JPH0423823A - Polyurethane resin composition and molding - Google Patents
Polyurethane resin composition and moldingInfo
- Publication number
- JPH0423823A JPH0423823A JP2125337A JP12533790A JPH0423823A JP H0423823 A JPH0423823 A JP H0423823A JP 2125337 A JP2125337 A JP 2125337A JP 12533790 A JP12533790 A JP 12533790A JP H0423823 A JPH0423823 A JP H0423823A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- molding
- resin
- isocyanate groups
- various
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 38
- 238000000465 moulding Methods 0.000 title claims description 28
- 239000011342 resin composition Substances 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims 1
- -1 polyethylene adipate Polymers 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 4
- 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 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 229920000921 polyethylene adipate Polymers 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 description 12
- 150000003077 polyols Chemical class 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical class O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリウレタン樹脂組成物及び成形方法に関し、
更に詳しくは、成形容易な熱可塑性ポリウレタン樹脂か
ら各種物性に優れたポリウレタン樹脂成形品を容易に提
供することが出来るポリウレタン樹脂組成物及びその成
形方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a polyurethane resin composition and a molding method,
More specifically, the present invention relates to a polyurethane resin composition and a method for molding the same, which can easily provide polyurethane resin molded products with excellent various physical properties from an easily moldable thermoplastic polyurethane resin.
（従来の技術及びその問題点）
従来、ポリウレタン樹脂は、各種コーティング剤、塗料
、インキ等のバインダー、フィルム、成形品等として広
く使用されており、各々の用途に適したポリウレタン樹
脂が提案されている。(Prior art and its problems) Polyurethane resins have traditionally been widely used as binders for various coating agents, paints, and inks, films, molded products, etc., and polyurethane resins suitable for each use have been proposed. There is.
これらのポリウレタン樹脂は、基本的にはマクロポリオ
ール、ポリイソシアネート及び鎖伸長剤を反応させて得
られるものであり、これら各成分の種類、組合せ等によ
って種々の物性のポリウレタン樹脂が提供されており、
各種成形用のポリウレタン樹脂としては熱可塑性ポリウ
レタン樹脂が広く使用されている。These polyurethane resins are basically obtained by reacting macropolyols, polyisocyanates, and chain extenders, and polyurethane resins with various physical properties are provided depending on the types and combinations of these components.
Thermoplastic polyurethane resins are widely used as polyurethane resins for various molding applications.
上記熱可塑性ポリウレタン樹脂は、線状構造であって、
熱によって可塑化し、加熱溶融させることによって押比
し成形や射出成形等で任意の形状に成形し得るが、これ
らの成形物は当然のことながら、耐熱性、耐溶剤性、耐
摩耗性、圧縮永久歪等の各種物性に劣る。The thermoplastic polyurethane resin has a linear structure,
By plasticizing and melting with heat, it can be molded into any shape by extrusion molding, injection molding, etc., but these molded products naturally have good heat resistance, solvent resistance, abrasion resistance, and compression resistance. Poor in various physical properties such as permanent deformation.
これらの各種物性を向上させる方法としては、成形時に
ポリウレタン樹脂中にイソシアネート化合物とポリオー
ル化合物とを混合させて、成形と同時に架橋構造を生成
させる方法があるが、この方法では使用する樹脂組成物
の安定性が劣るという問題があり、又、成形中に架橋構
造が生成して成形不能となる等の種々の問題がある。One way to improve these various physical properties is to mix an isocyanate compound and a polyol compound into a polyurethane resin during molding to generate a crosslinked structure at the same time as the molding. There is a problem that stability is poor, and there are various other problems such as formation of a crosslinked structure during molding, which makes molding impossible.
