JPH03292320A - Thermoplastic polyurethane - Google Patents
Thermoplastic polyurethaneInfo
- Publication number
- JPH03292320A JPH03292320A JP2093213A JP9321390A JPH03292320A JP H03292320 A JPH03292320 A JP H03292320A JP 2093213 A JP2093213 A JP 2093213A JP 9321390 A JP9321390 A JP 9321390A JP H03292320 A JPH03292320 A JP H03292320A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic polyurethane
- compound
- parts
- chain extender
- polyester
- 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
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 23
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 150000002009 diols Chemical class 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 229940126062 Compound A Drugs 0.000 abstract 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000002649 leather substitute Substances 0.000 description 8
- -1 aliphatic diamine Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001610 polycaprolactone Polymers 0.000 description 6
- 239000004632 polycaprolactone Substances 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明は、ポリヒドロキシル化合物、有機イソノアナー
ト、鎖伸長剤を重合し、耐加水分解性、耐候性及び耐熱
性の改良されて、コーティング用途に適した熱可塑性ポ
リウレタン樹脂の製造方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention involves polymerizing a polyhydroxyl compound, an organic isonoanate, and a chain extender to improve hydrolysis resistance, weather resistance, and heat resistance, and to use the resulting product in coating applications. The present invention relates to a method for producing suitable thermoplastic polyurethane resins.
従来より、コーティング用途に適した熱可塑性ポリウレ
タン樹脂は、耐候性、耐摩耗性、ゴム的物性が良い事か
ら、合成皮革、塩ビレザー、人工皮革等のトップコート
（表面処理剤）として使用されている。Thermoplastic polyurethane resins, which are suitable for coating applications, have traditionally been used as top coats (surface treatment agents) for synthetic leather, PVC leather, artificial leather, etc. due to their good weather resistance, abrasion resistance, and rubber-like physical properties. There is.
これらの熱可塑性ポリウレタン樹脂としては、ポリエス
テル系ポリウレタン、ポリエーテル系ポリウレタン、ポ
リカーボネート系等が知られているが、耐候性、耐水性
、耐熱性の点から、ポリエステル系ポリウレタン、ポリ
カーボネート系ポリウレタンが用いられている。Polyester-based polyurethane, polyether-based polyurethane, polycarbonate-based, etc. are known as these thermoplastic polyurethane resins, but polyester-based polyurethane and polycarbonate-based polyurethane are used from the viewpoint of weather resistance, water resistance, and heat resistance. ing.
しかしながら、ポリカーボネート系ボリウレタンは高価
な点から、ポリエステル系ポリウレタンが主に用いられ
ている。However, since polycarbonate polyurethane is expensive, polyester polyurethane is mainly used.
ポリエステル系ポリウレタンとしては、１．４ブタンジ
オール、アジピン酸を主構成成分とするポリエステルジ
オール、ポリカプロラクトンジオール等のポリエステル
ポリオール、有機イソシアナートとしては、ヘキサメチ
レンジイソシアナート、イソホロンジイソシアナート、
４，４゛−ジシクロヘキシルメタンジイソシアナート、
水添化キシリレンジイソシアナート等の脂肪族又は脂環
族ジイソシアナートを用い、鎖伸長剤としては、エチレ
ンジアミン、プロピレンジアミン等の脂肪族ジアミン、
イソホロンジアミン、４，４゛−ジシクロヘキシルメタ
ンジアミン等の脂環族ジアミンからなるポリウレタンが
知られている。Examples of polyester polyurethanes include 1.4-butanediol, polyester diols containing adipic acid as a main component, and polyester polyols such as polycaprolactone diol; examples of organic isocyanates include hexamethylene diisocyanate, isophorone diisocyanate,
4,4゛-dicyclohexylmethane diisocyanate,
An aliphatic or alicyclic diisocyanate such as hydrogenated xylylene diisocyanate is used, and as a chain extender, an aliphatic diamine such as ethylene diamine or propylene diamine,
Polyurethanes made of alicyclic diamines such as isophorone diamine and 4,4'-dicyclohexylmethane diamine are known.
しかしながら、上述の熱可塑性ポリウレタンは、合成皮
革、人工皮革、塩ビレザーのトップコートとして使用さ
れた時、耐候性、耐水性、特に耐加水分解性が充分でな
く問題であった。However, when the above-mentioned thermoplastic polyurethane is used as a top coat for synthetic leather, artificial leather, or vinyl chloride leather, it is problematic because it does not have sufficient weather resistance, water resistance, and especially hydrolysis resistance.
