JPH01145110A - Manufacture of polyurethane/polyurea molded product - Google Patents
Manufacture of polyurethane/polyurea molded productInfo
- Publication number
- JPH01145110A JPH01145110A JP62256780A JP25678087A JPH01145110A JP H01145110 A JPH01145110 A JP H01145110A JP 62256780 A JP62256780 A JP 62256780A JP 25678087 A JP25678087 A JP 25678087A JP H01145110 A JPH01145110 A JP H01145110A
- Authority
- JP
- Japan
- Prior art keywords
- molded product
- polyurethane
- making use
- catalyst
- composition
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 8
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 7
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical group CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 4
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 30
- 239000007789 gas Substances 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000002845 discoloration Methods 0.000 abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 abstract description 4
- 239000005056 polyisocyanate Substances 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 238000001746 injection moulding Methods 0.000 abstract 1
- 229920005906 polyester polyol Polymers 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 1
- VVNDEUQQZUVMNA-UHFFFAOYSA-N 2,6-bis(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC(C(C)(C)CC(C)(C)C)=C1O VVNDEUQQZUVMNA-UHFFFAOYSA-N 0.000 description 1
- PZPVXSMCRLNVRD-UHFFFAOYSA-N 2,6-dibutylphenol Chemical compound CCCCC1=CC=CC(CCCC)=C1O PZPVXSMCRLNVRD-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- -1 N'-tetramethyl-1 Chemical class 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (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、自動車用バンパー、ウィンドガスケットなど
に用いられるポリウレタン／ポリウレア成形品を製造す
る方法である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is a method for manufacturing polyurethane/polyurea molded products used for automobile bumpers, window gaskets, and the like.
［従来の技術］
従来、ポリウレタン成形品は、活性水素含有組成物中の
鎖延長剤として多価アルコールを用いて反応射出成形法
（以下ＲＩＭ法と略す）によって成形されているが、硬
化時間が長く、生産効率が悪い。この為、多価アルコー
ルの代りに芳香族ポリアミンを用いる方法が提案されて
いる（特公昭５４−１７３５９号公報参照）。芳香族ポ
リアミンを用いると、成形時間が短縮され、生産効率が
極めて高くなるが、ポリイソシアネートとの反応が急激
であり、ハロゲン化炭化水素による発泡の制御が困難と
なる。この為、活性水素含有組成物に気体を強制的に吹
き込み分散溶解させる（以下ガスローディングと略す）
方法がとられ、一般に気体としては空気などの酸素を含
有する気体が用いられている。[Prior Art] Conventionally, polyurethane molded products have been molded by reaction injection molding (hereinafter referred to as RIM method) using polyhydric alcohol as a chain extender in an active hydrogen-containing composition, but the curing time is Long and inefficient production. For this reason, a method has been proposed in which an aromatic polyamine is used instead of a polyhydric alcohol (see Japanese Patent Publication No. 17359/1983). When aromatic polyamines are used, molding time is shortened and production efficiency is extremely high, but the reaction with polyisocyanates is rapid, making it difficult to control foaming caused by halogenated hydrocarbons. For this purpose, gas is forcibly blown into the active hydrogen-containing composition to disperse and dissolve it (hereinafter abbreviated as gas loading).
Generally, a gas containing oxygen such as air is used as the gas.
［発明が解決しようとする問題点］
酸素含有気体でガスローディングした活性水素含有組成
物を長時間貯蔵すると、ポリイソシアネートとの反応性
が低下し、得られる成形品の初期強度が不十分である。[Problems to be solved by the invention] When an active hydrogen-containing composition loaded with an oxygen-containing gas is stored for a long time, the reactivity with polyisocyanate decreases, and the initial strength of the resulting molded product is insufficient. .
このような成形品は脱型時に破損したり貯蔵中に変形し
たりする。Such molded products may be damaged during demolding or deformed during storage.