別の方法としては、成形後のポリウレタン樹脂成形品に
、その表面から架橋剤を浸透させて表面を架橋させる方
法もあるが、この方法では浸透させる架橋剤の量及び種
類に限度があり、又、大型成形品の場合には表面のみが
架橋される為、各種物性の向上が不満足である。更に架
橋剤の浸透には有機溶剤の使用が必要であって、有機溶
剤の使用に基づ（種々の問題が発生する。Another method is to crosslink the surface of the polyurethane resin molded product by infiltrating the surface with a crosslinking agent, but this method has limitations on the amount and type of crosslinking agent that can be infiltrated, and In the case of large molded products, only the surface is crosslinked, so improvements in various physical properties are unsatisfactory. Furthermore, the penetration of the crosslinking agent requires the use of organic solvents, and various problems arise due to the use of organic solvents.
従って、本発明の目的は、成形容易な熱可塑性ポリウレ
タン樹脂から各種物性に優れたポリウレタン樹脂成形品
を容易に提供することが出来るポリウレタン樹脂組成物
及びその成形方法を提供することである。Therefore, an object of the present invention is to provide a polyurethane resin composition and a method for molding the same, which can easily produce polyurethane resin molded articles with excellent various physical properties from an easily moldable thermoplastic polyurethane resin.
（問題点を解決する為の手段） 上記目的は以下の本発明によって達成される。(Means for solving problems) The above objects are achieved by the present invention as described below.
即ち、本発明は、実質上遊離のイソシアネート基を含有
しない熱可塑性ポリウレタン樹脂と、イソシアネート基
と反応性を有する基を２個以上含有する樹脂（以下イソ
シアネート反応性樹脂という）とからなることを特徴と
するポリウレタン樹脂組成物、及び実質上遊離のイソシ
アネート基を含有しない熱可塑性ポリウレタン樹脂と、
イソシアネート反応性樹脂とを混合し、上記ポリウレタ
ン樹脂のポリウレタン結合、アロファネート結合又はビ
ユレット結合が解離してイソシアネート基が生成する温
度条件下で混線及び成形することを特徴とする架橋結合
を有すポリウレタン樹脂の成形方法である。That is, the present invention is characterized in that it consists of a thermoplastic polyurethane resin that does not substantially contain free isocyanate groups, and a resin that contains two or more groups that are reactive with isocyanate groups (hereinafter referred to as isocyanate-reactive resin). a thermoplastic polyurethane resin containing substantially no free isocyanate groups;
A polyurethane resin having a crosslinked bond, which is obtained by mixing a polyurethane resin with an isocyanate-reactive resin, crosslinking and molding the polyurethane resin under temperature conditions such that the polyurethane bonds, allophanate bonds, or billet bonds dissociate to form isocyanate groups. This is a molding method.
（作 用）
ポリウレタン樹脂の成形に際して、ポリウレタン樹脂に
イソシアネート反応性樹脂を添加し、上記ポリウレタン
樹脂のポリウレタン結合、アロファネート結合又はビユ
レット結合が解離してイソシアネート基が生成する温度
条件下で混練及び成形することによって、成形と同時に
上記遊離したイソシアネート基と上記反応性樹脂とが反
応して架橋構造が形成される。(Function) When molding a polyurethane resin, an isocyanate-reactive resin is added to the polyurethane resin, and the polyurethane resin is kneaded and molded under temperature conditions such that the polyurethane bonds, allophanate bonds, or billet bonds dissociate to form isocyanate groups. As a result, the free isocyanate group reacts with the reactive resin simultaneously with molding, and a crosslinked structure is formed.
（好ましい実施態様）
次に好ましい実施態様を挙げて本発明を更に詳しく説明
する。(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.
本発明において使用するポリウレタン樹脂は、実質上遊
離のイソシアネート基を有さない従来公知の熱可塑性ポ
リウレタン樹脂であり、例えば、下記の如き比較的高分
子量の２官能性ポリオール、ポリイソシアネート及び鎖
伸長剤を反応させて得られるポリウレタン樹脂であって
、種々のグレードのものが市場から入手８来、いずれも
本発明において使用することが出来る。The polyurethane resin used in the present invention is a conventionally known thermoplastic polyurethane resin having substantially no free isocyanate groups, and includes, for example, relatively high molecular weight bifunctional polyols, polyisocyanates, and chain extenders such as those described below. Various grades of polyurethane resins are available on the market, and any of them can be used in the present invention.