本発明者等は、上述した従来技術の問題に鑑み、耐候性
、耐加水分解性及び耐熱性の優れた熱可塑性ポリウレタ
ンを提供する目的で鋭意検討を重ね、本発明を完成する
に至った。In view of the problems of the prior art described above, the present inventors have conducted extensive studies with the aim of providing a thermoplastic polyurethane with excellent weather resistance, hydrolysis resistance, and heat resistance, and have completed the present invention.
本発明によれば、末端に水酸基を有するポリヒドロキシ
化合物、有機ジイソシアナート及び鎖伸長剤を重合して
熱可塑性ポリウレタンを製造するにあたり
ｉ）前記ポリヒドロキシル化合物として平均分子量５０
０〜５０００のポリエステルジオールを用いｉｉ）前記
有機ジイソシアナートとして次式（１）で示される化合
物を用い
ｉｊ）前記鎖伸長剤として、次式（ＩＩ）で示される化
合物を用いること
より成る熱可塑性ポリウレタンによって達成され本発明
に於いて、ポリエステルポリオールとしては、例えばエ
チレングリコール、１．４−ブタンジオール、ネオペン
チルグリコール、１．６−ヘキサンジオール等のジオー
ルと、アジピン酸等のジカルボン酸と脱水縮合反応によ
って得られるポリエステルポリオール又は、カプロラク
トンの開環重合で得られるポリカプロラクトンのポリエ
ステルポリオールを言う。According to the present invention, in producing a thermoplastic polyurethane by polymerizing a polyhydroxy compound having a hydroxyl group at the terminal, an organic diisocyanate, and a chain extender, i) the polyhydroxy compound has an average molecular weight of 50
0 to 5000 polyester diol; ii) as the organic diisocyanate, a compound represented by the following formula (1); and ij) as the chain extender, a compound represented by the following formula (II). In the present invention, polyester polyols include diols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol, dicarboxylic acids such as adipic acid, and dehydration. It refers to a polyester polyol obtained by a condensation reaction or a polyester polyol of polycaprolactone obtained by ring-opening polymerization of caprolactone.
ポリエステルポリオールの平均分子量としては５００〜
５ｏｏｏ、更に好ましくは５００〜３０００のポリエス
テルが耐候性、耐水性の点から好ましい。The average molecular weight of polyester polyol is 500~
500, more preferably 500 to 3,000 polyester is preferred from the viewpoint of weather resistance and water resistance.
分子量が５００より少ないものを用いると、熱可塑性ポ
リウレタンが硬く、柔軟性に乏しく、合成皮革、人工皮
革、塩ビレザーのトップコートとして使用出来ない。If a polyurethane having a molecular weight of less than 500 is used, the thermoplastic polyurethane will be hard and have poor flexibility, and cannot be used as a top coat for synthetic leather, artificial leather, or vinyl chloride leather.
一方、ポリエステルの分子量が５０００より大きい時は
、熱可塑性ポリウレタン樹脂が軟く、ブロッキング性に
問題があり、トップコートとして使用出来ない。On the other hand, when the molecular weight of the polyester is greater than 5,000, the thermoplastic polyurethane resin is soft and has a problem with blocking properties, and cannot be used as a top coat.
本発明の熱可塑性ポリウレタンの製造方法としては、次
の如き方法である。The method for producing the thermoplastic polyurethane of the present invention is as follows.
末端に水酸基を有するポリヒドロキシル化合物に、過剰
の前記（１）式で示される有機イソシアナート化合物を
混合し、加熱により、通常５０°Ｃ〜１５０°Ｃの如き
温度で反応させて得た、末端にイソンアナートを有する
、重合中間体であるプレポリマーを、ジメチルホルムア
ミド、ジメチルスルホキンド、又はジメチルアセトアミ
ドの如き有機溶剤、又はヘンゼン、トルエン、キンレン
、エチルベンゼン等の芳香族系溶剤、酢酸メチル、酢酸
エチル、酢酸ブチル等のエステル系溶剤、アセトン、メ
チルエチルケトン、メチルイソブチルケトン等のケトン
系溶剤の如き溶剤等の、少なくとも１種又は１種以上を
混合してなる混合溶剤に溶解させることによりプレポリ
マー溶液を得る。A polyhydroxyl compound having a hydroxyl group at the end is mixed with an excess of the organic isocyanate compound represented by the formula (1) above, and the mixture is heated to react at a temperature of usually 50°C to 150°C. The prepolymer, which is a polymerization intermediate, has isoneanate in an organic solvent such as dimethylformamide, dimethylsulfoquinde, or dimethylacetamide, or an aromatic solvent such as henzene, toluene, kylene, ethylbenzene, methyl acetate, ethyl acetate, A prepolymer solution is obtained by dissolving it in a mixed solvent of at least one or more of ester solvents such as butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. .
