く、品質の安定性にも欠けるという問
題があるとともｉこ、胛被と靴底とを確実に接着するた
めに、胛被下端部外周の実際に靴底と接合する部分より
広い部分にプライマー塗布を行っておシ、このため胛被
表面にプライマーが現れて外観上好ましくないという問
題があっ九。[Prior art and problems to be solved by the invention] A shoe sole material mainly composed of polyvinyl chloride is injection molded on the bottom of a shoe cover made of synthetic leather to form an integrated sole. When manufacturing leather shoes, diphenylmethane diincyanate (MDI) has traditionally been used as a polyisocyanate to produce synthetic leather shoes with a good heat softening point of 190 to 2.
Synthetic leather with a polyurethane skin layer at a temperature of about 00°C is used, but since the injection temperature of shoe sole materials whose main component is polyvinyl chloride is about 190 to 200°C, injected shoe sole materials When it comes into contact with the outer skin layer of the shoe shoe, the temperature is not high enough to reliably melt the outer layer of the shoe shoe due to the temperature drop, resulting in insufficient adhesion between the shoe sole and the shoe shoe. For this reason, conventionally, the joint between the shoe cover and the sole (the outer periphery of the lower end of the shoe cover)
In order to improve adhesion to the sole of the shoe, a primer was applied in advance, and then injection molding was performed. However, the application of this primer is done manually with a brush, etc., which causes problems such as low production efficiency and lack of quality stability. Therefore, the primer is applied to a wider area of the outer periphery of the lower end of the shoe than the part that actually joins with the sole of the shoe, resulting in the problem that the primer appears on the surface of the shoe, resulting in an unfavorable appearance.
本発明者は上記の点に鑑み鋭意研究した結果、表皮層を
ポリカプロラクトングリコール及び／又はポリブチレン
アジペートをポリエステル成分とする無黄変塁ポリウレ
タンエンストマーにより形成することにより、プライマ
ーなしでも胛被と靴底とを充分接着することができるこ
とを見出したが、上記無黄変凰ポリウレタンエラストマ
ーよ〕表皮層を形成する場合、表皮層と合成皮革基材と
を接着する接着剤として従来よ）用いられているエチレ
ングリコール及び／又はブタンジオールとアジピン酸と
のポリエステルと、トリレンジイソシアネー）（ＴＤＩ
）とからなるポリウレタン系２液屋接着剤を用いると表
皮層の屈曲性が低下せしめられて柔軟性に乏しいものと
なり、しかもこの合成皮革より得た胛被を用いて靴底材
を射出成型すると、−担接着した表皮層が合成皮革基材
から剥離しやすくなるという欠点があった。As a result of extensive research in view of the above points, the inventors of the present invention have found that by forming the skin layer from a non-yellowing polyurethane entomer containing polycaprolactone glycol and/or polybutylene adipate as the polyester component, it is possible to prevent fly damage even without a primer. It has been found that the non-yellowing polyurethane elastomer described above can be used as an adhesive to bond the skin layer and the synthetic leather base material (conventionally) when forming the skin layer. Polyester of ethylene glycol and/or butanediol and adipic acid and tolylene diisocyanate (TDI)
) If a two-component polyurethane adhesive is used, the flexibility of the skin layer will be reduced, resulting in poor flexibility.Furthermore, if a shoe sole material is injection molded using a cover obtained from this synthetic leather, , - There was a drawback that the supported skin layer easily peeled off from the synthetic leather base material.
本発明は上記の点に鑑みなされたもので、プライマー塗
布を行なわずとも胛被と靴底とを確実に接合一体化でき
、しかも胛被の天然皮革様の柔軟性低下や、靴底材を射
出成型した後に胛被の表皮層と基材との剥離を生じるこ
となく、優れた合成皮革靴を効率よく製造し得る合成皮
革靴の製造方法を提供することを目的とする。The present invention has been developed in view of the above points, and it is possible to reliably bond and integrate the shoe cover and the sole without applying a primer, and to reduce the flexibility of the shoe cover like natural leather, and to reduce the flexibility of the shoe sole material. To provide a method for manufacturing synthetic leather shoes that can efficiently manufacture excellent synthetic leather shoes without causing peeling between the skin layer of a shoelace and a base material after injection molding.