又、本発明においては上記の熱可塑性ポリウレタン樹脂
において、ＮＧＯ１０Ｆ＋の比を１以下とした完全熱可
塑性の熱可塑性ポリウレタン樹脂が使用出来ると共に、
更に１．５≧ＮＣ０１０Ｈ＞ １である不完全熱可塑性
ポリウレタン樹脂も使用することが出来る。Further, in the present invention, in the above thermoplastic polyurethane resin, a completely thermoplastic thermoplastic polyurethane resin in which the ratio of NGO10F+ is 1 or less can be used, and
Furthermore, incompletely thermoplastic polyurethane resins in which 1.5≧NC010H>1 can also be used.
上記のポリオールとしては、従来公知のものはいずれも
使用出来、例えば、好ましいものとして分子量が５００
〜３，０００の
ポリエチレンアジペート。As the above-mentioned polyol, any conventionally known polyol can be used. For example, a preferable one has a molecular weight of 500.
~3,000 polyethylene adipate.
ポリエチレンプロピレンアジベート、
ポリエチレンブチレンアジベート、
ポリジエチレンアジベート、
ポリブチレンアジペート、
ポリエチレンサクシネート、
ポリブチレンサクシネート、
ポリエチレンセバケート、
ポリブチレンセバケート、
ポリテトラメチレンエーテルグリコール、ポリ−Ｃ−カ
プロラクトンジオール、
ポリへキサメチレンアジペート、
ポリカーボネートポリオール、
ポリブタジェンポリオール、
水添化ポリブタジェンポリオール、
ポリエチレンポリオール、
ポリプロピレングリコール等、及び上言己ポリオール中
に適当な量のポリオキシエチレン鎖を含有するものが挙
げられる。Polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-C-caprolactone diol, Examples include polyhexamethylene adipate, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyethylene polyol, polypropylene glycol, and those containing an appropriate amount of polyoxyethylene chains in the above-mentioned polyol. It will be done.
特に好適なポリオールは、分子量が１，０００〜２，０
００のポリブ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εカプロラクトン、ポリテトラメチルエ
ーテルグリコール及びポリカーボネートポリオールであ
る。Particularly suitable polyols have a molecular weight of 1,000 to 2,0
00 polybutylene adipate polyethylene butylene adipate, poly epsilon caprolactone, polytetramethyl ether glycol and polycarbonate polyol.
又、ポリイソシアネートとしては、従来公知のいずれの
ものも使用出来るが、例えば、好ましいものとして、
４４′−ジフェニルメタンジイソシアネート（ＭＤＩ、
）、
水添化ＭＤＩ。Further, as the polyisocyanate, any conventionally known polyisocyanate can be used, but for example, 44'-diphenylmethane diisocyanate (MDI,
), hydrogenated MDI.
イソホロンジイソシアネート、
１．３−キシリレンジイソシアネート、１．４−キシリ
レンジイソシアネート、２．４−トリレンジイソシアネ
ート、
２．６−）リレンジイソシアネート、
１．５−ナフタリンジイソシアネート、ｍ−フェニレン
ジイソシアネート、
ｐ−フェニレンジイソシアネート
トリジンジイソシアネート等があり、
或いはこれらのポリイソシアネートと低分子量のポリオ
ールやポリアミンとを末端イソシアネートとなる様に反
応させて得られるウレタンプレポリマー等も当然使用す
ることが出来る。Isophorone diisocyanate, 1.3-xylylene diisocyanate, 1.4-xylylene diisocyanate, 2.4-tolylene diisocyanate, 2.6-)lylene diisocyanate, 1.5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene Diisocyanates include toridine diisocyanate, and urethane prepolymers obtained by reacting these polyisocyanates with low molecular weight polyols or polyamines to form terminal isocyanates can also be used.
鎖伸長剤としては従来公知の鎖伸長剤が使用ａ来、例え
ば、好ましいものとしては、
エチレングリコール、
プロピレングリコール。As the chain extender, conventionally known chain extenders can be used. For example, preferred ones include ethylene glycol and propylene glycol.
