JPH02102215A - Moisture-curable urethane prepolymer composition and moisture-curable fixing material for medical use - Google Patents
Moisture-curable urethane prepolymer composition and moisture-curable fixing material for medical useInfo
- Publication number
- JPH02102215A JPH02102215A JP63255551A JP25555188A JPH02102215A JP H02102215 A JPH02102215 A JP H02102215A JP 63255551 A JP63255551 A JP 63255551A JP 25555188 A JP25555188 A JP 25555188A JP H02102215 A JPH02102215 A JP H02102215A
- Authority
- JP
- Japan
- Prior art keywords
- urethane prepolymer
- moisture
- weight
- curable
- parts
- 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 title claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- -1 diisocyanate compound Chemical class 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 7
- 239000011342 resin composition Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 24
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 20
- 230000000399 orthopedic effect Effects 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 150000003077 polyols Chemical class 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000011505 plaster Substances 0.000 abstract 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 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 2
- 238000001356 surgical procedure Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000004744 fabric Substances 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002518 antifoaming agent Substances 0.000 description 12
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- 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 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000834 fixative Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000013008 moisture curing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- CEOCVKWBUWKBKA-UHFFFAOYSA-N 2,4-dichlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1Cl CEOCVKWBUWKBKA-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- GPZXFICWCMCQPF-UHFFFAOYSA-N 2-methylbenzoyl chloride Chemical compound CC1=CC=CC=C1C(Cl)=O GPZXFICWCMCQPF-UHFFFAOYSA-N 0.000 description 1
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- WOGITNXCNOTRLK-UHFFFAOYSA-N 3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)C=CC1=CC=CC=C1 WOGITNXCNOTRLK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NTQYXUJLILNTFH-UHFFFAOYSA-N nonanoyl chloride Chemical compound CCCCCCCCC(Cl)=O NTQYXUJLILNTFH-UHFFFAOYSA-N 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 210000002268 wool Anatomy 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、塗料、接着剤等として利用することができる
。貯蔵安定性に優れ、かつ、水中に浸漬した後の硬化速
度が適度な湿気硬化型ウレタンプレポリマー組成物およ
び該ウレタンプレポリマー組成物を網状支持体に含浸さ
せて整形外科用ギプス包帯として利用することができる
貯蔵安定性に優れ、かつ2手頃な硬化速度を有する医療
用固定材に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention can be used as a paint, an adhesive, and the like. Moisture-curing urethane prepolymer composition with excellent storage stability and moderate curing speed after immersion in water, and use as an orthopedic cast bandage by impregnating a mesh support with the urethane prepolymer composition The present invention relates to a medical fixative having excellent storage stability and a reasonable curing speed.
(従来の技術)
湿気硬化型ウレタンプレポリマー組成物は、塗料、接着
剤等として利用される他に、近年、ガラス布、ポリエス
テル布等の網状支持体に担持させることにより整形外科
用ギプス包帯などの医療用固定材としての利用が活発化
している。(Prior Art) Moisture-curable urethane prepolymer compositions are used as paints, adhesives, etc., and in recent years, they have been applied to orthopedic cast bandages by supporting them on net-like supports such as glass cloth and polyester cloth. is increasingly being used as a medical fixative.
中でも整形外科用ギプス包帯としての必須要件は以下
■水中に浸漬して湿潤させたものを患部にセットした後
、適度な時間で硬化すること
■硬化後のギプス包帯が適度の強度を有すること■ギプ
ス包帯として製品を長期に保管しておいても製品に変化
、劣化が生じないこと
などがあげられる。The following are the essential requirements for an orthopedic cast bandage: - It must be moistened by soaking it in water and set on the affected area, and then harden in an appropriate amount of time. - The cast bandage must have appropriate strength after hardening. The product does not change or deteriorate even if it is stored as a cast bandage for a long period of time.
上記必須要件のうち■はウレタンプレポリマーの分子構
造を工夫することにより以前から処方が確立されている
が、必須要件である■と■は言わば相反する性質である
ため十分に要求を満たしていないものがほとんであり、
ウレタンプレポリマーのメーカー、医療用固定材メーカ
ー、医用品ディーラー1医院等で在庫、保管している最
中に製品形態が変化し、使用に耐えなくなる場合が極め
て多い。Among the above essential requirements, ■ has been formulated for some time by devising the molecular structure of the urethane prepolymer, but the essential requirements ■ and ■ have contradictory properties, so the requirements are not fully met. Most things are
It is extremely common for products to change shape and become unusable while being stocked and stored by urethane prepolymer manufacturers, medical fixing material manufacturers, medical supplies dealers, and clinics.
具体的な製品形態の変化としては、在庫、保管中にガラ
ス布、ポリエステル布等に担持されたウレタンプレポリ
マー組成物が固化してしまう場合がほとんである。As for specific changes in product form, in most cases the urethane prepolymer composition supported on glass cloth, polyester cloth, etc. solidifies during inventory and storage.
それは、包装が不十分であり、空気中の湿分を吸収して
整形外科用ギプス包帯として使用する前に固化している
こともあるが、必須要件■を満たすことを目的として硬
化触媒の添加量を増加し、その結果、在庫、貯蔵保管中
にウレタンプレポリマー中でアロハネート反応の進行速
度が増し、自己重合のために固化してしまう場合かはと
んである。It may be poorly packaged, absorb moisture in the air and harden before being used as an orthopedic cast dressing, but the addition of a curing catalyst aims to meet the essential requirements ■ If the amount is increased, the rate of progress of the allophanate reaction in the urethane prepolymer increases during inventory and storage, resulting in solidification due to self-polymerization.
(発明の目的)
本発明の目的は、整形外科用ギプス包帯としての前記の
必須要件■を満足させることはもちろんのこと、従来製
品に欠除している■と■の相反する性質に起因する要件
をも同時に満足させ得る湿気硬化型ウレタンプレポリマ
ー組成物および医療用固定材を提供することにある。(Objective of the Invention) The object of the present invention is not only to satisfy the above-mentioned essential requirement (■) as an orthopedic cast bandage, but also to satisfy the contradictory characteristics (■) and (2) which are lacking in conventional products. It is an object of the present invention to provide a moisture-curable urethane prepolymer composition and a medical fixing material that can simultaneously satisfy these requirements.