このプレポリマー溶液に、前記（Ｉｔ）式で示される化
合物を、室温近くで加えて鎖伸長反応を行い、熱可塑性
ポリウレタン溶液を得る。A compound represented by the formula (It) above is added to this prepolymer solution near room temperature to carry out a chain extension reaction to obtain a thermoplastic polyurethane solution.
尚、前記ポリヒドロキシ化合物と、前記（１）式で示さ
れる化合物の混合割合は、モル比で１対１．１〜４．０
、好ましくは１対１．５〜３．０である。The mixing ratio of the polyhydroxy compound and the compound represented by formula (1) is 1:1.1 to 4.0 in molar ratio.
, preferably 1:1.5 to 3.0.
更に前記ポリヒドロキシル化合物と、前記（Ｉ）式で示
される化合物を混合し、反応させて得た末端にイソシア
ナート基を有する重合中間体であるプレポリマーと、前
記（Ｉｆ）式で示される化合物の混合割合は、当量比で
１対０．９〜０．９９が適当である。Further, a prepolymer which is a polymerization intermediate having isocyanate groups at the terminals obtained by mixing and reacting the polyhydroxyl compound with the compound represented by the formula (I), and the compound represented by the formula (If) The appropriate mixing ratio is 1:0.9 to 0.99 in terms of equivalent ratio.
したがって、反応が所望の分子量に達した後、残存する
イソシアナート基を、メタノール、エタノール、イソプ
ロピルアルコール等の１価のアルコールを添加混合して
、消滅させるのが望ましい。Therefore, after the reaction reaches a desired molecular weight, it is desirable to eliminate the remaining isocyanate groups by adding and mixing a monohydric alcohol such as methanol, ethanol, or isopropyl alcohol.
本発明によって得られた熱可塑性ポリウレタンは、数平
均分子量が１０．０００〜１００，０００程度の分子量
を有し、耐候性、耐薬品性、耐水性、耐加水分解性、引
張り強さ、伸度等の物性の経日変化に伴う著しい低下も
なく、かつ又、合成皮革、人工皮革、塩ビレザーのトッ
プコート剤として、耐ブロッキング性等に問題のない優
れた熱可塑性ポリウレタンである。The thermoplastic polyurethane obtained by the present invention has a number average molecular weight of about 10.000 to 100,000, and has good weather resistance, chemical resistance, water resistance, hydrolysis resistance, tensile strength, and elongation. It is an excellent thermoplastic polyurethane that does not show any significant deterioration in its physical properties over time, and can be used as a top coat agent for synthetic leather, artificial leather, and vinyl chloride leather without any problems in blocking resistance or the like.
以下、本発明を、更に具体的に説明するため、実施例及
び比較例をあげて説明するが、本発明しまこれらの実施
例に限定されるものではなし１゜尚、各実施例中に於け
る部及び％はすべで重量値で示す。Hereinafter, in order to explain the present invention more specifically, Examples and Comparative Examples will be given to explain the present invention, but the present invention is not limited to these Examples. All parts and percentages are expressed by weight.
実施例１
１．４ブタンジオールとアジピン酸とを重縮合した平均
分子量１０００のポリエステル１００部（０，１モル）
と、 （１）式で示されるイソシアナート２８５（６）
−ジイソシアナートメチル−ビシクロ（２，２，１）へ
ブタン４１．２部（０，２モル）とを、窒素気流中にて
１００°Ｃで３時間反応させて、残存ＮＣＯ含有量５．
９％のプレポリマーを得た。Example 1 100 parts (0.1 mol) of polyester with an average molecular weight of 1000 obtained by polycondensation of 1.4-butanediol and adipic acid
and isocyanate 285(6) represented by formula (1)
-diisocyanatomethyl-bicyclo(2,2,1)butane (41.2 parts (0.2 mol)) was reacted with 41.2 parts (0.2 mol) of butane in a nitrogen stream at 100°C for 3 hours, resulting in a residual NCO content of 5.
9% prepolymer was obtained.