ジエチレングリコール、
１．４−ブタンジオール、
１．６−ヘキサンジオール、
１．４−シクロヘキサンジメタツール
ｍ−キシリレングリコール
水添化ビスフェノールＡ
１．４−ビス（２−ヒドロキシエトキシ）ベンゼン、
ビス（ヒドロキシエチル）テレフタレート、１．２−プ
ロピレンジアミン、
トリメチレンジアミン、
テトラメチレンジアミン、
ヘキサメチレンジアミン、
デカメチレンジアミン、
イソホロンジアミン、
ｍ−キシリレンジアミン、
ヒドラジン、
水等がある。Diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexane dimetatool m-xylylene glycol hydrogenated bisphenol A 1,4-bis(2-hydroxyethoxy)benzene, bis(hydroxy) Examples include ethyl) terephthalate, 1,2-propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, decamethylene diamine, isophorone diamine, m-xylylene diamine, hydrazine, and water.
以上の如き原料からなるポリウレタン樹脂は、従来公知
の製造方法、例えば、各成分の一括反応方法や、プレポ
リマーを経由するプレポリマー法等によって容易に得る
ことが出来る。A polyurethane resin made from the above-mentioned raw materials can be easily obtained by conventionally known manufacturing methods, such as a batch reaction method of each component, a prepolymer method using a prepolymer, and the like.
本発明のポリウレタン樹脂組成物は、上記の如き熱可塑
性ポリウレタン樹脂に、イソシアネート反応性樹脂を添
加したことを特徴としている。このイソシアネート反応
性樹脂としては、例えば、分子中に２個以上の水酸基、
アミノ基、カルボキシル基等のイソシアネートと反応性
を有する基を有する樹脂であって、具体的にはポリビニ
ルアルコール、ポリ酢酸ビニルの部分鹸化物、エチレン
・酢酸ビニル共重合体、塩化ビニル・酢酸ビニル共重合
体等の酢酸ビニル共重合体の完全又は部分鹸化物、ヒド
ロキシエチル（メタ）アクリレート等の水酸基含有モノ
マーを少なくとも一部使用した各種アクリル樹脂又はそ
の共重合体、末端水酸基含有のポリエステル樹脂、ポリ
エーテル樹脂、セルロース誘導体等、公知の各種樹脂が
挙げられ、特に好適な樹脂は３個以上の水酸基を含有す
る樹脂であり、これらの樹脂はいずれも種々のグレード
のものが市場から容易に入手され、本発明で使用するこ
とが出来る。The polyurethane resin composition of the present invention is characterized by adding an isocyanate-reactive resin to the above thermoplastic polyurethane resin. This isocyanate-reactive resin includes, for example, two or more hydroxyl groups in the molecule,
Resins having groups reactive with isocyanates such as amino groups and carboxyl groups, specifically polyvinyl alcohol, partially saponified polyvinyl acetate, ethylene/vinyl acetate copolymer, vinyl chloride/vinyl acetate copolymer, etc. Fully or partially saponified products of vinyl acetate copolymers such as polymers, various acrylic resins or copolymers thereof using at least a portion of hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate, polyester resins containing terminal hydroxyl groups, polyester resins containing terminal hydroxyl groups, etc. Examples include various known resins such as ether resins and cellulose derivatives, and particularly preferred resins are resins containing three or more hydroxyl groups, and these resins are easily available in various grades on the market. , can be used in the present invention.
上記イソシアネート反応性樹脂の使用量は、該樹脂の水
酸基の個数や分子量によって一概には決定８来ないが、
通常は前記熱可塑性ポリウレタン樹脂１００重量部に対
して１〜５０重量部の割合で使用するのが好適である。The amount of the above-mentioned isocyanate-reactive resin to be used cannot be unconditionally determined depending on the number of hydroxyl groups and molecular weight of the resin, but
Usually, it is suitable to use it in a proportion of 1 to 50 parts by weight per 100 parts by weight of the thermoplastic polyurethane resin.
両者の混合方法は任意であり、単なるブレンドでもよい
。The mixing method for both may be arbitrary, and simple blending may be used.