この傾向はヒンダードフェノール系安定剤を用いると特
に著しい。しかしながら成形品は美観上あるいは耐候性
向上のために塗装されるが、成形品中にヒンダードフェ
ノール系安定剤が存在していないとその塗膜の変色性が
著しい。そのためにヒンダードフェノール系安定剤は不
可欠である。This tendency is particularly remarkable when using hindered phenol stabilizers. However, molded products are painted for aesthetic reasons or to improve weather resistance, but if the hindered phenol stabilizer is not present in the molded product, the paint film will be significantly discolored. For this purpose, hindered phenol stabilizers are essential.
従って、週末や連体前には、成形機のタンク内の原料を
抜取っておき、休み明けに新たに活性水素含有組成物を
調製して充填しなおさなければならない等の問題があっ
た。Therefore, there were problems such as having to drain the raw material in the tank of the molding machine on weekends or before the assembly, and then having to prepare a new active hydrogen-containing composition and refill it after the holidays.
本発明者らは、ガスローディングした状態で長時間貯蔵
してもポリイソシアネートとの反応性が低下せず、初期
強度が高く、かつ塗膜の変色が少ない成形品が得られる
活性水素含有組成物中二ついて鋭意検討を重ねた結果、
触媒としてジメチルチンジラウレートを用いることによ
り、上記問題点が解決されることを見い出し、本発明を
完成した。The present inventors have developed an active hydrogen-containing composition that does not reduce its reactivity with polyisocyanate even when stored for a long time under gas loading, and can provide molded products with high initial strength and little discoloration of the coating film. As a result of careful consideration while in middle school,
The inventors have discovered that the above problems can be solved by using dimethyltin dilaurate as a catalyst, and have completed the present invention.
［問題点を解決するための手段］
本発明は、
（ａ）分子量が１８００ないし １２０００であり末端
１級化率が９０％以上のポリエーテルポリオール（ｂ）
芳香族ポリアミン
（ｃ）ヒンダードフェノール系安定剤 および（ｄ）必
要に応じてその他の助剤
からなる混合物に触媒としてジメチルチンジラウレート
を加え、酸素含有気体をガスローディングした活性水素
含有組成物と、変性ジフェニルメタンジイソシアネート
組成物（以下変性ＭＤＩ組成物と略す）とを用いてＲＩ
Ｍ法により成形することによりポリウレタン／ポリウレ
ア成形品を製造する方法である。[Means for Solving the Problems] The present invention provides (a) a polyether polyol having a molecular weight of 1,800 to 12,000 and a terminal primaryization rate of 90% or more;
An active hydrogen-containing composition obtained by adding dimethyltin dilaurate as a catalyst to a mixture consisting of an aromatic polyamine (c) a hindered phenol stabilizer and (d) other auxiliary agents as necessary, and gas-loading with an oxygen-containing gas; RI using a modified diphenylmethane diisocyanate composition (hereinafter abbreviated as modified MDI composition)
This is a method for producing polyurethane/polyurea molded products by molding using the M method.
本発明で用いられる活性水素含有組成物中のポリエーテ
ルポリオールは、プロピレングリコール、グリセリンな
どの出発物質にエチレンオキシドおよびプロピレンオキ
シドを付加させた分子量が１８００ないし １２００Ｇ
であり、末端１級化率が９０％以上のものである。通常
プロピレンオキシドを付加させると末端水酸基は２級と
なりイソシアネート基との反応性が低くなり、エチレン
オキシドを付加させると末端水酸基は１級となりイソシ
アネート基との反応性が高い。出発Ｉｆｆ、エチレンオ
キシドとプロピレンオキシドとの比率、分子量などが異
るポリエーテルポリオールを混合して用いることもでき
る。The polyether polyol in the active hydrogen-containing composition used in the present invention is obtained by adding ethylene oxide and propylene oxide to a starting material such as propylene glycol or glycerin and has a molecular weight of 1800 to 1200G.