(発明の構成)
すなわち1本発明は
「(1)ジイソシアネート化合物とポリオール化合物か
らなる末端に−NCO基を有するウレタンプレポリマー
と下記化学構造
を有するジモルホリノトリエチルエーテルを硬化触媒と
して含有することを特徴とする湿気硬化型ウレタンプレ
ポリマー組成物」
および
「(2)ジイソシアネート化合物とポリオール化合物か
らなる末端に−NCO基を有するウレタンプレポリマー
と下記化学構造
を有するジモルホリノトリエチルエーテルを硬化触媒と
して含有する樹脂組成物が網状支持体に担持されている
ことを特徴とする湿気硬化型医療用固定材」
である。(Structure of the Invention) That is, 1. The present invention is characterized in that: (1) it contains a urethane prepolymer having an -NCO group at the end, which is composed of a diisocyanate compound and a polyol compound, and dimorpholinotriethyl ether having the following chemical structure as a curing catalyst. and (2) a resin containing a urethane prepolymer having an -NCO group at the terminal consisting of a diisocyanate compound and a polyol compound and dimorpholinotriethyl ether having the following chemical structure as a curing catalyst. A moisture-curable medical fixing material characterized in that the composition is supported on a net-like support.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
まず、ウレタンプレポリマー組成物の中の主要な樹脂成
分であるウレタンプレポリマーを構成する一方の化合物
であるジイソシアネート化合物について述べる。First, the diisocyanate compound, which is one of the compounds constituting the urethane prepolymer, which is the main resin component in the urethane prepolymer composition, will be described.
本発明の湿気硬化型ウレタンプレポリマー組成物および
湿気硬化型医療用固定材に用い得るジイソシアネート化
合物の分子構造は特に制限されることは無いが、中でも
芳香、族ジイソシアネート化合物が好適である。The molecular structure of the diisocyanate compound that can be used in the moisture-curing urethane prepolymer composition and moisture-curing medical fixing material of the present invention is not particularly limited, but aromatic and group diisocyanate compounds are particularly preferred.
芳香族ジイソシアネート化合物の具体的な例としては2
.4−)ルエンジイソシアネート、2゜6−トルエンジ
イソシアネート、それらの異性体混合物、2.4−ジフ
ェニルメタンジイソシアネート、1,4−ジフェニルメ
タンジイソシアネート、2.2−−ジフェニルメタンジ
イソシアネ)、4.4°−ジフェニルメタンジイソシア
ネートおよびそれらの混合物などがある。Specific examples of aromatic diisocyanate compounds include 2
.. 4-) toluene diisocyanate, 2°6-toluene diisocyanate, isomer mixtures thereof, 2.4-diphenylmethane diisocyanate, 1,4-diphenylmethane diisocyanate, 2.2-diphenylmethane diisocyanate), 4.4°-diphenylmethane These include diisocyanates and mixtures thereof.
その中でも4.4′−ジフェニルメタンジイソシアネー
トを用いるのが特に好ましい。Among them, it is particularly preferable to use 4,4'-diphenylmethane diisocyanate.
ウレタンプレポリマーを構成するもう一方の化合物であ
るポリオール化合物としては
第1級ヒドロキシル基を有するポリオールが特に好適で
ある。As the other polyol compound constituting the urethane prepolymer, a polyol having a primary hydroxyl group is particularly suitable.
第1級ヒドロキシル基を有するポリオールの具体的な例
としてはポリテトラメチレンオキシドグリコール、ポリ
プロピレングリコール、ポリエチレングリコール、ポリ
エステルポリオール(ポリカプロラクトンポリオールな
ど)が挙げられる。Specific examples of polyols having primary hydroxyl groups include polytetramethylene oxide glycol, polypropylene glycol, polyethylene glycol, and polyester polyols (such as polycaprolactone polyol).
中でも価格2種々のグレードのものが量産されており、
入手のし易いことなどから、ポリプロピレングリコール
が特に好ましい。Among them, two grades of various prices are mass-produced,
Polypropylene glycol is particularly preferred because it is easily available.
このポリオール化合物の中でも、1分子中に2個の水酸
基を有し、かつ数平均分子量が400〜2500の範囲
にあるもの、または1分子中に3個の水酸基を有しかつ
数平均分子量が400〜2500の範囲にあるものを混
合し、1分子当りの平均水酸基数が2以上、2.5以下
になるよう調合したものが特に好ましい。Among these polyol compounds, those having two hydroxyl groups in one molecule and a number average molecular weight in the range of 400 to 2,500, or those having three hydroxyl groups in one molecule and a number average molecular weight in the range of 400 to 2,500. Particularly preferred are those in the range of 2,500 to 2,500, prepared so that the average number of hydroxyl groups per molecule is 2 or more and 2.5 or less.
従って、1分子中に2個の水酸基を有し、かつ数平均分
子量が400〜2500の範囲にあるものを単独で使用
することも可能である。Therefore, it is also possible to use alone one having two hydroxyl groups in one molecule and having a number average molecular weight in the range of 400 to 2,500.
ここで1分子当りの平均水酸基が2未満の場合には、ウ
レタンプレポリマーの末端に必ずしもインシアネート基
が存在するとは限らないために水との反応による分子の
伸長に制限が加えられることにより、長鎖の分子構造を
取ることができなくなる。If the average hydroxyl group per molecule is less than 2, inocyanate groups are not necessarily present at the ends of the urethane prepolymer, which limits the elongation of the molecule due to reaction with water. It becomes impossible to form long-chain molecular structures.
従って水との反応による硬化終了後のポリマーは塗料、
接着剤、整形外科用ギプス包帯として適用した場合には
十分な強度を発現することができず使用に耐えない。Therefore, the polymer after curing due to reaction with water can be used as a paint.
When applied as an adhesive or an orthopedic cast bandage, it cannot exhibit sufficient strength and cannot withstand use.
一方、ポリオール化合物の1分子当りの平均水酸基数が
2.0を超える場合には、得られたウレタンプレポリマ
ーと水との反応によって網目構造を形成する部分が生じ
、この網目構造が増えるに従って次第に硬さを増して行
く。On the other hand, when the average number of hydroxyl groups per molecule of the polyol compound exceeds 2.0, the reaction between the obtained urethane prepolymer and water causes parts that form a network structure, and as the network structure increases, the number of hydroxyl groups gradually increases. It will increase in hardness.