即ち本発明はポリエチレンアジペート、ポリエチレンブ
チレンアジベート、ポリブチレンアジペート、ポリブチ
レンヘキシレンアジペート、ポリカプロラクトングリコ
ールの少なくとも１種と、低分子量グリコール及び芳香
族ジイソシアネートとを構成成分とするポリウレタンエ
ラストマーよりなる１液型接着剤により合成皮革基材に
接着された、ポリカプロラクトングリコール及び／又は
ポリブチレンアジペートをポリエステル成分とする無黄
変型ポリウレタンエラストマーよりなる表皮層を有する
合成皮革より胛被を形成し、次いで該胛被の底部に、ポ
リ塩化ビニルを主成分とする靴底材を射出成型して一体
化された靴底を形成することを特徴とする合成皮革靴の
製造方法を要旨とするものである。That is, the present invention provides a one-liquid polyurethane elastomer containing at least one of polyethylene adipate, polyethylene butylene adipate, polybutylene adipate, polybutylene hexylene adipate, and polycaprolactone glycol, as well as a low molecular weight glycol and an aromatic diisocyanate. A coat is formed from synthetic leather having a skin layer made of a non-yellowing polyurethane elastomer containing polycaprolactone glycol and/or polybutylene adipate as a polyester component, which is bonded to a synthetic leather base material with a mold adhesive, and then the coat is made of synthetic leather. The gist of this invention is to provide a method for manufacturing synthetic leather shoes, which is characterized by forming an integrated sole by injection molding a sole material containing polyvinyl chloride as a main component on the bottom of the shoe.
本発明において用いる胛被を形成する合成皮革の表皮層
はポリカプロラクトングリコール及び／又はポリブチレ
ンアジペートをポリエステル成分とする無黄変型ポリウ
レタンエラストマーよりナリ、該無黄変型ポリウレタン
ニジストマーは、インシアネート成分としてインホロン
ジインシアネート、４．４’−ジシクロヘキシルメタン
ジイソシアネート、ヘキサメチレンジイソシアネート等
の脂肪族ポリイソシアネート、脂環式ポリインシアネー
トの単独又は２種以上の混合物が用いられる。The skin layer of the synthetic leather forming the cover used in the present invention is made of a non-yellowing polyurethane elastomer containing polycaprolactone glycol and/or polybutylene adipate as a polyester component; Aliphatic polyisocyanates such as inphorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate, and alicyclic polyincyanates can be used alone or in combination of two or more.
また鎖伸長剤としてはエチレングリコール、ジエチレン
グリコール、プロピレングリコール、シグロピレングリ
コール、ブタンジオール等のグリコール類；エチレンジ
アミン、プロピレンジアミン、ジプロピレンジアミン、
ブチレンジアミン、ヘキサメチレンジアミン等の脂肪族
ジアミン；インホロンジアミン、４．４’−ジアミノジ
シクロヘキシルメタン等の脂環式ジアミン等が単独又は
２種以上混合して用いられる。上記無黄変型ポリウレタ
ンニラスト１−には射出成呈時の熱による表皮層のブロ
ッキング防止のためにシリカを添加することが好ましく
、ブロッキングが防止されることによってより射出成型
後の靴の取扱いが容易となる他、表面の粘着性が軽減さ
れ、汚れ防止に好都合となる。シリカの添加量はポリウ
レタンエラストマー１００重量部当り１．５〜６． Ｏ
ｉ全部が好ましい。In addition, as chain extenders, glycols such as ethylene glycol, diethylene glycol, propylene glycol, cyglopylene glycol, butanediol; ethylene diamine, propylene diamine, dipropylene diamine,
Aliphatic diamines such as butylene diamine and hexamethylene diamine; alicyclic diamines such as inphorone diamine and 4,4'-diaminodicyclohexylmethane are used alone or in combination of two or more. It is preferable to add silica to the above-mentioned non-yellowing polyurethane nilast 1- to prevent blocking of the skin layer due to heat during injection molding, and by preventing blocking, it is easier to handle the shoes after injection molding. In addition to being easier to clean, the surface is less sticky, which is convenient for preventing stains. The amount of silica added is 1.5 to 6.0 parts per 100 parts by weight of the polyurethane elastomer. O
All i are preferred.