本発明の成形方法は、前記の如き実質上遊離のイソシア
ネート基を含有しない熱可塑性ポリウレタン樹脂に、前
記の如きイソシアネート反応性樹脂を添加混合し、上記
ポリウレタン樹脂のポリウレタン結合、アロファネート
結合又はビユレット結合が解離してイソシアネート基が
生成する温度条件下で混線及び成形することを特徴とす
る。The molding method of the present invention includes adding and mixing the above-mentioned isocyanate-reactive resin to the above-mentioned thermoplastic polyurethane resin that does not substantially contain free isocyanate groups, so that the polyurethane bonds, allophanate bonds, or billet bonds of the above-mentioned polyurethane resin are dissolved. It is characterized in that it is mixed and molded under temperature conditions that dissociate to produce isocyanate groups.
即ち、ポリウレタン樹脂は分子中にウレタン結合、アロ
ファネート結合、ビユレット結合等を有しており、これ
らの基は特定の温度以上になると解離してイソシアネー
ト基を生成すること及び冷却すると生成したイソシアネ
ート基が元のウレタン結合等に復帰することは公知であ
るが、この際ポリウレタン樹脂にイソシアネート反応性
多官能樹脂を混合しておくことによって、上言己遊離し
たイソシアネート基がこれらの多官能樹脂と反応して架
橋結合を生じることを見出した。That is, polyurethane resins have urethane bonds, allophanate bonds, billet bonds, etc. in their molecules, and these groups dissociate to produce isocyanate groups when the temperature exceeds a certain level, and when cooled, the produced isocyanate groups It is known that the original urethane bonds are restored, but at this time, by mixing an isocyanate-reactive polyfunctional resin with the polyurethane resin, the self-liberated isocyanate groups react with these polyfunctional resins. It was found that cross-linking occurs when
成形方法は、ポリウレタン樹脂が一旦溶融する状態を経
る限り、従来公知の押比し成形、射出成形、詩形、２色
成形等公知の方法でよく特に限定されない。又、成形条
件としては、使用するポリウレタン樹脂によっである程
度変化するが、例えば、１２０〜２７０℃程度の温度が
よ（、加圧は必須ではなく、成形時のいずれの加圧条件
でもよい。The molding method is not particularly limited, and may be any conventionally known method such as extrusion molding, injection molding, cylindrical molding, or two-color molding, as long as the polyurethane resin is once melted. Further, the molding conditions vary to some extent depending on the polyurethane resin used, but for example, the temperature is about 120 to 270°C (pressure is not essential, and any pressure conditions during molding may be used).
又、成形品の形状はブロック状、フィルム状等任意であ
り、例えば、射出成形法によるボールジヨイント類、各
種ブツシュ、各種ダストカバー、各種ショックアブソー
バ−、ブレーキストッパー類、０−リング類、給油リン
グ類、板バネのスペーサー、ドアロックストライカ−１
各種ギアー類、パツキン類、シール材、プレート材、ピ
ッカー、ＫＰホルダー、ウレタンボール類、各種キャス
ター類、スラストワッシャー、チューナ一部品、水道水
給水栓、各種スポーツシューズの靴底材、各種リフト、
ヒールトップ類、スキーのグリップ材、スノーモービル
用スプロケット、キャタピラ−類、軍靴及び安全靴等の
靴底材、ゴルフボール、ベルト類、ガスケット、プラグ
類、ソケット類等、又、押圧成形法による各種コンベア
ベルト類、水容器、醸造用容器、フレキシブルコンテナ
ー類、モーター油用・煮沸用小袋、粉粒体の輸送用シー
ト、各種カッパ類、衣類、各種テープ類の如きフィルム
押出加工物、インフレーション加工物や各種チューブ類
、各種ホース類の如きチューブ押出加工物や、地下ケー
ブル、海底ケーブル、電力・通信ケーブル類、リード線
、コンピューター配線、自動車配線、各種エナメル線等
の被覆押出加工物や、各種ベルト類のベルト押出加工物
等が挙げられる。The shape of the molded product can be arbitrary, such as block or film, such as ball joints made by injection molding, various bushes, various dust covers, various shock absorbers, brake stoppers, O-rings, and oil supply. Rings, leaf spring spacer, door lock striker-1
Various gears, packings, sealing materials, plate materials, pickers, KP holders, urethane balls, various casters, thrust washers, tuner parts, tap water faucets, sole materials for various sports shoes, various lifts,
Heel tops, ski grip materials, sprockets for snowmobiles, caterpillars, sole materials for military boots and safety shoes, golf balls, belts, gaskets, plugs, sockets, etc., and various products made by press molding. Conveyor belts, water containers, brewing containers, flexible containers, motor oil and boiling bags, sheets for transporting powder and granules, various raincoats, clothing, film extrusion products such as various tapes, and inflation products. tube extrusion products such as various tubes, various hoses, covered extrusion products such as underground cables, submarine cables, power/communication cables, lead wires, computer wiring, automobile wiring, various enameled wires, and various belts. Examples include belt extrusion products of the same type.