このようにして、ポリプロピレングリコールの1分子当
りの平均水酸基数が2.5を超えてくると、逆に構成分
子中の網目構造がかなりの数を占めてくるために、セグ
メントの長さが短くなりすぎ、硬さの増加とともにもろ
さの発現が目立ち始め、塗料、接着剤、整形外科用ギプ
ス包帯等として利用する場合には適当ではなくなる。In this way, when the average number of hydroxyl groups per molecule of polypropylene glycol exceeds 2.5, on the contrary, the network structure in the constituent molecules occupies a considerable number, and the length of the segment becomes short. If the material becomes too stiff, brittleness becomes noticeable as the hardness increases, making it unsuitable for use as paint, adhesive, orthopedic cast bandage, etc.
硬化触媒と貯蔵安定剤とを上記のようなウレタンプレポ
リマーに対しそれぞれ0.1〜2.0重量部添加するこ
とによって本発明ウレタンプレポリマー組成物が調整さ
れる。The urethane prepolymer composition of the present invention is prepared by adding 0.1 to 2.0 parts by weight of a curing catalyst and a storage stabilizer, respectively, to the urethane prepolymer as described above.
本発明の湿気硬化型ウレタンプレポリマー組成物を特に
整形外科用ギプス包帯として利用する場合には、ポリオ
ール化合物とジイソシアネート化合物とを末端−NCO
基が7〜15%の範囲になるように反応させると適度な
強度、ねばりを有しているグレードのものが得られる。When the moisture-curable urethane prepolymer composition of the present invention is used particularly as an orthopedic cast bandage, the polyol compound and the diisocyanate compound are combined with a terminal -NCO
If the reaction is carried out so that the group content is in the range of 7 to 15%, a grade having appropriate strength and tenacity can be obtained.
−NCO基が7〜15重量%の範囲にあるウレタンプレ
ポリマーを合成する際に、ポリオール化合物の数平均分
子量が400以下のものを使用すると、ウレタンプレポ
リマーの粘度が上昇しすぎるために網状体に含浸させに
くくなるという欠点を生じる。When synthesizing a urethane prepolymer containing -NCO groups in the range of 7 to 15% by weight, if a polyol compound with a number average molecular weight of 400 or less is used, the viscosity of the urethane prepolymer increases too much, resulting in a network formation. This results in the disadvantage that it becomes difficult to impregnate.
このものを仮に含浸させることができたとしても、水と
の反応による硬化物は硬く、もろすぎるために、塗料、
接着剤、整形外科用ギプス包帯等の使用には適さない。Even if it were possible to impregnate this material, the cured product caused by the reaction with water would be too hard and brittle, so paints,
Not suitable for use with adhesives, orthopedic plaster bandages, etc.
逆に、ポリオール化合物の数平均分子量が2500以上
のものを使用し、−NCO基が7〜15重量%の範囲に
あるウレタンプレポリマーは、粘度が低くなりすぎるた
めに塗工量が確保できず、十分なバインダー効果の発現
を期待できない。On the other hand, when using a polyol compound with a number average molecular weight of 2,500 or more and a urethane prepolymer containing -NCO groups in the range of 7 to 15% by weight, the viscosity becomes too low, making it difficult to secure a coating amount. , a sufficient binder effect cannot be expected.
仮に整形外科用ギプス包帯として、ガラス繊維布などに
含浸したとしても、包装後、貯蔵保管中及び運搬中に液
ブレが生じ、使用にたえなくなる。Even if glass fiber cloth or the like is impregnated as an orthopedic cast bandage, liquid will bleed during packaging, storage, and transportation, making it unusable.
さらに水との反応による硬化物は硬さが十分でなくギプ
ス包帯として患部を固定するという役割を果たすことは
できない。Furthermore, the hardened product resulting from the reaction with water is not sufficiently hard and cannot serve the role of fixing the affected area as a cast bandage.
本発明の水酸基数調整による調合の効果としては、官能
基数を調整してやることによって、同一の−NCO基含
有数(本発明においては7〜15重量%)のプレポリマ
ーであっても、
(1)粘度の調整が可能になり、所望の粘度のものが得
られる
(2)硬化塗膜の硬さ及び強度の調整が可能になる
ことがあげられる。The effect of the formulation by adjusting the number of hydroxyl groups of the present invention is that by adjusting the number of functional groups, even if the prepolymer has the same -NCO group content (7 to 15% by weight in the present invention), (1) The viscosity can be adjusted to obtain a desired viscosity (2) The hardness and strength of the cured coating film can be adjusted.
本発明の湿気硬化型ウレタンプレポリマー組成物および
湿気硬化型医療用固定材に用いられる硬化触媒であるジ
モルホリノトリエチルエーテルは以下のような化学構造
を有しており、モルホリンとトリエチレングリコールを
例えば、Cu−Ni−Pt族元素からなる触媒存在下で
脱水縮合反応させて製造することができる(例えば、特
開昭62−149647号公報など参照)。Dimorpholinotriethyl ether, which is a curing catalyst used in the moisture-curable urethane prepolymer composition and moisture-curable medical fixative of the present invention, has the following chemical structure, and contains morpholine and triethylene glycol, for example. , can be produced by dehydration condensation reaction in the presence of a catalyst consisting of a Cu--Ni--Pt group element (see, for example, JP-A-62-149647).
なお2モルホリンはジェタノールアミンと硫酸を過熱反
応させることによって製造することができる。Note that 2-morpholine can be produced by subjecting jetanolamine and sulfuric acid to a superheated reaction.
この硬化触媒をウレタンプレポリマーに対して0.1〜
2重量部添加すると良い。Add this curing catalyst to the urethane prepolymer at a rate of 0.1~
It is recommended to add 2 parts by weight.
触媒とともに本発明に用いる貯蔵安定剤として酸クロラ
イド化合物を添加することによりウレタンプレポリマー
の貯蔵安定性を増すことができる。The storage stability of the urethane prepolymer can be increased by adding an acid chloride compound as a storage stabilizer used in the present invention together with a catalyst.
酸クロライド化合物の具体的な例としては以下のものが
ある。Specific examples of acid chloride compounds include the following.