The terminal primaryization rate is 90% or more. Usually, when propylene oxide is added, the terminal hydroxyl group becomes secondary and has low reactivity with isocyanate groups, and when ethylene oxide is added, the terminal hydroxyl group becomes primary and has high reactivity with isocyanate groups. It is also possible to use a mixture of polyether polyols having different starting Iff, ratio of ethylene oxide to propylene oxide, molecular weight, etc.
鎖延長剤として用いられる芳香族ポリアミンとしては、
１，３．５−１−ジエチル−２，６−ジアミツベンゼン
、３，３°、５．５’−テトラエチル −４゜４°−ジ
アミノジフェニルメタン、１−メチル−３，５−ジエチ
ル−２，４−ジアミノベンゼン、１−メチル −３，５
−ジエチル −２，６−ジアミノベンゼン、モノ −ｔ
ａｒｔ−ブチルトルエンジアミンなどが用いられるが、
１−メチル −３，５−ジエチル −２，４−ジアミノ
ベンゼン、１−メチル−３，５−ジエチル−２，６−ジ
アミノベンゼンが好ましい。また、その使用量は通常ポ
リエーテルポリオール １００重量部′当り１ないし
１００重量部である。Aromatic polyamines used as chain extenders include:
1,3.5-1-diethyl-2,6-diamitbenzene, 3,3°,5.5'-tetraethyl-4°4°-diaminodiphenylmethane, 1-methyl-3,5-diethyl-2, 4-diaminobenzene, 1-methyl-3,5
-diethyl-2,6-diaminobenzene, mono-t
art-butyltoluenediamine etc. are used,
1-methyl-3,5-diethyl-2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diaminobenzene are preferred. The amount used is usually 1 to 100 parts by weight of polyether polyol.
It is 100 parts by weight.
触媒としては、ジメチルチンジラウレートが用いられる
。従来触媒として知られているトリエチルアミン、Ｎ−
メチルモルホリン、Ｎ−エチルモルホリン、ビス（Ｍ、
Ｎ−ジメチルアミノエチル）エーテル、１，４−ジメチ
ルピペラジン、トリエチレンジアミン、に、Ｎ、Ｎ’、
Ｎ’−テトラメチル −１，３−ブタンジアミンなどの
第３級アミンやジブチルチンジラウレート、スタナスオ
フテートなどと混合して用いてもよい。Dimethyltin dilaurate is used as the catalyst. Triethylamine, N-, which is conventionally known as a catalyst
Methylmorpholine, N-ethylmorpholine, bis(M,
N-dimethylaminoethyl) ether, 1,4-dimethylpiperazine, triethylenediamine, N, N',
It may be used in combination with a tertiary amine such as N'-tetramethyl-1,3-butanediamine, dibutyltin dilaurate, stannathoftate, or the like.
ヒンダードフェノール系安定剤としては、市販のＩｒｇ
ａｎｏｘ １０１０ （チバガイギー社品） Ｓｕｍｉ
−１ｉｚｅｒ ＧＷ （住友化学社品）、２，６−ジ
−ｔｅｒｔ−オクチルフェノール、２．６−ジイツブチ
ルフエノール、２，６−ジ −ｔａｒｔ−ブチル −４
−メチルフェノール（以下ＢＨＴと略す）が用いられる
が、Ｉｒｇａｎｏｘ １０１０． Ｂ Ｉ Ｔが好ま
しい。As a hindered phenol stabilizer, commercially available Irg
anox 1010 (Ciba Geigy product) Sumi
-1izer GW (Sumitomo Chemical), 2,6-di
-tert-octylphenol, 2,6-dibutylphenol, 2,6-di-tart-butyl-4
-Methylphenol (hereinafter abbreviated as BHT) is used, and Irganox 1010. BIT is preferred.
また、その使用量は通常ポリエーテルポリオール １０
０重量部当り０．１ないし２−．０重量部である。In addition, the amount used is usually polyether polyol 10
0.1 to 2-.0 parts by weight. It is 0 parts by weight.