合成皮革基材としては、ポリウレタンエラストマーを含
浸させた織布、不織布、編布等が挙げられ、具体的な合
成皮革基材の例としては、ポリエステル、レーヨン混紡
の片面又は両面起毛布上にポリウレタンエラストマーの
ジメチルフォルムアミド溶液を塗布した後、水中に浸漬
してポリウレタンニジストマーを凝固させて得られたも
のが挙げられる。この合成皮革基材としてはポリウレタ
ンニジストマーよ〕なる緻密な気泡構造のミクロポーラ
ス層を有するものが好ましい。Examples of synthetic leather base materials include woven fabrics, nonwoven fabrics, knitted fabrics, etc. impregnated with polyurethane elastomer. Specific examples of synthetic leather base materials include polyurethane on one or both sides of a polyester or rayon blend fabric. Examples include those obtained by coating a dimethylformamide solution of an elastomer and then immersing it in water to coagulate the polyurethane disstomer. The synthetic leather base material is preferably one having a microporous layer with a dense cell structure and made of polyurethane distomer.
上記合成皮革基材と表皮層とを接着する接着剤としては
ポリエチレンアジペート、ポリエチレンブチレンアジベ
ート、ポリブチレンアジペート、ポリブチレンヘキシレ
ンアジペート、ポリカプロラクトングリコールの少なく
とも１種と、低分子量グリコール及び芳香族ジイソシア
ネートとを構成成分とするポリウレタンエラストマーよ
りナル１液型接着剤が用いられるが、このエラストマー
を構成する低分子量グリコールとしては例えばエチレン
グリコール、１．４−ブタンジオール、１．３−ブタン
ジオール、ジエチレングリコール、ジプロピレングリコ
ール等が挙げられ、芳香族ジイソシアネートとしては例
えば４．４′−ジフェニルメタンジイソシアネート、２
．４− ）リレンジイソシアネート、２．６−）リレン
ジイソシアネート等が挙げられるが、接着性の上から特
に４．４′−ジフェニルメタンジインシアネートが好ま
しく、これに−部２．４−）リレンジインシアネート及
び／又は２゜６−ドリレンジイソシアネートを併用して
もよい。The adhesive for bonding the synthetic leather base material and the skin layer includes at least one of polyethylene adipate, polyethylene butylene adipate, polybutylene adipate, polybutylene hexylene adipate, polycaprolactone glycol, low molecular weight glycol, and aromatic diisocyanate. A one-component adhesive is used from a polyurethane elastomer having the following constituents. Examples of low molecular weight glycols constituting this elastomer include ethylene glycol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, Examples of aromatic diisocyanates include dipropylene glycol and the like; examples of aromatic diisocyanates include 4,4'-diphenylmethane diisocyanate, 2
．． 4-) lylene diisocyanate, 2.6-) lylene diisocyanate, etc., but 4,4'-diphenylmethane diisocyanate is particularly preferable from the viewpoint of adhesiveness, and in addition to this, 2.4-) lylene diisocyanate and /or 2°6-Dylene diisocyanate may be used in combination.
合成皮革基材に上記接着剤を介して表皮層を形成する方
法としては、離型紙上に、必要により顔料を添加して着
色した表皮層形成用のポリウレタンエンストマーの有機
溶媒溶液を塗布して乾燥させ、次いでこの上に接着剤用
のポリウレタンエラストマーの有機溶媒溶液を塗布して
乾燥させた後、合成皮革基材と重ね合わせて加熱圧着し
、離型紙を剥離して表皮層を合成皮革基材に転写する方
法が挙げられる。A method for forming a skin layer on a synthetic leather base material via the above-mentioned adhesive is to apply an organic solvent solution of a polyurethane entomer for forming a skin layer, which is colored by adding a pigment if necessary, onto a release paper. After drying, an organic solvent solution of a polyurethane elastomer for adhesives is applied on top of this, and after drying, it is overlapped with a synthetic leather base material and heat-pressed, the release paper is peeled off, and the outer layer is bonded to the synthetic leather base material. One example is a method of transferring the image to a material.
