JPH01229023A - Production of rigid polyurethane foam - Google Patents
Production of rigid polyurethane foamInfo
- Publication number
- JPH01229023A JPH01229023A JP63053463A JP5346388A JPH01229023A JP H01229023 A JPH01229023 A JP H01229023A JP 63053463 A JP63053463 A JP 63053463A JP 5346388 A JP5346388 A JP 5346388A JP H01229023 A JPH01229023 A JP H01229023A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- hydroxyl value
- rigid polyurethane
- polyurethane foam
- foam
- 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
- 229920005830 Polyurethane Foam Polymers 0.000 title claims description 15
- 239000011496 polyurethane foam Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 150000003077 polyols Chemical class 0.000 claims abstract description 31
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 10
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000004604 Blowing Agent Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 abstract description 10
- 239000003381 stabilizer Substances 0.000 abstract description 7
- 239000004088 foaming agent Substances 0.000 abstract description 5
- 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 4
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 229920005903 polyol mixture Polymers 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 abstract 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 12
- 229940029284 trichlorofluoromethane Drugs 0.000 description 8
- -1 tertiary amine compounds Chemical class 0.000 description 7
- 238000005187 foaming Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002323 Silicone foam Polymers 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
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 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 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は硬質ポリウレタンフォームの製造方法に関する
ある。さらに詳しくは低温寸法安定性の優れた硬質ポリ
ウレタンフォームの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing rigid polyurethane foam. More specifically, the present invention relates to a method for producing rigid polyurethane foam with excellent low-temperature dimensional stability.
硬質ポリウレタンフォームは、発泡剤としてトリクロロ
フルオロメタン（Ｆ−１１）を使用しているため、断熱
特性に優れ、冷蔵庫、冷凍庫等の保冷材分野で広く使用
されている。Rigid polyurethane foam uses trichlorofluoromethane (F-11) as a blowing agent, so it has excellent heat insulation properties and is widely used in the field of cold insulation materials such as refrigerators and freezers.
近年、地球のオゾン層保護のため、クロロフルオロカー
ボン類の規制が考えられ、近い将来実施に移されようと
している。In recent years, regulations on chlorofluorocarbons have been considered in order to protect the earth's ozone layer, and are expected to be implemented in the near future.
この規制対象には、今まで硬質ポリウレタンフォームの
発泡剤として用いられていた、トリクロロフルオロメタ
ン（Ｆ−１１）も含まれている。This regulation also includes trichlorofluoromethane (F-11), which has been used as a blowing agent for rigid polyurethane foams.
そのためトリクロロフルオロメタン（Ｆ−１１）に替わ
る、硬質ポリウレタンフォーム用発泡剤の開発が必要と
なり、諸物性から見て、ジクロロトリフルオロエタン（
Ｆ−１２３）が代替物の候補と考えられるに到ったと言
われている。Therefore, it is necessary to develop a blowing agent for rigid polyurethane foam to replace trichlorofluoromethane (F-11), and from the viewpoint of various physical properties, dichlorotrifluoroethane (
F-123) is said to have come to be considered as a candidate for replacement.
発泡剤として、ジクロロトリフルオ口エタン（Ｆ−１２
３）を用いた場合、従来のトリクロロフルオロメタン（
Ｆ−１１）を用い発泡したフオームに比べ、
イ）低温寸法安定性が悪い
口）発泡効率が悪い
ハ）初期の反応性が遅い
等の問題点が確認されている。As a blowing agent, dichlorotrifluoroethane (F-12
3), conventional trichlorofluoromethane (
Compared to the foam foamed using F-11), problems such as a) poor low-temperature dimensional stability, poor foaming efficiency, and c) slow initial reactivity have been confirmed.
発泡剤として、ジクロロトリフルオロエタン（Ｆ−１２
３）を用いて断熱材を製造する場合、同一の密度では、
トリクロロフルオロメタンＣＦ−１１）を発泡剤とした
物に比べ、特に低温寸法安定性が劣る欠点があった。Dichlorotrifluoroethane (F-12
3) When manufacturing insulation materials using the same density,
Compared to those using trichlorofluoromethane CF-11) as a blowing agent, there was a drawback in that the low-temperature dimensional stability was particularly poor.