その他の助剤としては、必要に応じて着色剤、有機ある
いは無機充填剤、有機シリコーンなどの整泡剤、ステア
リン酸亜鉛などの内部離型剤、水、ハロゲン化炭化水素
などの発泡剤などが用いられる。Other auxiliary agents include colorants, organic or inorganic fillers, foam stabilizers such as organic silicones, internal mold release agents such as zinc stearate, water, and foaming agents such as halogenated hydrocarbons, etc., as necessary. used.
酸素含有気体としては、空気が好ましいが、酸素と他の
不活性な気体との混合気体を用いてもよい。As the oxygen-containing gas, air is preferred, but a mixed gas of oxygen and other inert gases may also be used.
変性ＭＤＩ組成物としては、ＭＤＩを多価アルコールや
多価アミンと反応させたウレタン結合やウレア結合を含
有するＭＤＩ組成物、ＭＤＩを触媒の存在下あるいは加
熱下に反応させたイソシアヌレート、カルボジイミド、
ウレトニミンなどの結合を含有するＭＤＩ組成物または
これらの混合物が用いられる。変性ＭＤＩ組成物のイソ
シアネート基と活性水素含有組成物の活性水素含有基と
の比率（以下イソシアネートインデックスと略す）が、
０．８ないし１．５になるようにして使用される。Examples of modified MDI compositions include MDI compositions containing urethane bonds and urea bonds obtained by reacting MDI with polyhydric alcohols and polyvalent amines, isocyanurates and carbodiimides obtained by reacting MDI in the presence of a catalyst or under heating,
MDI compositions containing linkages such as uretonimine or mixtures thereof are used. The ratio of the isocyanate groups of the modified MDI composition to the active hydrogen-containing groups of the active hydrogen-containing composition (hereinafter abbreviated as isocyanate index) is
It is used so that it becomes 0.8 to 1.5.
上記の活性水素含有組成物と変性ＭＤＩ組成物とを用い
て、ＲＩＭ用高圧発泡機を用いてＲＩＭ法によって製造
されるポリウレタン／ポリウレア成形品は自動車用バン
パー、ウィンドガスケットなどに用いることができる。Polyurethane/polyurea molded products produced by the RIM method using the above active hydrogen-containing composition and modified MDI composition using a high-pressure foaming machine for RIM can be used for automobile bumpers, window gaskets, and the like.
この様にして得られる成形品は、そのままあるいはウレ
タン系などの塗料で塗装して実用に供される。The molded product obtained in this way is put into practical use as it is or after being painted with a urethane-based paint or the like.
［実施例および比較例］
グリセリンにエチレンオキシドとプロピレンオキシドを
付加させた分子量が６０００であり末端１級化率が９５
％のポリエーテルポリオール７９重量部と、１−メチル
−３，５−ジエチル−２，４−ジアミノベンゼンおよび
１−メチル−３，５−ジエチル −２，６−ジアミツ
ベンゼンの混合物２１重量部を均一に混合し、これに第
１表に記載の重量部数の安定剤および触媒を加えた。空
気を用いて比重が ０．６になるまでガスローディング
し、２ｋｇ／ｃｒｒｒの加圧下に撹拌しながら４０℃で
３日間タンク内に貯蔵した。この活性水素含有組成物を
ＲＩＭ用高圧発泡機を用いて、イソシアネートインデッ
クスが ｌＯフとなるようにウレタン変性ＭＤＩ組成物
（イソシアネート含有量２３％）５４重量部と混合し、
７０℃に加温された板形状の金型に注入した。２０秒後
金型を開け、縦、横、厚みが１００ ｃｍ、３０ｃｍ、
ＩＣ閣の板形状の成形品を脱型した。この成形品をただ
ちに１８０度折り曲げ、折り曲げた所にクラックが起こ
るかどうかを調べ初期強度の評価を行った。さらに、こ
の様にして得られた成形品にウレタン系塗料（フレキセ
ン１０１： 日本ペイント社品）をスプレーガンで塗装
し１２０°Ｃの乾燥室で２０分間乾燥した。[Examples and Comparative Examples] The molecular weight of glycerin with ethylene oxide and propylene oxide added is 6000 and the terminal primaryization rate is 95.