例えば塩化イソフタロイル、塩化2−エチルヘキサイノ
イル、塩化オクタノイル、塩化−クロロベンゾイル、塩
化ベンゾイル、塩化ステプロイル、塩化セバコイル、塩
化デカノイル、塩化ドデカノイル、塩化ノナノイル、塩
化バルミトイル、塩化3−フェニルプロペノイル、塩化
n−ブタノイル、塩化ヘキサノイル、塩化2−メチルプ
ロパノイル、2.4−ジクロロ塩化ベンゾイル、2,6
−ジク0口塩化ベンゾイル、塩化ラウロイル、メチル塩
化ベンゾイル等である。For example, isophthaloyl chloride, 2-ethylhexinoyl chloride, octanoyl chloride, chlorobenzoyl chloride, benzoyl chloride, steproyl chloride, sebacoyl chloride, decanoyl chloride, dodecanoyl chloride, nonanoyl chloride, balmitoyl chloride, 3-phenylpropenoyl chloride, n chloride -butanoyl, hexanoyl chloride, 2-methylpropanoyl chloride, 2,4-dichlorobenzoyl chloride, 2,6
- Diku0 benzoyl chloride, lauroyl chloride, methyl benzoyl chloride, etc.
上記の酸クロライド化合物のうちの1種又は2種以上の
組み合わせで用いることが可能である。It is possible to use one kind or a combination of two or more kinds of the above acid chloride compounds.
酸クロライド化合物の添加量がウレタンプレポリマー1
00重量部に対して0.1重量部より少ない場合には、
塗工、包装等の過程でわずかな空気中の湿分と反応して
しまい、貯蔵安定剤としての効果が失われるために貯蔵
安定性付与効果が発揮されない。The amount of acid chloride compound added is 1 of urethane prepolymer.
If it is less than 0.1 part by weight per 00 parts by weight,
During the coating, packaging, etc. process, it reacts with a small amount of moisture in the air and loses its effect as a storage stabilizer, so it cannot exhibit its storage stability imparting effect.
また空気中の湿分に十分に注意を払って処理した場合で
も効果は見られなかった。Moreover, no effect was observed even when treatment was performed with sufficient attention paid to the moisture in the air.
逆に酸クロライド化合物の添加量が2.0重量部より多
い場合には、貯蔵安定剤は優れた効果をもたらすものの
、使用時の水との反応による効果速度が違いすぎるため
に、塗料、接着剤、整形外科用ギプス包帯として使用す
る場合の作業性が悪い、さらに酸クロライド化合物独特
の刺激臭が発生し、作業に悪影響を及ぼすことにもなる
。On the other hand, if the amount of acid chloride compound added is more than 2.0 parts by weight, although the storage stabilizer has excellent effects, the rate of effect due to the reaction with water during use is too different, resulting in poor performance in paints, adhesives, etc. It has poor workability when used as an agent or orthopedic cast bandage, and it also generates a pungent odor unique to acid chloride compounds, which has a negative impact on work.
又湿気硬化型ウレタンプレポリマー組成物は、水分と反
応して高分子化してゆく反応に伴って炭酸ガスを生成す
るため、塗料、接着剤、整形外科用ギプス包帯等に使用
する際、樹脂が発泡して強度低下を引き起こしたり、外
観上の汚点となったりする場合がある。この炭酸ガスの
発生による発泡を押える方法としては、シリコン系の消
泡剤をウレタンプレポリマーに対して0.01〜1.0
重量部添加することで満足される。このシリコン系消泡
剤は、常に用いるというのではなく、その時々のケース
に合わせて用いれば良い。In addition, moisture-curable urethane prepolymer compositions generate carbon dioxide gas as they react with moisture and become polymerized, so when used in paints, adhesives, orthopedic cast bandages, etc., the resin may It may foam and cause a decrease in strength or cause a blemish on the appearance. As a method of suppressing foaming caused by the generation of carbon dioxide gas, a silicone-based antifoaming agent is added to the urethane prepolymer at a concentration of 0.01 to 1.0%.
It is satisfied by adding part by weight. This silicone antifoaming agent is not always used, but may be used depending on the case.
次に前記操作により、硬化触媒、貯蔵安定剤、消泡剤等
を配合した湿気硬化型ウレタンプレポリマー組成物を整
形外科用ギプス包帯として利用する場合のことを述べる
。Next, a case will be described in which a moisture-curable urethane prepolymer composition containing a curing catalyst, a storage stabilizer, an antifoaming agent, etc. is used as an orthopedic cast bandage by the above-mentioned operation.
前記各種の添加剤を配合した後・のウレタンプレポリマ
ー組成物をガラス、ポリエステル、ケブラ、ポリアラミ
ド、セラミック、ホウ素、ステンレスウール等の繊維か
らなる布、網状体等に含浸させ、空気中の湿分から保護
すべく包装する。The urethane prepolymer composition after blending with the various additives mentioned above is impregnated into a cloth, net, etc. made of fibers such as glass, polyester, Kevlar, polyaramid, ceramic, boron, stainless wool, etc., and is removed from moisture in the air. Pack for protection.
包装材料としては、アルミとプラスチックのうミネート
フィルムなどが好適である。Suitable packaging materials include aluminum and plastic laminate films.
使用の際には湿気硬化型ウレタンプレポリマーを含浸さ
せた布、又は網状体などを包装を破って取り出した後水
中に浸漬し、速やかに患部に巻きつけ、ウレタンプレポ
リマー組成物が硬化し強度が発現してくるまで静置して
おくことによって患部が固定される。When in use, tear a cloth or mesh impregnated with moisture-curable urethane prepolymer, tear the packaging, take it out, soak it in water, and immediately wrap it around the affected area to harden the urethane prepolymer composition and increase its strength. The affected area is fixed by leaving it as it is until it appears.
なお、布または網状体など基布に対するウレタンプレポ
リマー組成物の含浸量は基布の重量を100としたとき
30〜300の範囲が望ましい。The amount of the urethane prepolymer composition impregnated into the base fabric such as cloth or net-like material is preferably in the range of 30 to 300% when the weight of the base fabric is 100%.