従って、ジクロロトリフルオロエタン（Ｆ−１２３）を
用いる場合、同一の性能を持たせるためには、密度を高
くする必要が有り、従来よりコストの上昇をきたし、実
用的なものではなかった。Therefore, when dichlorotrifluoroethane (F-123) is used, in order to provide the same performance, it is necessary to increase the density, which results in higher costs than in the past, and is not practical.
ジクロロトリフルオロエタン（Ｆ−１２３）がトリクロ
ロフルオロメタン（Ｆ−１１）の代替品と考えられるよ
うになったのは、ごく最近のことであり、前記の様な問
題点があることから、まだ実用に供される物ではなかっ
た。Dichlorotrifluoroethane (F-123) has only recently come to be considered as a substitute for trichlorofluoromethane (F-11), and due to the problems mentioned above, it is still not widely used. It was not intended for practical use.
上記の低温寸法安定性を改良するためには、高い平均官
能基数を有するポリオールを使用する方法が有効である
と考えられるが、従来、この様な高い平均官能基数を有
するポリオールを使用することは、発泡剤（Ｆ−１１）
との相溶性を悪くし、かつ高粘度となって、発泡が困難
となと考えられていた。In order to improve the above-mentioned low-temperature dimensional stability, it is thought that it is effective to use a polyol with a high average number of functional groups, but conventionally, it has not been possible to use polyols with such a high average number of functional groups. , foaming agent (F-11)
It was thought that this would impair the compatibility with the foam and result in a high viscosity, making foaming difficult.
本発明者らは、低温寸法安定性を改良するため、色々検
討した結果、ジクロロトリフルオロエタン（Ｆ−１２３
）は、高い平均官能基数を有する高粘度のポリオールに
も相溶性がよく、かつ高粘度のポリオールの減粘剤とな
って、従来使用できなかった高い平均官能基数を有する
高粘度のポリオールの使用も可能となり、その結果低温
寸法安定性を改良することを知り、漸く本発明に到達で
きた。As a result of various studies to improve low-temperature dimensional stability, the present inventors discovered dichlorotrifluoroethane (F-123
) has good compatibility with high viscosity polyols having a high average number of functional groups, and serves as a viscosity reducing agent for high viscosity polyols, allowing the use of high viscosity polyols having a high average number of functional groups that could not be used in the past. It became possible to improve low-temperature dimensional stability as a result, and the present invention was finally achieved.
即ち本発明は、有機ポリイソシアナート、ポリオール、
発泡剤、触媒その他の助剤を原料として硬質ポリウレタ
ンフォームを製造する方法において、
（ｉ）発泡剤として、ジクロロトリフルオロエタン（Ｆ
−１２３）
（ｉ１）ポリオールとして、
ａ、平均官能基数３．０〜４．５、水酸基価３００〜８
００のポリオールをｌＯ〜９０重量部ｂ、平均官能基数
４．６〜８．０、水酸基価３００〜８００のポリオール
を９０〜１０重量部を使用することを特徴とする硬質ポ
リウレタンフォームの製造方法に関する。That is, the present invention provides organic polyisocyanates, polyols,
In a method for producing rigid polyurethane foam using a blowing agent, a catalyst, and other auxiliaries as raw materials, (i) dichlorotrifluoroethane (F
-123) (i1) As a polyol, a, average functional group number 3.0 to 4.5, hydroxyl value 300 to 8
00 to 90 parts by weight of a polyol having an average functional group number of 4.6 to 8.0 and a hydroxyl value of 300 to 800. .