本発明方法においては上記合成皮革よりなる胛被の底部
に、ポリ塩化ビニルを主成分とする靴底材を射出成型し
て一体化された靴底を形成するが、胛被の表皮層がポリ
カプロラクトングリコール及び／又はポリブチレンアジ
ペートをポリエステル成分とする無黄変盤ボリクレタン
エラストマーよりなるために、靴底との接合部に予めプ
ライマー塗布を行なっておかずとも胛被と靴底とを確実
に接合することができる。靴底材の射出温度は通常１８
５〜２００℃程度である。In the method of the present invention, an integrated shoe sole is formed by injection molding a shoe sole material mainly composed of polyvinyl chloride on the bottom of the shoe cover made of synthetic leather, but the outer skin layer of the shoe cover is made of polyvinyl chloride. Since it is made of non-yellowing polycrethane elastomer containing caprolactone glycol and/or polybutylene adipate as a polyester component, it is possible to securely bond the shoe cover and the sole without having to apply a primer to the joint with the sole in advance. can do. The injection temperature of shoe sole material is usually 18
The temperature is about 5 to 200°C.
本発明方法では胛被表皮層を構成する無黄変型ポリウレ
タンエラストマーのポリエステル成分がポリカプロラク
トングリコールのみからなる場合でも胛被と靴底との接
着性に優れた靴を提供できるが、ポリカプロラフ）ｙグ
リコールとポリブチレンアジペートとを併用した場合、
ポリカプロラクトングリコール単独の場合に比べてよ多
大きい接着強度が得られるとともに、ポリブチレンアジ
ペート単独の場合に比べて胛被の耐加水分解性が向上し
、雨水等にさらされても胛被が侵され難くなり討入性に
優れた靴を提供できる。ポリカプロラクトングリコール
とポリブチレンアジペートとを併用する場合、両者の混
合比は、ポリカプロラクトングリコール８０〜９５重量
％、ポリブチレンアジペート５〜２０重量％が好ましく
、特に前者のポリエステル８５〜９２重量％、後者のポ
リエステル８〜１５重量％であることが好ましい。In the method of the present invention, even when the polyester component of the non-yellowing polyurethane elastomer constituting the shoe cover layer consists only of polycaprolactone glycol, it is possible to provide shoes with excellent adhesion between the shoe cover and the sole. When used together with polybutylene adipate,
In addition to providing much greater adhesive strength than polycaprolactone glycol alone, the hydrolysis resistance of the sheathing is improved compared to polybutylene adipate alone, and the sheathing is resistant to erosion even when exposed to rainwater. It is possible to provide shoes that are difficult to penetrate and have excellent penetration properties. When polycaprolactone glycol and polybutylene adipate are used together, the mixing ratio of the two is preferably 80 to 95% by weight of polycaprolactone glycol and 5 to 20% by weight of polybutylene adipate, particularly 85 to 92% by weight of the former polyester and 85 to 92% by weight of the latter. It is preferable that the amount of polyester is 8 to 15% by weight.
以下、実施例を挙げて本発明を更に詳細に説明する。尚
、以下重量％を単に％で示す。Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, below, weight % is simply shown as %.
実施例１〜４
ポリエステル６５％、レーヨン３５％の混紡比よりなる
厚さ１．３ ＊の両面起毛布にポリウレタンエラストマ
ー（熱軟化点２１０℃、１００％モジェラス６０ ｋｇ
／ａｌ ）のジメチルフォルムアミド溶液（固聾分９．
５％）を含浸させ、次いで共に駆動機構を供えた上下一
対のロール間をクリアランス１、Ｏｎで通過させ、余剰
液を絞液した後、２５℃・の水中に浸漬してポリウレタ
ンエラストマーヲ凝固させ、更にこの片面にポリウレタ
ンエラストマー（熱軟化点１９５℃、１００％モジュラ
ス４２ｋｇ／ｃＩりのジメチルフォルムアミド溶液（固
形分１８％）を固形分の塗布量が１ｓｏｇ７ｒｒｌとな
るように塗布した後、２５℃の水中に浸漬し、緻密なミ
クロポーラス層を有する合成皮革基材を得た。Examples 1 to 4 Polyurethane elastomer (thermal softening point 210°C, 100% modulus 60 kg) was applied to a 1.3* thick double-sided fabric made of a blend of 65% polyester and 35% rayon.