30より少ない場合は基布へのバインダー効果が十分で
なく必要な強度を保持できない。When it is less than 30, the binder effect on the base fabric is insufficient and the necessary strength cannot be maintained.
また、300より多い場合は、含浸時に液ダレを起こし
たり、包装後保管中および運搬中に包装材料内底部に樹
脂だまりができて適当でない。On the other hand, if it is more than 300, liquid may drip during impregnation, or a resin pool may form at the inner bottom of the packaging material during storage and transportation after packaging, which is not appropriate.
さらに、水中に浸漬したときに内部まで水が浸入しにく
いために硬化時間が長くなって患者を長い時間待たせる
ことになったり、硬化時に発生する炭酸ガスの脱離が悪
くなり、発泡の原因になったりするので好ましくない。Furthermore, when immersed in water, it is difficult for water to penetrate into the interior, which lengthens the curing time, forcing patients to wait for a long time, and the desorption of carbon dioxide generated during curing becomes difficult, causing foaming. This is not desirable as it may cause
また、材料の無駄となる。Also, material is wasted.
本発明の湿気硬化型ウレタンプレポリマー組成物および
湿気硬化型医療用固定材の具体的実施態様としては以下
のようなものがある。Specific embodiments of the moisture-curable urethane prepolymer composition and moisture-curable medical fixative of the present invention are as follows.
(a)ジイソシアネート化合物が芳香族ジイソシアネー
ト化合物である特許請求の範囲第(1)項記載の湿気硬
化型ウレタンプレポリマー組成物。The moisture-curable urethane prepolymer composition according to claim (1), wherein the diisocyanate compound (a) is an aromatic diisocyanate compound.
(b)芳香族ジイソシアネート化合物が4,4′ジフエ
ニルメタンジイソシアネートでポリオール化合物がポリ
プロピレングリコールである特許請求の範囲第(1)項
記載の湿気硬化型ウレタンプレポリマー組成物。(b) The moisture-curable urethane prepolymer composition according to claim 1, wherein the aromatic diisocyanate compound is 4,4' diphenylmethane diisocyanate and the polyol compound is polypropylene glycol.
(C)ポリプロピレンポリオールが1分子中に2または
3個の水酸基を有し、かつ1分子当りの平均水酸基数が
2以上2.5以下、数平均分子量が400〜2500の
範囲にあるポリオールである特許請求の範囲第項記載の
(1)湿気硬化型ウレタンプレポリマー組成物。(C) The polypropylene polyol has 2 or 3 hydroxyl groups in one molecule, the average number of hydroxyl groups per molecule is 2 or more and 2.5 or less, and the number average molecular weight is in the range of 400 to 2,500. (1) Moisture-curable urethane prepolymer composition as described in claim 1.
(d)酸クロライドの1種または2種以上の組合せから
なる貯蔵安定剤を含有することを特徴とする特
許
レタンプレポリマー組成物。(d) A patented rethane prepolymer composition characterized in that it contains a storage stabilizer consisting of one or a combination of two or more acid chlorides.
[実施例] 以下、本発明を実施例及び比較例について説明する。[Example] The present invention will be described below with reference to Examples and Comparative Examples.
〔比較例−1〕
三ツ口のセパプルフラスコに4.4゛−ジフェニルメタ
ンジイソシアネートを775g秤り取り、50℃に昇温
しな。[Comparative Example-1] Weigh out 775 g of 4.4'-diphenylmethane diisocyanate into a three-neck seperate flask, and heat it to 50°C.
次いで平均分子量2700のポリプロピレングリコール
を2700g滴下ロートに秤り取り、フラスコを攪拌し
ながら1時間をかけてポリプロピレングリコールの全量
をセパラブルフラスコ中に滴下した。Next, 2700 g of polypropylene glycol having an average molecular weight of 2700 was weighed into a dropping funnel, and the entire amount of polypropylene glycol was dropped into the separable flask over 1 hour while stirring the flask.
このときフラスコの内温か50〜80℃の範囲にあるよ
う温度をコントロールした。At this time, the temperature was controlled so that the internal temperature of the flask was within the range of 50 to 80°C.
ポリプロピレングリコールの全量の滴下終了後、フラス
コ内温を75℃に保持し、3時間撹拌を続けてウレタン
プレポリマーを合成した。After dropping the entire amount of polypropylene glycol, the internal temperature of the flask was maintained at 75° C., and stirring was continued for 3 hours to synthesize a urethane prepolymer.
次いでウレタンプレポリマー100重量部に対して硬化
触媒としてジメチルアミノエタノールを0、3重量部、
貯蔵安定剤としての塩化ラウロイルを0.5重量部添加
し、さらにシリコン系消泡剤を0.1重量部加え、十分
に混合攪拌した。Next, 0.3 parts by weight of dimethylaminoethanol was added as a curing catalyst to 100 parts by weight of the urethane prepolymer.
0.5 part by weight of lauroyl chloride as a storage stabilizer was added, and further 0.1 part by weight of a silicone antifoaming agent was added, followed by thorough mixing and stirring.
このものを5 0 0 mlの容器に分取、密栓し、湿
気硬化型ウレタンプレポリマー組成物の調整を終了した
。This material was taken out into a 500 ml container and sealed tightly to complete the preparation of a moisture-curable urethane prepolymer composition.
〔実施例−1〕
比較例−1と同様の装置を用い、4,4′−ジフェニル
メタンジイソシアネートを775g平均分子量1700
のポリプロピレングリコール1700gを秤り、比較例
−1と同様の操作によるウレタンプレポリマーを合成し
た。[Example-1] Using the same apparatus as in Comparative Example-1, 775 g of 4,4'-diphenylmethane diisocyanate was prepared with an average molecular weight of 1700.
1700 g of polypropylene glycol was weighed out and a urethane prepolymer was synthesized in the same manner as in Comparative Example-1.
次いで上記ウレタンプレポリマー100重量部に対して
、硬化触媒としてジモルホリノトリエチルエーテルを0
.3重量部、貯蔵安定剤として塩化ラウロイルを0.5
重量部、シリコン消泡剤を0、1重量部加え、十分に混
合操作して、500mlの容器に分取、密栓した。Next, 0 parts of dimorpholinotriethyl ether was added as a curing catalyst to 100 parts by weight of the above urethane prepolymer.