硬質ポリウレタンフォームを製造するに当り、原料とし
てのポリエーテルポリオールは従来公知の物で、例えば
活性水素原子を２個以上有する化合物（例えば、シュー
クロース、ソルビット、ペンタエリスリトール、グリセ
リン等のポリヒドロキシ化合物、エチレンジアミン、ト
リレンジアミン、ジフェニルメタンジアミン等のアミン
類など）の単体、あるいはその混合物を開始剤とし、そ
れにアルキレンオキサイドを付加重合して得られたもの
が使用される。In producing rigid polyurethane foam, polyether polyols used as raw materials are conventionally known materials, such as compounds having two or more active hydrogen atoms (e.g., polyhydroxy compounds such as sucrose, sorbitol, pentaerythritol, glycerin, etc.). The initiator used is one obtained by addition-polymerizing alkylene oxide with a single amine (such as ethylenediamine, tolylenediamine, diphenylmethanediamine, etc.) or a mixture thereof as an initiator.
本発明に用いるポリオール（ａ）としては、活性水素原
子を分子内に３〜４個有する化合物単体、あるいは活性
水素原子数が異なる数種の化合物を、平均官能基数が３
．０〜４．５になる様に混合したものに、アルキレンオ
キサイドを付加重合した水酸基価３００〜８００の化合
物が挙げられる。As the polyol (a) used in the present invention, a single compound having 3 to 4 active hydrogen atoms in the molecule, or several compounds having different numbers of active hydrogen atoms, with an average functional group number of 3
．． A compound having a hydroxyl value of 300 to 800 obtained by addition polymerization of alkylene oxide may be added to a mixture such that the hydroxyl value is 0 to 4.5.
好ましいものは、平均官能基数が３．３〜４．５、水酸
基価４００〜５００の化合物である。Preferred are compounds having an average number of functional groups of 3.3 to 4.5 and a hydroxyl value of 400 to 500.
本発明に用いるポリオール（ｂ）は、活性水素原子を分
子内に５．６〜８個有する化合物単体あるいは各々活性
水素原子数が異なる数種の化合物を、平均官能基数が４
．６〜８．０になるように混合したものにアルキレンオ
キサイドを付加重合した水酸基価３００〜８００の化合
物が挙げられる。The polyol (b) used in the present invention is a single compound having 5.6 to 8 active hydrogen atoms in the molecule or several compounds each having a different number of active hydrogen atoms, and the average number of functional groups is 4.
．． Examples include compounds having a hydroxyl value of 300 to 800, which are obtained by adding and polymerizing alkylene oxide to a mixture having a hydroxyl value of 6 to 8.0.
好ましいものは、平均官能基数が４．７〜７．５、水酸
基価４００〜５００の化合物である。Preferred are compounds having an average number of functional groups of 4.7 to 7.5 and a hydroxyl value of 400 to 500.
本発明に於ける上記（ａ ）、（ｂ ）の組み合わせ遣
は、ポリオールの合計量に基づいて１０〜９０重量％の
（ａ ） 、９０＝１０の重量％の（ｂ ）を用いるの
が好ましく、特に好ましいのは１０〜５０重量％の（ａ
）１，５０〜９０の重量％の（ｂ ）を用いる組み合わ
せである。In the combination of (a) and (b) in the present invention, it is preferable to use 10 to 90% by weight of (a) and 90=10% by weight of (b) based on the total amount of polyol. , particularly preferred is 10 to 50% by weight of (a
) 1,50-90% by weight of (b).
本発明に於いて使用する有機ポリイソシアナートとして
は、従来公知のもので、特に限定はないく、芳香族、芳
香脂肪族、脂肪族、脂環式ポリイソシアナートおよびそ
れらの変性物、例えばジフェニルメタンジイソシアナー
ト、粗ジフェニルメタンジイソシアナート、トリレンジ
イソシアナート、粗トリレンジイソシアナート、キシリ
レンジイソシアナート、ヘキサメチレンジイソシアナー
ト、イソホロンジイソシアナート、水添ジフェニルメタ
ンジイソシアナート、水添トリレンジイソシアナート、
トリフェニルメチレントリイソシアナート、トリレント
リイソシアナート、変性（カーボンジイミドｅｔｃ ）
ジフェニルメタンジイソシアナート等およびそれらの混
合物ならびにこれらのポリイソシアナートの過剰量とポ
リオール（例えば低分子ポリオール／またはポリマーポ
リオール）とを反応して得られるＮＣＯ末端プレポリマ
ー（ＮＧＯ含有例えば５〜３５％）およびこれらの併用
が挙げられる。The organic polyisocyanates used in the present invention include conventionally known organic polyisocyanates, and are not particularly limited. Diisocyanate, crude diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate ,
Triphenylmethylene triisocyanate, tolylene triisocyanate, modified (carbon diimide etc.)