（実施例）
次に、実施例及び比較例を挙げて本発明を更に具体的に
説明する。尚、文中部又は％とあるのは特に断りの無い
限り重量基準である。(Example) Next, the present invention will be described in more detail by giving examples and comparative examples. It should be noted that unless otherwise specified, the terms in the text or % are based on weight.
実施例１
ポリカーボネート系ＭＤＩベース熱可塑性ポリウレタン
樹脂（ＮＧＯ１０Ｈ＝１．１５１１００部に、エチレン
・酢酸ビニル（酢酸ビニル４０モル％含有）共重合体の
酢酸ビニル２モル％鹸化物１０部を混合して本発明のポ
リウレタン樹脂組成物を得た。Example 1 10 parts of a 2 mol% vinyl acetate saponified product of an ethylene/vinyl acetate (containing 40 mol% vinyl acetate) copolymer was mixed with 100 parts of a polycarbonate MDI-based thermoplastic polyurethane resin (NGO10H=1.151). A polyurethane resin composition of the invention was obtained.
この組成物を１５０〜１７０℃で射出成形機によりＵ字
状パツキンを成形した。一方、比較の目的で原料として
使用した熱可塑性ポリウレタン樹脂を単独で同一条件で
同一の成形物を成形し、それらの常態物性を測定した結
果を下記第１表に、圧縮永久歪試験結果を第２表に示し
た。This composition was molded into a U-shaped packing using an injection molding machine at 150 to 170°C. On the other hand, for comparison purposes, the thermoplastic polyurethane resin used as a raw material was molded into the same molded products under the same conditions, and the normal state physical properties of the products were measured. Table 1 below shows the results of the compression set test. It is shown in Table 2.
（以下余白）
第
表
１）圧縮永久歪試験条件：
１３Φ×２ｔ１
３０％
圧縮
第
表
１）試験片の形状：Ｕ字パツキンを切削して、断面を４
．５ｍｍ角にしたものを１インチの長さに切って試験片
とした。(Leaving space below) Table 1) Compression set test conditions: 13Φ
．． A 5 mm square piece was cut into 1 inch length to prepare a test piece.
２）圧縮率＝２２〜２４％の圧縮
（発明の効果）
以上の様に本発明によれば、成形原料は各成分が相互に
反応せず安定しているので、取り扱い容易で且つ長期間
保存可能である。2) Compression ratio = 22-24% compression (effects of the invention) As described above, according to the present invention, the molding raw materials are stable because the components do not react with each other, so they are easy to handle and can be stored for a long time. It is possible.
又、成形に際しては単に成形するのみで、成形性の良好
な熱可塑性ポリウレタン樹脂から、各種物性、例えば、
耐熱性、耐溶剤性、破断強度、伸度、モジュラス、永久
圧縮歪等の各種物性に優れた架橋ポリウレタン樹脂成形
品が極めて容易に得られる。In addition, when molding, by simply molding, various physical properties such as thermoplastic polyurethane resin with good moldability can be obtained.