.. 3 parts by weight, 0.5 parts by weight of lauroyl chloride as a storage stabilizer
0.1 parts by weight of a silicone antifoaming agent were added, thoroughly mixed, and the mixture was placed in a 500 ml container and sealed.
〔実施例−2〕
比較例−1と同様の装置を用い、4,4°−ジフェニル
メタンジイソシアネート1550g、平均分子量700
のポリプロピレングリコール1400gを秤り取り、比
較例−1と同様の操作により、ウレタンプレポリマー組
成物を調整した。[Example-2] Using the same apparatus as in Comparative Example-1, 1550 g of 4,4°-diphenylmethane diisocyanate, average molecular weight 700
1400 g of polypropylene glycol was weighed out and a urethane prepolymer composition was prepared in the same manner as in Comparative Example-1.
次いでウレタンプレポリマー100重量部に対して、硬
化触媒としてジモルホリノトリエチルエーテルを0.3
重量部、貯蔵安定剤として塩化ラウロイルを0.5重量
部シリコン消泡剤を0.1重量部加え、十分に混合撹拌
した後、500m1の容器に分取、密栓しな。Next, 0.3 parts of dimorpholino triethyl ether was added as a curing catalyst to 100 parts by weight of the urethane prepolymer.
0.5 parts by weight of lauroyl chloride as a storage stabilizer and 0.1 parts by weight of a silicone antifoaming agent were added, and after thorough mixing and stirring, the mixture was placed in a 500 ml container and sealed tightly.
〔実施例−3〕
比較例−1と同様の装置を用い、4,4′−ジフェニル
メタンジイソシアネート1550g、平均分子量400
のポリプロピレングリコール8゜Ogを秤り取り、比較
例−1と同様の操作により、ウレタンプレポリマーを合
成した。[Example-3] Using the same apparatus as in Comparative Example-1, 1550 g of 4,4'-diphenylmethane diisocyanate and an average molecular weight of 400
8°Og of polypropylene glycol was weighed out, and a urethane prepolymer was synthesized in the same manner as in Comparative Example-1.
次いでウレタンプレポリマー100重量部に対して、硬
化触媒としてジモルホリノトリエチルエテルを0.8重
量部、貯蔵安定剤として塩化ラウロイルを0.5重量部
、シリコン消泡剤を0゜1重量部加え、十分に混合攪拌
した後、500 allの容器に分取、密栓しな。Next, to 100 parts by weight of the urethane prepolymer, 0.8 parts by weight of dimorpholinotriethyl ether as a curing catalyst, 0.5 parts by weight of lauroyl chloride as a storage stabilizer, and 0.1 part by weight of a silicone antifoaming agent were added. After thoroughly mixing and stirring, divide into a 500-all container and seal tightly.
〔比較例−2〕
比較例−1と同様の装置を用い、4.4゛−ジフェニル
メタンジイソシアネート1550g、平均分子量300
のポリプロピレングリコール6゜Ogを秤り取り、比較
例−1と同様の操作により、ウレタンプレポリマーを合
成した。[Comparative Example-2] Using the same apparatus as in Comparative Example-1, 1550 g of 4.4'-diphenylmethane diisocyanate, average molecular weight 300
6°Og of polypropylene glycol was weighed out and a urethane prepolymer was synthesized in the same manner as in Comparative Example-1.
次いでウレタンプレポリマー100重量部に対して、硬
化触媒としてジメチルアミノエタノールを0,8重量部
、塩化ラウロイルを0.5重量部、シリコン消泡剤を0
.1重量部加え、十分に混合撹拌した後、500 mr
の容器に分取、密栓した。Next, to 100 parts by weight of the urethane prepolymer, 0.8 parts by weight of dimethylaminoethanol as a curing catalyst, 0.5 parts by weight of lauroyl chloride, and 0 parts by weight of a silicone antifoaming agent were added.
.. After adding 1 part by weight and stirring thoroughly, 500 mr
Aliquot it into a container and seal it tightly.
前記の実施例1,2.3及び比較例1.2の5サンプル
について、それぞれ以下の操作を行い、整形外科用ギプ
ス包帯としての評価を行なった。The five samples of Examples 1 and 2.3 and Comparative Example 1.2 described above were subjected to the following operations and evaluated as orthopedic cast bandages.
B−ガラス繊維からなる商用密度0.035g/−、メ
ツシュ数90開口数/in2で布帛幅7゜5C11の有
用テープに湿気硬化型ウレタンプレポリ7−を2本ロー
ラーのコーターヘッドを用いて含浸し、長さ4mの含浸
テープを作成し、そのテープを直径10cI+のプラス
チック円筒に5層になるよう巻き付け、水中に30秒間
浸漬した後空気中で1時間放置し、直ちにプラスチック
円筒を抜き取り、5層テープの直径方向に押圧荷重をか
けて、その耐圧荷重及び破断ひずみを測定した。B-A useful tape made of glass fiber with a commercial density of 0.035 g/-, a mesh number of 90 numerical apertures/in2, and a fabric width of 7°5C11 is impregnated with moisture-curable urethane prepoly 7- using a coater head of two rollers. Then, create an impregnated tape with a length of 4 m, wrap the tape around a plastic cylinder with a diameter of 10 cI+ in 5 layers, immerse it in water for 30 seconds, leave it in the air for 1 hour, and immediately pull out the plastic cylinder. A pressure load was applied in the diametrical direction of the layered tape, and its pressure resistance and breaking strain were measured.
ここで、整形外科用ギプス包帯としての必要条件は、耐
圧荷重10kf以上、破断ひすみ20%以上の両条件を
有することである。Here, the necessary conditions for an orthopedic cast bandage are that it has both a pressure resistance of 10 kf or more and a fracture strain of 20% or more.
〔実施例−4〕
比較例−1と同様の装置を用い、4,4°−ジフェニル
メタンジイソシアネート885gに平均分子量700の
ポリプロピレングリコール490gと平均分子量100
0のポリプロピレントリオール300gを混合したもの
から、比較例−1と同様の操作によってウレタンプレポ
リマーを合成した。[Example-4] Using the same apparatus as in Comparative Example-1, 490 g of polypropylene glycol with an average molecular weight of 700 and 490 g of polypropylene glycol with an average molecular weight of 100 were added to 885 g of 4,4°-diphenylmethane diisocyanate.