% polyether polyol and 21 parts by weight of a mixture of 1-methyl-3,5-diethyl-2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diamitbenzene. Mixed homogeneously, to which were added the parts by weight of stabilizer and catalyst listed in Table 1. Gas loading was performed using air until the specific gravity reached 0.6, and the product was stored in a tank at 40° C. for 3 days while stirring under a pressure of 2 kg/crrr. This active hydrogen-containing composition was mixed with 54 parts by weight of a urethane-modified MDI composition (isocyanate content 23%) so that the isocyanate index was 10% using a high-pressure foaming machine for RIM.
The mixture was poured into a plate-shaped mold heated to 70°C. After 20 seconds, the mold was opened and the length, width and thickness were 100 cm, 30 cm,
The plate-shaped molded product of the IC cabinet was demolded. This molded product was immediately bent by 180 degrees, and the initial strength was evaluated by examining whether or not cracks occurred at the bent portion. Further, the molded article thus obtained was coated with a urethane paint (Flexene 101, manufactured by Nippon Paint Co., Ltd.) using a spray gun and dried for 20 minutes in a drying room at 120°C.
その後９０℃の換気付のオープンに入れて加熱し、４０
日徨に取り出した。８Ｍカラーコンピューター（スガ試
験機社品）を用いて、加熱前の色調を基準として加熱後
の塗１！表面の色差値ΔＥを測定し塗膜の変色の評価を
行った。After that, heat it in a ventilated open room at 90℃ and heat it for 40℃.
I took it out on a daily basis. Using an 8M color computer (manufactured by Suga Test Instruments Co., Ltd.), the color tone before heating was used as a reference, and the color tone after heating was 1! The color difference value ΔE of the surface was measured to evaluate the discoloration of the coating film.
比較例４として１日間タンク内に貯蔵した活性水素含有
組成物を用いて同様に行った。結果を第１−！ｔに示す
。As Comparative Example 4, the same procedure was carried out using an active hydrogen-containing composition stored in a tank for one day. First result! Shown at t.
実施例および比較例から明らかなように、ヒンダードフ
ェノール系安定剤を用い酸素含有気体でガスローディン
グした活性水素含有組成物の触媒としてジメチルチンジ
ラウレートを用いることにより、長時間貯蔵した後にお
いても変性ＭＤＩ組成物と反応させて得られた成形品の
初期強度は充分であり、塗膜の熱による変色も少なかっ
た。As is clear from the Examples and Comparative Examples, by using dimethyltin dilaurate as a catalyst for an active hydrogen-containing composition gas-loaded with an oxygen-containing gas using a hindered phenol stabilizer, denaturation can be achieved even after long-term storage. The initial strength of the molded product obtained by reacting with the MDI composition was sufficient, and there was little discoloration of the coating film due to heat.