/al) in dimethylformamide (solid hearing content 9.
5%), and then passed between a pair of upper and lower rolls, both equipped with a drive mechanism, with a clearance of 1, ON, and after squeezing out excess liquid, the polyurethane elastomer was immersed in water at 25°C to solidify it. Further, polyurethane elastomer (thermal softening point 195°C, 100% modulus 42 kg/cI dimethyl formamide solution (solid content 18%) was applied to one side of this so that the solid content was 1 sog 7 rrl, and then 25°C A synthetic leather base material having a dense microporous layer was obtained.
次いで天然皮革様の絞を有する離型紙上に、表皮層形成
用ポリウレタンニジストマーとして第１表に示すポリエ
ステルと４．４′−ジシクロヘキシルメタンジインシア
ネート、１．３−ブタンジオール、４．４′−ジアミノ
ジシクロヘキシルメタンよりなるポリウレタンニジスト
マー（熱軟化点及び１ｏ。Next, on a release paper having a natural leather-like squeeze, polyesters shown in Table 1, 4,4'-dicyclohexylmethane diincyanate, 1,3-butanediol, and 4,4'- as a polyurethane disstomer for forming a skin layer were placed. A polyurethane disstomer made of diaminodicyclohexylmethane (thermal softening point and 1o.
％モジーラスの値を第１表に示す。）を２５％含む、ジ
メチルフォルムアミド、イソプロピルアルコール、トル
エン、シクロヘキサノンａ合ｓ媒ｓ液を１００．！ｉｌ
／ｍの目付量で塗布し、８０℃にて乾燥した後、この上
に接着剤として第１表に示すポリエステルとジエチレン
グリコール及び４．４’−ジフェニルメタンジイソシア
ネートとからなるポリウレタンニジストマー（熱軟化点
及び１００％モジュラスの値を第１表１ζ示す。）を２
０％、顔料３％を含有するジメチルフォルムアミド、メ
チルエチルケトン混合溶媒溶液を１２０．Ｆ／ｍの目伺
量で塗布し、８０℃で２分、１２０℃で２分乾燥し九後
、合成皮革基材と重ね合わせて離型紙側より１５０℃の
表面温度を有する熱ロールで加熱加圧し、冷却後離型紙
を剥離して転写された表皮層を有する合成皮革を得た。The values of % modulus are shown in Table 1. ) containing 25% of dimethylformamide, isopropyl alcohol, toluene, and cyclohexanone (a) at 100%. ! il
/m, and after drying at 80°C, a polyurethane disstomer (thermal softening point and The value of 100% modulus is shown in Table 1.
A mixed solvent solution of dimethyl formamide and methyl ethyl ketone containing 0% pigment and 3% pigment was mixed at 120%. F/m coating amount, dried at 80℃ for 2 minutes and 120℃ for 2 minutes, then overlapped with the synthetic leather base material and heated from the release paper side with a heat roll with a surface temperature of 150℃. After applying pressure and cooling, the release paper was peeled off to obtain synthetic leather having a transferred skin layer.
次にこの合成皮革を裁断、縫製して胛被を製造し、この
胛被を靴底射出成製用金型にセットしてポリ塩化ビニル
靴底材を１９４℃で射出して胛被と一体化された靴底を
形成した。この胛被と靴底との接着強度を、胛被と靴底
との接合部分を幅８鵡、長さ１０００に切シ取ったサン
プルを記録計付き引張）試験機で剥離速度５０ｍ／ｍに
て測定した。結果を第１表に示す。Next, this synthetic leather is cut and sewn to produce a shoe cover, which is set in a shoe sole injection mold, and polyvinyl chloride sole material is injected at 194°C to integrate it with the shoe sole. formed the sole of the shoe. The adhesive strength between the shoe cover and the sole was measured using a tensile tester equipped with a recorder, using a sample cut from the joint between the shoe cover and the sole to a width of 8 mm and a length of 1,000 mm, at a peeling speed of 50 m/m. It was measured using The results are shown in Table 1.