NCO-terminated prepolymers (NGO content, e.g. 5-35%) obtained by reacting diphenylmethane diisocyanate, etc. and mixtures thereof and excess amounts of these polyisocyanates with polyols (e.g. low-molecular polyols/or polymer polyols) and combinations thereof.
本発明に於いて用いられる発泡剤はジクロロジフルオロ
メタン（Ｆ−１２３） 、メチレンクロライドなどの低
沸点溶剤および／または水などが用いられる。The blowing agent used in the present invention includes dichlorodifluoromethane (F-123), a low boiling point solvent such as methylene chloride, and/or water.
好ましいものは（Ｆ−１２３）と水の併用または（Ｆ−
１２３）単独である。Preferable ones are the combination of (F-123) and water or (F-123) and water.
123) Alone.
触媒としては通常用いられるものが使用でき、第３級ア
ミン化合物、例えばテトラメチルへキサメチレンジアミ
ン、ペンクメチルジエチレントリアミン、ジアザビシク
ロオクタンなど、有機錫化合物例えばジブチル錫ジラウ
レート、オクタン酸第−錫が挙げられる。Commonly used catalysts can be used, including tertiary amine compounds such as tetramethylhexamethylene diamine, pencmethyldiethylenetriamine, and diazabicyclooctane, and organotin compounds such as dibutyltin dilaurate and stannous octoate. It will be done.
整泡剤は従来より用いられるシリコン系整泡剤が使用さ
れる。As the foam stabilizer, a conventionally used silicone foam stabilizer is used.
その他の助剤としては安定剤、充填側、Ｈ燃剤、着色剤
などが挙げられる。Other auxiliary agents include stabilizers, filling agents, H refueling agents, coloring agents, and the like.
本発明を実施するには、ポリオール、触媒、発泡剤、整
泡剤、及び難燃剤その他の助剤類の所定量を混合してレ
ジン液とする。To carry out the present invention, predetermined amounts of a polyol, a catalyst, a blowing agent, a foam stabilizer, a flame retardant, and other auxiliary agents are mixed to form a resin liquid.
ポリウレタン発泡機を使用し、レジン液とポリイソシア
ナートを、一定の比率で連続的に急速混合する。Using a polyurethane foaming machine, resin liquid and polyisocyanate are continuously and rapidly mixed at a fixed ratio.
得られた硬質ポリウレタンフォーム原液を空隙又は型に
注入する。この際、有機ポリイソシアナートと活性水素
含有化合物との当量比が 、０．８〜３．０となる様に
、レジン液とポリイソシアナートとの流量比を調整する
。注入後、数分間で硬質ポリウレタンフォームは発泡硬
化する。The resulting rigid polyurethane foam stock solution is injected into the cavity or mold. At this time, the flow rate ratio of the resin liquid and the polyisocyanate is adjusted so that the equivalent ratio of the organic polyisocyanate and the active hydrogen-containing compound is 0.8 to 3.0. After injection, the rigid polyurethane foam will expand and harden within a few minutes.
発泡剤として、ジクロロトリフルオロメタン（Ｆ−１２
３）を用いた、無公害で実用できる硬質ポリウレタンフ
ォームが製造できる。Dichlorotrifluoromethane (F-12
3), it is possible to produce a rigid polyurethane foam that is pollution-free and can be used for practical purposes.
以下に実施例をかかげて、本発明を具体的に説明する。 The present invention will be specifically described below with reference to Examples.
実施例において、使用した原料は次の通りである。また
部は重量部を示す。In the examples, the raw materials used are as follows. In addition, parts indicate parts by weight.