Claims (1)
１級化率が９０％以上のポリエーテルポリオール （ｂ）芳香族ポリアミン （ｃ）ヒンダードフェノール系安定剤および （ｄ）必要に応じてその他の助剤 からなる混合物に触媒としてジメチルチンジラウレート
を加え、酸素含有気体でガスローディングした活性水素
含有組成物と、変性ジフェニルメタンジイソシアネート
組成物とを用いて反応射出成形法によりポリウレタン／
ポリウレア成形品を製造する方法 ２、芳香族ポリアミンが１−メチル−３，５−ジエチル
−２，４−ジアミノベンゼンおよび／または１−メチル
−３，５−ジエチル−２，６−ジアミノベンゼンである
ことを特徴とする特許請求の範囲第１項記載のポリウレ
タン／ポリウレア成形品を製造する方法[Scope of Claims] 1 (a) a polyether polyol having a molecular weight of 1,800 to 12,000 and a terminal primaryization rate of 90% or more, (b) an aromatic polyamine, (c) a hindered phenol stabilizer, and (d) necessary. Polyurethane /
Method 2 for producing a polyurea molded article, the aromatic polyamine is 1-methyl-3,5-diethyl-2,4-diaminobenzene and/or 1-methyl-3,5-diethyl-2,6-diaminobenzene A method for producing a polyurethane/polyurea molded article according to claim 1, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62256780A JPH07115374B2 (en) | 1987-10-12 | 1987-10-12 | Method for producing polyurethane / polyurea molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62256780A JPH07115374B2 (en) | 1987-10-12 | 1987-10-12 | Method for producing polyurethane / polyurea molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01145110A true JPH01145110A (en) | 1989-06-07 |
| JPH07115374B2 JPH07115374B2 (en) | 1995-12-13 |
Family
ID=17297343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62256780A Expired - Lifetime JPH07115374B2 (en) | 1987-10-12 | 1987-10-12 | Method for producing polyurethane / polyurea molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07115374B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0408317A2 (en) * | 1989-07-11 | 1991-01-16 | LOCTITE (IRELAND) Ltd. | Method of forming gaskets by injection and compositions for use therein |
| WO1998032580A1 (en) * | 1997-01-23 | 1998-07-30 | Sunstar Giken Kabushiki Kaisha | Two-pack urethane foam composition, and two-pack urethane foam composition packing apparatus and method |
| JP2004502814A (en) * | 2000-07-05 | 2004-01-29 | ビーエーエスエフ アクチェンゲゼルシャフト | Stabilizers especially for thermoplastic polyurethanes |
| JP2011040599A (en) * | 2009-08-12 | 2011-02-24 | Tdk Corp | Method of manufacturing coil component |
| JP2018095875A (en) * | 2016-12-15 | 2018-06-21 | 東ソー株式会社 | Allophanate group-containing polyisocyanate prepolymer |
-
1987
- 1987-10-12 JP JP62256780A patent/JPH07115374B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0408317A2 (en) * | 1989-07-11 | 1991-01-16 | LOCTITE (IRELAND) Ltd. | Method of forming gaskets by injection and compositions for use therein |
| US5116558A (en) * | 1989-07-11 | 1992-05-26 | Loctite (Ireland) Limited | Method of forming gaskets by injection and compositions for use therein |
| AU625425B2 (en) * | 1989-07-11 | 1992-07-09 | Loctite (Ireland) Limited | Method of forming gaskets by injection and compositions for use therein |
| WO1998032580A1 (en) * | 1997-01-23 | 1998-07-30 | Sunstar Giken Kabushiki Kaisha | Two-pack urethane foam composition, and two-pack urethane foam composition packing apparatus and method |
| US6337355B1 (en) | 1997-01-23 | 2002-01-08 | Sunstar Giken Kabushiki Kaisha | Two-pack urethane foam composition |
| US6866804B2 (en) | 1997-01-23 | 2005-03-15 | Sunstar Suisse Sa | Two-pack urethane foam composition, and two-pack urethane foam composition injecting apparatus and method |
| US7459107B2 (en) | 1997-01-23 | 2008-12-02 | Sunstar Suisse Sa | Two-pack urethane foam composition, and two-pack urethane foam composition injecting apparatus and method |
| JP2004502814A (en) * | 2000-07-05 | 2004-01-29 | ビーエーエスエフ アクチェンゲゼルシャフト | Stabilizers especially for thermoplastic polyurethanes |
| JP2011040599A (en) * | 2009-08-12 | 2011-02-24 | Tdk Corp | Method of manufacturing coil component |
| JP2018095875A (en) * | 2016-12-15 | 2018-06-21 | 東ソー株式会社 | Allophanate group-containing polyisocyanate prepolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07115374B2 (en) | 1995-12-13 |
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