比較例１
ポリカプロラクトングリコール、１，４−ブタンジオー
ル、４．４’−ジフェニルメタンジイソシアネートより
なる黄変型ポリウレタンエラストマー（熱軟化点１６０
℃、１００％モジ−ラス ４５ｋ１９／ｉ ）を２５％
、カーボンブラック（顔料）を３％含むジメチルフォル
ムアミド、メチルエチルケトン混合溶媒溶液を１２０
ｉ／ゼの目付量で塗布して表皮層を形成した以外は実施
例１と同様にして靴を製造した。この靴の胛被と靴底と
の接着強度は１．８ ｋｇ／ ｔｘ Ｌ／かなく靴底と
胛被とが剥離しやすかった。Comparative Example 1 Yellowing type polyurethane elastomer (thermal softening point: 160
°C, 100% modulus 45k19/i) to 25%
, a mixed solvent solution of dimethylformamide and methyl ethyl ketone containing 3% carbon black (pigment) at 120%
Shoes were manufactured in the same manner as in Example 1, except that the skin layer was formed by coating at a basis weight of i/ze. The adhesive strength between the shoe cover and the sole of this shoe was 1.8 kg/tx L/, and the sole and shoe cover were easily peeled off.
比較例２
胛被における接着剤としてトリレンジインシアネートを
イソシアネート成分とするウレタン系２液型接着剤（ク
リズボン４０フ０：大日本インキ化学工業製）を用いた
他は実施例２と同様にして靴を製造した。この靴は胛被
が皮革様の柔軟性に欠けておシ、また胛被と靴底とはプ
ライマーなしに接着することができたが、靴底を射出成
型した後に、靴底との接合部付近において胛被の表皮層
が基材より剥離してしまった。Comparative Example 2 The same procedure as in Example 2 was used except that a urethane-based two-component adhesive (Crybon 40 F0: manufactured by Dainippon Ink and Chemicals) containing tolylene diincyanate as the isocyanate component was used as the adhesive for the cover. manufactured shoes. These shoes lacked leather-like flexibility, and although it was possible to bond the hem and sole without a primer, after the sole was injection molded, the joint with the sole was bonded. The epidermal layer of the flycover peeled off from the base material in the vicinity.
実施例５〜８
天然皮革様の絞を有する離型紙上に、表皮層形成用ポリ
ウレタンエラストマーとして第２表に示すポリエステル
とへキサメチレンジイソシアネート、ヘキサメチレンジ
アミン、１．３−ブタンジオールとからなるポリウレタ
ンニジストマー（熱軟化点及び１００％モジュラスの値
を第２表に示す−を２５％とシリカ１．２％を含むジメ
チルフォルムアミド、イソプロピルアルコール、トルエ
ン、シクロヘキケシ混合溶媒溶液をＺｏｏ、９／ｍＪの
目付量で塗布し、８０℃で乾燥した後、更にこの上に接
着剤として第２表に示すポリエステルと１，４−ブタン
ジオール及び４．４′−ジフェニルメタンジイソシアネ
ートとからなるポリウレタンエラストマー（熱軟化点及
び１００％モジュラスの値を第２表に示す。）を２０％
、顔料３％を含有するジメチルフォルムアミド、メチル
エチルケトン混合溶媒溶液を１２０ｆ！／ｍの目付量で
塗布し、８０℃で２分、１２０℃で２分乾燥した後、実
施例１〜４と同様の合成皮革基材と重ね合せて加熱加圧
して表皮層を転写し、合成皮革とした。この合成皮革か
ら作成した胛被を用いて実施例１〜４と同様にして射出
成型を行ない、一体化された靴底を形成した。Examples 5 to 8 A polyurethane consisting of the polyester shown in Table 2, hexamethylene diisocyanate, hexamethylene diamine, and 1,3-butanediol was applied as a polyurethane elastomer for forming a skin layer on a release paper having a natural leather-like draw. A mixed solvent solution of dimethylformamide, isopropyl alcohol, toluene, and cyclohexyl chloride containing 25% of silica and 1.2% of silica was added to Zoo, 9/mJ. After drying at 80°C, a polyurethane elastomer (heat softenable The values of point and 100% modulus are shown in Table 2.) to 20%
, dimethylformamide and methyl ethyl ketone mixed solvent solution containing 3% of pigment at 120 f! /m, and after drying at 80°C for 2 minutes and 120°C for 2 minutes, it was layered with the same synthetic leather base material as in Examples 1 to 4 and heated and pressed to transfer the skin layer. Made of synthetic leather. Injection molding was carried out in the same manner as in Examples 1 to 4 using a shoe cover made from this synthetic leather to form an integrated shoe sole.