Cross-linked polyurethane resin molded products having excellent physical properties such as heat resistance, solvent resistance, breaking strength, elongation, modulus, and permanent compression set can be obtained very easily.
又、イソシアネート反応性樹脂として任意の樹脂が使用
出来るので、用途に応じた適切な物性の成形材料及び成
形品が提供される。Moreover, since any resin can be used as the isocyanate-reactive resin, molding materials and molded products with appropriate physical properties depending on the application can be provided.
Claims (5)
塑性ポリウレタン樹脂と、イソシアネート基と反応性を
有する基を２個以上含有する樹脂とからなることを特徴
とするポリウレタン樹脂組成物。(1) A polyurethane resin composition comprising a thermoplastic polyurethane resin that does not substantially contain free isocyanate groups and a resin that contains two or more groups that are reactive with isocyanate groups.
請求項１に記載のポリウレタン樹脂組成物。(2) The polyurethane resin composition according to claim 1, wherein the group reactive with the polyurethane resin is a hydroxyl group.
塑性ポリウレタン樹脂と、イソシアネート基と反応性を
有する基を２個以上含有する樹脂とを混合し、上記ポリ
ウレタン樹脂のポリウレタン結合、アロファネート結合
又はビュレット結合が解離してイソシアネート基が生成
する温度条件下で混練及び成形することを特徴とする架
橋結合を有すポリウレタン樹脂の成形方法。(3) A thermoplastic polyurethane resin that does not substantially contain free isocyanate groups and a resin that contains two or more groups that are reactive with isocyanate groups are mixed, and the polyurethane bond, allophanate bond, or bullet bond of the above polyurethane resin is formed. 1. A method for molding a polyurethane resin having crosslinked bonds, the method comprising kneading and molding under temperature conditions such that isocyanate groups are dissociated to form isocyanate groups.
請求項３に記載の成形方法。(4) The molding method according to claim 3, wherein the group reactive with the polyurethane resin is a hydroxyl group.
に記載の成形方法。(5) Claim 3, wherein the temperature during molding is 120 to 270°C.
The molding method described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2125337A JPH0423823A (en) | 1990-05-17 | 1990-05-17 | Polyurethane resin composition and molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2125337A JPH0423823A (en) | 1990-05-17 | 1990-05-17 | Polyurethane resin composition and molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0423823A true JPH0423823A (en) | 1992-01-28 |
Family
ID=14907619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2125337A Pending JPH0423823A (en) | 1990-05-17 | 1990-05-17 | Polyurethane resin composition and molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0423823A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002336386A (en) * | 2001-05-17 | 2002-11-26 | Bridgestone Sports Co Ltd | Method of manufacturing golf ball |
| JP2003000764A (en) * | 2001-06-25 | 2003-01-07 | Bridgestone Sports Co Ltd | Two-piece sold golf ball |
| WO2010113888A1 (en) * | 2009-03-30 | 2010-10-07 | 株式会社クラレ | Resin composition and multi-layered structure |
| CN107353627A (en) * | 2017-08-10 | 2017-11-17 | 福建师范大学 | A kind of TPU/ dendritic phthalocyanines load SiO with photocatalysis effect2Composite wire and preparation method thereof |
-
1990
- 1990-05-17 JP JP2125337A patent/JPH0423823A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002336386A (en) * | 2001-05-17 | 2002-11-26 | Bridgestone Sports Co Ltd | Method of manufacturing golf ball |
| JP2003000764A (en) * | 2001-06-25 | 2003-01-07 | Bridgestone Sports Co Ltd | Two-piece sold golf ball |
| WO2010113888A1 (en) * | 2009-03-30 | 2010-10-07 | 株式会社クラレ | Resin composition and multi-layered structure |
| CN107353627A (en) * | 2017-08-10 | 2017-11-17 | 福建师范大学 | A kind of TPU/ dendritic phthalocyanines load SiO with photocatalysis effect2Composite wire and preparation method thereof |
| CN107353627B (en) * | 2017-08-10 | 2020-04-28 | 福建师范大学 | TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2Composite wire and preparation method thereof |
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