ＭＯｌ −ＣＲ； 三井東圧化学０菊製粗ジフェニル
メタンジイソシア
ナート ＮＣ０％−３１゜０
ポリオールＡ； 平均官能基数３．５、水酸基価４００
■ＫＯＨ／ｇの芳香族アミ
ン系ポリオール
ポリオールＢ； 平均官能基数４．４、水酸基価４５ｋ
Ｋ ＯＨ／ ｇのショ糖／ア
ミン系ポリオール
ポリオールＣ； 平均官能基数５．６、水酸基価４５０
＋ａｇ Ｋ ＯＨ／ ｇのショ糖系ポリオール
ポリオールＤ； 平均官能基数６．５、水酸基価４５０
■ＫＯＨ／ｇのショ糖系ポ
リオール
ポリオールＥ； 平均官能基数６．２、水酸基価４５０
■ＫＯＨ／ｇのシｇ塘／ア
ミン系ポリオール
ポリオールＦ； 平均官能基数５．５、水酸基価４５０
＋ａｇＫＯＨ／ｇのソルビトー
ル系ポリオール
整泡剤 ； 日本ユニカー製Ｌ−５４２０触媒
； 活材ケミカル製ＭｉｎｉｃｏＴ Ｍ ＨＤ（テ
トラメチルへキサメチレン
ジアミン）
発泡剤 ； 三井デュポンクロロケミカル製トリク
ロロフルオロメタン
（ＦＩＩＡ）
三井デュポンクロロケミカル製
トリクロロフルオロメタン
（Ｆ −１２３）
表−１に示される発泡処方に従って、ポリオールに触媒
、発泡剤および整泡剤を加えたレジン液とイソシアナー
ト成分とを各々２０°Ｃに保ち２液を５００Ｏｒｐｍで
８秒間撹拌混合し２０Ｘ２０Ｘ２０（ｃｍ）の木箱中に
注入し自由発泡させ反応速度を測定した。MOl-CR; Crude diphenylmethane diisocyanate manufactured by Mitsui Toatsu Kagaku Okiku NC0%-31゜0 Polyol A; Average number of functional groups 3.5, hydroxyl value 400
■KOH/g aromatic amine polyol Polyol B; average functional group number 4.4, hydroxyl value 45k
K OH/g sucrose/amine polyol Polyol C; average functional group number 5.6, hydroxyl value 450
+ag K OH/g sucrose-based polyol Polyol D; average functional group number 6.5, hydroxyl value 450
■KOH/g sucrose-based polyol Polyol E; average number of functional groups 6.2, hydroxyl value 450
■KOH/g sig/amine polyol Polyol F; average number of functional groups 5.5, hydroxyl value 450
+agKOH/g sorbitol polyol foam stabilizer; Nippon Unicar L-5420 catalyst
; MinicoTM HD (Tetramethylhexamethylenediamine) manufactured by Active Zai Chemical; Foaming agent; Trichlorofluoromethane (FIIA) manufactured by DuPont Mitsui Chlorochemicals; Trichlorofluoromethane (F-123 manufactured by DuPont Mitsui Chlorochemicals) Foaming shown in Table-1 According to the recipe, a resin solution containing a polyol, a catalyst, a blowing agent, and a foam stabilizer, and an isocyanate component were each kept at 20°C, and the two solutions were stirred and mixed at 500 rpm for 8 seconds, and poured into a 20 x 20 x 20 (cm) wooden box. The reaction rate was measured by allowing free foaming.
また、得られたフオームを常法に従い、サンプリングし
低温試験等の諸物性の測定を行なった。In addition, the obtained foam was sampled and various physical properties such as low temperature tests were measured according to conventional methods.
（比較例１〜３）
発泡剤として（Ｆ−１２３）を用いたものは、Ｆ−１１
を使用したものに比べ、低温寸法安定性が悪い。ポリオ
ールＢを添加しても低温寸法安定性は改良されていない
。(Comparative Examples 1 to 3) Those using (F-123) as a blowing agent were F-11
Poor low temperature dimensional stability compared to those using Addition of polyol B does not improve low temperature dimensional stability.