このプレポリマー１４１゜２部を、ジメチＪレホＪレム
アミド１４１．２部、酢酸エチル２２３部で希釈して、
室温まで冷却した。141.2 parts of this prepolymer was diluted with 141.2 parts of dimethyJrehoJ remamide and 223 parts of ethyl acetate.
Cooled to room temperature.
これに（ｎ）式で示される２、５（６）−ジアミノメチ
ル−ビシクロ（２，２，１）へブタンを１５部加えて反
応させ、最後にメタノール１部を加えて、熱可塑性ポリ
ウレタン溶液を得た。To this, 15 parts of butane was added to 2,5(6)-diaminomethyl-bicyclo(2,2,1) represented by formula (n) to react, and finally 1 part of methanol was added to form a thermoplastic polyurethane solution. I got it.
このポリウレタン溶液を、ガラス板上に塗布し、８０’
Ｃで１時間乾燥して、約０ 、１５〜０ 、２ ａｍ
ｌ￥さのフィルムを作製した。This polyurethane solution was applied onto a glass plate, and
Dry for 1 hour at
A film of 1 yen was made.
次いで、該フィルムを冷却後、そのフィルムの性能試験
を行った。After cooling the film, the film was then tested for performance.
その試験結果を表１に示す。The test results are shown in Table 1.
実施例２
分子量２０００のポリカプロラクトンポリオール７６部
（０，０３８モル）、分子量７００のポリカプロラクト
ンポリオール４３．４部（０，０６２モル’） 、２．
５（６）−ジイソシアナートメチル−ビシクロ（２，２
，１）へブタン４１．２部（０，２モル）とを、実施例
１と同様な条件で反応を行い、残存ＮＣＯ％＝５．２％
のプレポリマーを得た。Example 2 76 parts (0,038 mol) of polycaprolactone polyol with a molecular weight of 2000, 43.4 parts (0,062 mol') of polycaprolactone polyol with a molecular weight of 700, 2.
5(6)-Diisocyanatomethyl-bicyclo(2,2
, 1) 41.2 parts (0.2 mol) of hebutane was reacted under the same conditions as in Example 1, and residual NCO% = 5.2%.
A prepolymer was obtained.
これに１５部の２．５（６）−ジアミノメチルビシクロ
（２，２，１）へブタンを、実施例１と同様な方法で用
いて熱可塑性ポリウレタン溶液を得た。To this, 15 parts of 2.5(6)-diaminomethylbicyclo(2,2,1)hebutane was used in the same manner as in Example 1 to obtain a thermoplastic polyurethane solution.
このポリウレタン溶液を用いて、実施例１と同様に、フ
ィルムを作成し性能試験を行った。Using this polyurethane solution, a film was prepared and a performance test was conducted in the same manner as in Example 1.
その試験結果を表１に示す。The test results are shown in Table 1.
比較例１
１．４ブタンジオールとアジピン酸とを重縮合した平均
分子量１０００のポリエステル１００部（０，１モル）
とイソホロンジイソシアナート４４．４部（０，２モル
）とを反応させて、残存ＮＣＯ％＝５．８％のプレポリ
マーを得た。Comparative Example 1 100 parts (0.1 mol) of polyester with an average molecular weight of 1000 obtained by polycondensing 1.4-butanediol and adipic acid
was reacted with 44.4 parts (0.2 mol) of isophorone diisocyanate to obtain a prepolymer with residual NCO%=5.8%.
このプレポリマー１４４．４部とイソホロンジアミン１
６部にて、実施例１と同様な方法で、熱可塑性ポリウレ
タン溶液を得た。144.4 parts of this prepolymer and 1 part of isophoronediamine
A thermoplastic polyurethane solution was obtained in 6 parts in the same manner as in Example 1.
この溶液を用いてフィルムを作成し性能試験を行った。A film was made using this solution and a performance test was conducted.
その試験結果を表１に示す。The test results are shown in Table 1.
比較例２
分子量２０００のポリカプロラクトンポリオール７６部
（０，０３８モル）、分子量７００のポリカプロラクト
ンポリオール４３．４部（０，０６２モル） 、４．４
’−ジシクロヘキシルメタンジイソシアナート５２．４
部（０，２モル）とを反応させて、残存ＮＣ○％＝４．
８％のプレポリマーを得た。Comparative Example 2 76 parts (0,038 mol) of polycaprolactone polyol with a molecular weight of 2000, 43.4 parts (0,062 mol) of polycaprolactone polyol with a molecular weight of 700, 4.4
'-dicyclohexylmethane diisocyanate 52.4
(0.2 mol) to give a residual NC○%=4.