A urethane prepolymer was synthesized from a mixture of 300 g of polypropylene triol of No. 0 in the same manner as in Comparative Example-1.
次に上記ウレタンプレポリマー100重量部に対して、
硬化触媒としてジモルホリノトリエチルエーテルを0.
3重量部、貯蔵安定剤として塩化ラウロイルを0.5重
量部、シリコン消泡剤を0゜1重量部加え、十分に操作
混合して後、500 mlの容器に分取した。Next, for 100 parts by weight of the above urethane prepolymer,
0.0% dimorpholinotriethyl ether as a curing catalyst.
3 parts by weight, 0.5 parts by weight of lauroyl chloride as a storage stabilizer, and 0.1 part by weight of a silicone antifoaming agent were added, and after thorough mixing, the mixture was dispensed into a 500 ml container.
〔実施例−5〕
比較例−1と同様の装置を用い、4,4°−ジフェニル
メタンジイソシアネート960gに平均分子量700の
ポリプロピレングリコール350gと平均分子量100
0のポリプロピレントリオール350gを混合したもの
から、比較例−1と同様の操作によってウレタンプレポ
リマーを合成した。[Example-5] Using the same apparatus as in Comparative Example-1, 960 g of 4,4°-diphenylmethane diisocyanate, 350 g of polypropylene glycol with an average molecular weight of 700, and 350 g of polypropylene glycol with an average molecular weight of 100 were added.
A urethane prepolymer was synthesized from a mixture of 350 g of polypropylene triol of No. 0 in the same manner as in Comparative Example-1.
次に上記ウレタンプレポリマー100重量部に対して、
硬化触媒としてジモルホリノトリエチルエーテルを0.
3重量部、塩化ラウロイルを0゜5重量部、シリコン消
泡剤を0.1重量部加え、十分に攪拌混合して後、50
0 mlの容器に分取した。Next, for 100 parts by weight of the above urethane prepolymer,
0.0% dimorpholinotriethyl ether as a curing catalyst.
Add 3 parts by weight of lauroyl chloride, 0.5 parts by weight of lauroyl chloride, and 0.1 part by weight of silicone antifoaming agent, stir thoroughly and mix.
Aliquoted into 0 ml containers.
〔比較例−3〕
比較例−1と同様の装置を用い、4,4′−ジフェニル
メタンジイソシアネート1030gに平均分子量700
のポリプロピレングリコール210gと平均分子量10
00のポリプロピレントリオール700gを混合したも
のから、比較例−1と同様の操作によってウレタンプレ
ポリマーを合成した。[Comparative Example-3] Using the same apparatus as in Comparative Example-1, 1030 g of 4,4'-diphenylmethane diisocyanate was mixed with an average molecular weight of 700.
210g of polypropylene glycol and average molecular weight 10
A urethane prepolymer was synthesized from a mixture of 700 g of polypropylene triol No. 00 in the same manner as in Comparative Example-1.
次に上記ウレタンプレポリマー100重量部に対して、
ジメチルアミノエタノールを0.3重量部、塩化ラウロ
イルを0.5重量部、シリコン消泡剤を0.1重量部加
え、十分に攪拌混合して後、500m1の容器に分取し
た。Next, for 100 parts by weight of the above urethane prepolymer,
0.3 parts by weight of dimethylaminoethanol, 0.5 parts by weight of lauroyl chloride, and 0.1 parts by weight of a silicone antifoaming agent were added, thoroughly stirred and mixed, and then fractionated into a 500 ml container.
これらの実施例−4,−5及び比較例−3について、前
記の評価方法に従って整形外科用ギプス包帯としての評
価を行なった結果を次に示す、なお先の実施例−2の結
果をも参考のため列挙した。These Examples-4, -5 and Comparative Example-3 were evaluated as orthopedic cast bandages according to the above-mentioned evaluation method, and the results are shown below.The results of the previous Example-2 are also referred to. Listed for.
[測定結果]
ここで
湿気硬化型ウレタンプレポリマー重量+布帛重量耐圧荷
量(kg)=降伏点を示す時の荷量= λ外
樹脂塗布 耐圧荷重 破断ひずみ
量(%) (kr ) (%)実施例−480
2542
実施例−5852725
実施例−2752250
比較例−3105339
次に同じプレポリマーに対し3鉄アミンと酸クロライド
を種々組合せた実施例について説明する。[Measurement results] Here, moisture-curable urethane prepolymer weight + fabric weight pressure load capacity (kg) = load at yield point = λ outside resin coating pressure load capacity at break (%) (kr) (%) Example-480
2542 Example-5852725 Example-2752250 Comparative Example-3105339 Next, examples will be described in which various combinations of 3-iron amine and acid chloride are used in the same prepolymer.
3ツロのセパラブルフラスコに4,4′−ジフェニルメ
タンジイソシアネートを3100g秤り取り、50℃に
昇温した。3100 g of 4,4'-diphenylmethane diisocyanate was weighed into a 3-meter separable flask, and the temperature was raised to 50°C.
次いで平均分子量700のポリプロピレングリコール2
800gを滴下用ロートに秤り取り、セパラブルフラス
コにセットし、フラスコを撹拌しながら1時間をかけて
ポリプロピレングリコールの全量を滴下した。Next, polypropylene glycol 2 with an average molecular weight of 700
800 g was weighed into a dropping funnel, set in a separable flask, and the entire amount of polypropylene glycol was added dropwise over 1 hour while stirring the flask.
このときフラスコの内温か50〜80℃の範囲にあるよ
うに温度をコントロールした。At this time, the temperature was controlled so that the internal temperature of the flask was within the range of 50 to 80°C.
ポリプロピレングリコールの全量を滴下終了後、フラス
コ内温を75℃に保持し、3時間撹拌を続けてウレタン
プレポリマーを合成した。After dropping the entire amount of polypropylene glycol, the internal temperature of the flask was maintained at 75° C., and stirring was continued for 3 hours to synthesize a urethane prepolymer.
合成した全ウレタンプレポリマーに対して0゜1重量部
のシリコン系消泡剤を添加し、更に30分間攪拌して、
500 mlの容器に分取密栓した。0.1 parts by weight of silicone antifoaming agent was added to the entire synthesized urethane prepolymer, and the mixture was further stirred for 30 minutes.