（実施例１〜８）
発泡剤として（Ｆ−１１）を用いたものは、ポリオール
との相溶性が悪く、発泡が困難である。(Examples 1 to 8) Those using (F-11) as a foaming agent have poor compatibility with polyols and are difficult to foam.
高官能基数を有するポリオールを添加したポリオールと
発泡剤（Ｆ−１２３）を併用することで低温物性を改良
することが可能である。It is possible to improve low-temperature physical properties by using a polyol containing a polyol having a high functional group number together with a blowing agent (F-123).
高官能基数を有するポリオールを、一定割合以上含むポ
リオールと発泡剤（Ｆ−１２３）を併用することにより
、低温寸法安定性の優れた硬質ポリウレタンフォームを
得ることができる。By using a blowing agent (F-123) and a polyol containing a certain proportion or more of a polyol having a high functional group number, a rigid polyurethane foam having excellent low-temperature dimensional stability can be obtained.
特許出願人 三井東圧化学株式会社
手続主甫正書 （自発）
昭和６３年７月８日
硬質ポリウレタンフォームの製造方法
３、補正をする者
事件との関係 特許出願人
住所 東京都千代田区霞が関三丁目２番５号４、補正の
対象
明細書の「発明の詳細な説明の欄」
５、補正の内容Patent Applicant: Mitsui Toatsu Chemical Co., Ltd. Procedural Supervisor's Letter (Spontaneous) July 8, 1985, Rigid Polyurethane Foam Manufacturing Method 3, Relationship with the Amendment Case Patent Applicant Address: Kasumigasekizo, Chiyoda-ku, Tokyo Chome 2-5 No. 4, “Detailed description of the invention column” of the specification to be amended 5. Contents of the amendment
Claims (1)
媒その他の助剤を原料として硬質ポリウレタンフォーム
を製造する方法において、 （ｉ）発泡剤として、ジクロロトリフルオロエタン（Ｆ
−１２３） （ｉｉ）ポリオールとして、 ａ、平均官能基数３．０〜４．５、水酸基価３００〜８
００のポリオールを１０〜９０重量部 ｂ、平均官能基数４．６〜８．０、水酸基価３００〜８
００のポリオールを９０〜１０重量部 を使用することを特徴とする硬質ポリウレタンフォーム
の製造方法。[Claims] 1) A method for producing rigid polyurethane foam using organic polyisocyanates, polyols, blowing agents, catalysts and other auxiliaries as raw materials, including: (i) dichlorotrifluoroethane (F) as a blowing agent;
-123) (ii) As a polyol, a, average functional group number 3.0 to 4.5, hydroxyl value 300 to 8
00 polyol 10 to 90 parts by weight b, average functional group number 4.6 to 8.0, hydroxyl value 300 to 8
1. A method for producing a rigid polyurethane foam, characterized in that 90 to 10 parts by weight of polyol No. 00 is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053463A JPH01229023A (en) | 1988-03-09 | 1988-03-09 | Production of rigid polyurethane foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053463A JPH01229023A (en) | 1988-03-09 | 1988-03-09 | Production of rigid polyurethane foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01229023A true JPH01229023A (en) | 1989-09-12 |
Family
ID=12943554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63053463A Pending JPH01229023A (en) | 1988-03-09 | 1988-03-09 | Production of rigid polyurethane foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01229023A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03121117A (en) * | 1989-07-14 | 1991-05-23 | Takeda Chem Ind Ltd | Production of low-density rigid urethane foam |
| JPH05306880A (en) * | 1992-04-10 | 1993-11-19 | Sanyo Electric Co Ltd | Heat insulating box body employing hard polyurethane |
-
1988
- 1988-03-09 JP JP63053463A patent/JPH01229023A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03121117A (en) * | 1989-07-14 | 1991-05-23 | Takeda Chem Ind Ltd | Production of low-density rigid urethane foam |
| JPH05306880A (en) * | 1992-04-10 | 1993-11-19 | Sanyo Electric Co Ltd | Heat insulating box body employing hard polyurethane |
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