得られた靴は、胛被表面が滑性に富み、柔軟で汚れも付
着しにくく、きわめて屈曲性に優れた天然皮革様外観、
風合を有していた。この靴の胛被と靴底との接着強度を
第２表に示す。The resulting shoes have a highly slippery surface, are flexible, do not easily attract dirt, and have a natural leather-like appearance with excellent flexibility.
It had a texture. Table 2 shows the adhesive strength between the shoe cover and the sole of this shoe.
Claims (3)
アジペート、ポリブチレンアジペート、ポリブチレンヘ
キシレンアジペート、ポリカプロラクトングリコールの
少なくとも１種と、低分子量グリコール及び芳香族ジイ
ソシアネートとを構成成分とするポリウレタンエラスト
マーよりなる１液型接着剤により合成皮革基材に接着さ
れた、ポリカプロラクトングリコール及び／又はポリブ
チレンアジペートをポリエステル成分とする無黄変型ポ
リウレタンエラストマーよりなる表皮層を有する合成皮
革より胛被を形成し、次いで該胛被の底部に、ポリ塩化
ビニルを主成分とする靴底材を射出成型して一体化され
た靴底を形成することを特徴とする合成皮革靴の製造方
法。(1) One-component adhesive made of a polyurethane elastomer containing at least one of polyethylene adipate, polyethylene butylene adipate, polybutylene adipate, polybutylene hexylene adipate, and polycaprolactone glycol, as well as a low molecular weight glycol and an aromatic diisocyanate. A jacket is formed from a synthetic leather having a skin layer made of a non-yellowing polyurethane elastomer containing polycaprolactone glycol and/or polybutylene adipate as a polyester component, which is adhered to a synthetic leather base material with an agent. A method for manufacturing synthetic leather shoes, characterized by forming an integrated sole by injection molding a sole material containing polyvinyl chloride as a main component.
求の範囲第１項記載の合成皮革靴の製造方法。(2) The method for manufacturing synthetic leather shoes according to claim 1, wherein the synthetic leather base material has a microporous layer.
た後、該表皮層をミクロポーラス層を有する合成皮革基
材に転写して形成されたものである特許請求の範囲第１
項記載の合成皮革靴の製造方法。(3) The skin layer of the synthetic leather is formed by forming the skin layer on a release paper and then transferring the skin layer to a synthetic leather base material having a microporous layer.
A method for manufacturing synthetic leather shoes as described in Section 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61203050A JPH085147B2 (en) | 1986-08-29 | 1986-08-29 | Method for manufacturing synthetic leather shoes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61203050A JPH085147B2 (en) | 1986-08-29 | 1986-08-29 | Method for manufacturing synthetic leather shoes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6357002A true JPS6357002A (en) | 1988-03-11 |
| JPH085147B2 JPH085147B2 (en) | 1996-01-24 |
Family
ID=16467511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61203050A Expired - Fee Related JPH085147B2 (en) | 1986-08-29 | 1986-08-29 | Method for manufacturing synthetic leather shoes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085147B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57154470A (en) * | 1981-03-16 | 1982-09-24 | Kohkoku Chem Ind | Synthetic leather excellent in durability and high frequency fusibility |
| JPS58118703A (en) * | 1982-01-07 | 1983-07-14 | 株式会社クラレ | Production of artificial leather shoes |
| JPS6154929A (en) * | 1984-08-28 | 1986-03-19 | 株式会社クラレ | Enamel-like leather-like sheet article |
-
1986
- 1986-08-29 JP JP61203050A patent/JPH085147B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57154470A (en) * | 1981-03-16 | 1982-09-24 | Kohkoku Chem Ind | Synthetic leather excellent in durability and high frequency fusibility |
| JPS58118703A (en) * | 1982-01-07 | 1983-07-14 | 株式会社クラレ | Production of artificial leather shoes |
| JPS6154929A (en) * | 1984-08-28 | 1986-03-19 | 株式会社クラレ | Enamel-like leather-like sheet article |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH085147B2 (en) | 1996-01-24 |
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