The sample was separated and sealed in a 500 ml container.
このものを以後プレポリマーAと称する。This product will be referred to as prepolymer A hereinafter.
上迅の方法で分取したプレポリマーAに以下示す配合に
より3級アミン、酸クロライドを添加し、前記評価方法
に従い、耐圧荷重、破断ひずみを測定し、更に、硬化時
間、貯蔵安定加速テストを測定した。A tertiary amine and acid chloride were added to prepolymer A separated by the above method, and the pressure resistance and breaking strain were measured according to the evaluation method described above, and the curing time and storage stability acceleration test were also conducted. It was measured.
ここで硬化時間とは、湿気硬化型ウレタンプレポリマー
をE−ガラ・ス繊維からなる布帛テープに含浸させたも
のを30秒間水中に浸漬した後、空気中に室温で放置し
、布帛面を指で触って、タックがなくなるまでの時間を
いい、好ましくは5分以上、20分以内である。Here, the curing time refers to a fabric tape made of E-glass fiber impregnated with a moisture-curable urethane prepolymer, immersed in water for 30 seconds, left in the air at room temperature, and the fabric surface is rubbed with a finger. It refers to the time it takes for the tack to disappear when touched, preferably 5 minutes or more and 20 minutes or less.
また、貯蔵安定性加速テストは次のように行なった。湿
気硬化型ウレタンプレポリマーを100ml容のポリプ
ロピレン製容器に50g秤り取り、密栓する。Further, an accelerated storage stability test was conducted as follows. Weigh out 50 g of moisture-curable urethane prepolymer into a 100 ml polypropylene container and seal the container.
このものを130℃の雰囲気に静置し、100分毎に容
器内のプレポリマーの流動性を観察する。This product was left standing in an atmosphere of 130°C, and the fluidity of the prepolymer in the container was observed every 100 minutes.
容器を傾けても容器内のプレポリマーの流動性が観察さ
れなくなった時点を終点とし、その時の経過した時間を
記録する。The end point is the time when the fluidity of the prepolymer in the container is no longer observed even when the container is tilted, and the time elapsed at that point is recorded.
この終点までの時間が長ければ長い程貯蔵安定性に優れ
たプレポリマーである。The longer the time to this end point, the better the storage stability of the prepolymer.
(発明の効果)
以上述べたように、本発明によれば、貯蔵安定性に優れ
、かつ使用時の硬化時間が適度に調整可能な湿気硬化型
ウレタンプレポリマー組成物を得ること
ができ、塗料、接着剤、整形外科用ギブス包帯等の分野
において優れた性能を発揮するものである。(Effects of the Invention) As described above, according to the present invention, it is possible to obtain a moisture-curable urethane prepolymer composition that has excellent storage stability and can appropriately adjust the curing time during use, and It exhibits excellent performance in the fields of adhesives, orthopedic casts, etc.
手続補正 書(自発)Procedural amendment (voluntary)
Claims (2)
なる末端に−NCO基を有するウレタンプレポリマーと
下記化学構造 ▲数式、化学式、表等があります▼ を有するジモルホリノトリエチルエーテルを硬化触媒と
して含有することを特徴とする湿気硬化型ウレタンプレ
ポリマー組成物。(1) It is characterized by containing a urethane prepolymer having a -NCO group at the end consisting of a diisocyanate compound and a polyol compound and dimorpholinotriethyl ether having the following chemical structure ▲Mathical formula, chemical formula, table, etc. ▼ as a curing catalyst. Moisture-curable urethane prepolymer composition.
なる末端に−NCO基を有するウレタンプレポリマーと
下記化学構造 ▲数式、化学式、表等があります▼ を有するジモルホリノトリエチルエーテルを硬化触媒と
して含有する樹脂組成物が網状支持体に担持されている
ことを特徴とする湿気硬化型医療用固定材。(2) A resin composition containing a urethane prepolymer having a -NCO group at the terminal consisting of a diisocyanate compound and a polyol compound and dimorpholinotriethyl ether having the following chemical structure ▲Mathical formula, chemical formula, table, etc.▼ as a curing catalyst. A moisture-curable medical fixing material, characterized in that it is supported on a net-like support.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63255551A JPH02102215A (en) | 1988-10-11 | 1988-10-11 | Moisture-curable urethane prepolymer composition and moisture-curable fixing material for medical use |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63255551A JPH02102215A (en) | 1988-10-11 | 1988-10-11 | Moisture-curable urethane prepolymer composition and moisture-curable fixing material for medical use |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02102215A true JPH02102215A (en) | 1990-04-13 |
Family
ID=17280296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63255551A Pending JPH02102215A (en) | 1988-10-11 | 1988-10-11 | Moisture-curable urethane prepolymer composition and moisture-curable fixing material for medical use |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02102215A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5342291A (en) * | 1991-08-29 | 1994-08-30 | Minnesota Mining And Manufacturing Company | Printed woven fiber materials and method |
KR20020071229A (en) * | 2001-03-05 | 2002-09-12 | 대한민국(부산대학교) | The composition of water curable polyurethane for orthopedic castings |
KR100541869B1 (en) * | 2002-10-04 | 2006-01-16 | 목동엽 | A resin composition of polyurethane for accessories used in shoes and clothing, and for substituting for PVC |
KR100654425B1 (en) * | 2002-09-04 | 2006-12-07 | 주식회사 티앤엘 | Water-setting polyurethane resin composition and there using semi-rigid casting tape |
-
1988
- 1988-10-11 JP JP63255551A patent/JPH02102215A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5342291A (en) * | 1991-08-29 | 1994-08-30 | Minnesota Mining And Manufacturing Company | Printed woven fiber materials and method |
KR20020071229A (en) * | 2001-03-05 | 2002-09-12 | 대한민국(부산대학교) | The composition of water curable polyurethane for orthopedic castings |
KR100654425B1 (en) * | 2002-09-04 | 2006-12-07 | 주식회사 티앤엘 | Water-setting polyurethane resin composition and there using semi-rigid casting tape |
KR100541869B1 (en) * | 2002-10-04 | 2006-01-16 | 목동엽 | A resin composition of polyurethane for accessories used in shoes and clothing, and for substituting for PVC |
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