8% prepolymer was obtained.
このプレポリマー１７１．８部、イソホロンジアミン１
６部にて、実施例１と同様な方法で熱可塑性ポリウレタ
ン溶液を得た。171.8 parts of this prepolymer, 1 part of isophoronediamine
6 parts of a thermoplastic polyurethane solution was obtained in the same manner as in Example 1.
この溶液を用いてフィルムを作成し性能試験を行った。A film was made using this solution and a performance test was conducted.
その試験結果を表１に示す。The test results are shown in Table 1.
本発明により得られた熱可塑性ポリウレタンは、従来の
ものに比べ、耐候性及び耐湿性が優れていることは、表
１から明らかである。It is clear from Table 1 that the thermoplastic polyurethane obtained according to the present invention has better weather resistance and moisture resistance than conventional polyurethanes.
・耐湿テスト ：５０’Ｃ１９５％湿度雰囲気中に７日
間放置後取り出し放冷後の外観フィルム物性測定イ直・
耐候性テスト：ウェザオフ−ター５００時間照射後の外
観、フィルム物性測定値・Moisture resistance test: After being left in a 50'C 195% humidity atmosphere for 7 days, it was taken out and left to cool, and the physical properties of the film were measured directly.
Weather resistance test: Appearance and film property measurements after 500 hours of weather exposure
Claims (1)
機ジイソシアナート及び鎖伸長剤を重合して熱可塑性ポ
リウレタンを製造するにあたり、ｉ）該ポリヒドロキシ
化合物として、平均分子量５００〜５０００のポリエス
テルジオールを用い、ｉｉ）該有機ジイソシアナートと
して、次式（ I ）▲数式、化学式、表等があります▼
（ I ） で示される化合物を用い、 ｉｉｉ）該鎖伸長剤として、次式（II） ▲数式、化学式、表等があります▼（II） で示される化合物を用いることを特徴とする耐候性、耐
水性に優れた熱可塑性ポリウレタン。[Claims] 1. In producing a thermoplastic polyurethane by polymerizing a polyhydroxy compound having a hydroxyl group at the end, an organic diisocyanate, and a chain extender, i) the polyhydroxy compound has an average molecular weight of 500 to 5000 polyester diol, ii) As the organic diisocyanate, the following formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Weather resistance characterized by using a compound represented by (I), and iii) using a compound represented by the following formula (II) as the chain extender: Thermoplastic polyurethane with excellent water resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2093213A JP3054424B2 (en) | 1990-04-10 | 1990-04-10 | Thermoplastic polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2093213A JP3054424B2 (en) | 1990-04-10 | 1990-04-10 | Thermoplastic polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03292320A true JPH03292320A (en) | 1991-12-24 |
| JP3054424B2 JP3054424B2 (en) | 2000-06-19 |
Family
ID=14076289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2093213A Expired - Fee Related JP3054424B2 (en) | 1990-04-10 | 1990-04-10 | Thermoplastic polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3054424B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140041A (en) * | 1997-11-07 | 1999-05-25 | Mitsui Chem Inc | Polyisocyanate and its production |
| WO2001019887A1 (en) * | 1999-09-10 | 2001-03-22 | Mitsui Chemicals, Inc. | Polyurethane resin with degradability |
| JP2009539053A (en) * | 2006-03-31 | 2009-11-12 | ハネウェル・インターナショナル・インコーポレーテッド | Improved liquid submerged ballistic resistance performance by hybridization |
-
1990
- 1990-04-10 JP JP2093213A patent/JP3054424B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140041A (en) * | 1997-11-07 | 1999-05-25 | Mitsui Chem Inc | Polyisocyanate and its production |
| WO2001019887A1 (en) * | 1999-09-10 | 2001-03-22 | Mitsui Chemicals, Inc. | Polyurethane resin with degradability |
| US6555645B1 (en) | 1999-09-10 | 2003-04-29 | Mitsui Chemicals, Inc. | Degradable polyurethane resin |
| KR100421246B1 (en) * | 1999-09-10 | 2004-03-04 | 미쯔이카가쿠 가부시기가이샤 | Polyurethane resin with degradability |
| JP2009539053A (en) * | 2006-03-31 | 2009-11-12 | ハネウェル・インターナショナル・インコーポレーテッド | Improved liquid submerged ballistic resistance performance by hybridization |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3054424B2 (en) | 2000-06-19 |
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