JPH03745A - Preparation of foamed synthetic resin - Google Patents
Preparation of foamed synthetic resinInfo
- Publication number
- JPH03745A JPH03745A JP13460489A JP13460489A JPH03745A JP H03745 A JPH03745 A JP H03745A JP 13460489 A JP13460489 A JP 13460489A JP 13460489 A JP13460489 A JP 13460489A JP H03745 A JPH03745 A JP H03745A
- Authority
- JP
- Japan
- Prior art keywords
- compd
- synthetic resin
- foamed synthetic
- active hydrogen
- compound
- 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
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 15
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000004604 Blowing Agent Substances 0.000 claims description 25
- -1 hydrogen compound Chemical class 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 12
- 239000011496 polyurethane foam Substances 0.000 abstract description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 3
- 150000003973 alkyl amines Chemical class 0.000 abstract description 2
- YPJHKJFGSWJFTM-UHFFFAOYSA-N 1,1,1-trifluoro-n,n-bis(trifluoromethyl)methanamine Chemical compound FC(F)(F)N(C(F)(F)F)C(F)(F)F YPJHKJFGSWJFTM-UHFFFAOYSA-N 0.000 abstract 1
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 description 22
- 150000003077 polyols Chemical class 0.000 description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000006260 foam Substances 0.000 description 11
- 150000008282 halocarbons Chemical class 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 6
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002483 hydrogen compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000768 polyamine Chemical class 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 229920002323 Silicone foam Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004872 foam stabilizing agent Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229920000582 polyisocyanurate Polymers 0.000 description 2
- 239000011495 polyisocyanurate Substances 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000013514 silicone foam Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 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
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 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 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、ポリウレタンフォームなどの発泡合成樹脂を
製造する方法に関するものであり、特に特定の発泡剤の
使用を特徴とする発泡合成樹脂の製造方法に関するもの
である。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing a foamed synthetic resin such as a polyurethane foam, and in particular a method for producing a foamed synthetic resin characterized by the use of a specific blowing agent. It is about the method.
[従来の技術]
イソシアネート基と反応しうる活性水素含有基を2以上
有する活性水素化合物とポリイソシアネート化合物とを
触媒と発泡剤の存在下に反応させて発泡合成樹脂を製造
することは広く行なわれている。活性水素化合物として
はたとえば、ポリヒドロキシ化合物やポリアミン化合物
がある。得られる発泡合成樹脂としては、たとえばポリ
ウレタンフォーム、ポリイソシアヌレートフオーム、ポ
リウレアフオームなどがある。また、比較的低発泡の発
泡合成樹脂としては、たとえばマイクロセルラーポリウ
レタンエラストマーやマイクロセルラーポリウレタンウ
レアエラストマーなどがある。[Prior Art] It is widely practiced to produce a foamed synthetic resin by reacting an active hydrogen compound having two or more active hydrogen-containing groups capable of reacting with an isocyanate group with a polyisocyanate compound in the presence of a catalyst and a blowing agent. ing. Examples of active hydrogen compounds include polyhydroxy compounds and polyamine compounds. Examples of the resulting foamed synthetic resin include polyurethane foam, polyisocyanurate foam, and polyurea foam. In addition, examples of foamed synthetic resins with relatively low foaming include microcellular polyurethane elastomer and microcellular polyurethane urea elastomer.
上記発泡合成樹脂を製造するための発泡剤としては種々
の化合物が知られているが、主にはトリクロロフルオロ
メタン(R−11)が使用されている。また、通常R−
11とともにさらに水が併用される。さらに、フロス法
等で発泡を行う場合には、これらとともにより低沸点の
(常温常圧下で気体の)ジクロロジフルオロメタン(R
−12)が併用されている。さらに他の比較的低沸点の
塩素化フッ素化炭化水素類が発泡剤として使用すること
ができるという提案は種々提出されているが、上記R−
11とR−12を除いてはいまだ広く使用されるには至
っていない。また、塩素化フッ素化炭化水素系発泡剤の
代りに塩化メチレンなどの他の低沸点ハロゲン化炭化水
素系発泡剤の使用も提案されている。Although various compounds are known as blowing agents for producing the above-mentioned foamed synthetic resin, trichlorofluoromethane (R-11) is mainly used. Also, usually R-
Water is further used in combination with 11. Furthermore, when foaming is carried out by the froth method etc., dichlorodifluoromethane (R
-12) is used in combination. Various proposals have been made that other relatively low-boiling chlorinated fluorinated hydrocarbons can be used as blowing agents;
With the exception of No. 11 and R-12, they have not yet come into widespread use. It has also been proposed to use other low boiling point halogenated hydrocarbon blowing agents, such as methylene chloride, in place of the chlorinated fluorinated hydrocarbon blowing agents.
[発明の解決しようとする課題]
従来広く使用されていたR−11やR−12などの大気
中で極めて安定な塩素化フッ素化炭化水素は分解されな
いまま大気層上空のオゾン層にまで達してそこで紫外線
などの作用で分解され、その分解物がオゾン層を破壊す
るのではないかと考えられるようになった。発泡剤とし
て使用された上記のような塩素化フッ素化炭化水素は、
その一部が大気中に漏出するため、その使用はオゾン層
破壊の原因の一部になるのではないかと危惧されている
。従って、このようなR−11やR−12に代えてそれ
よりオゾン層破壊のおそれの少ない発泡剤の開発が望ま
れる。[Problems to be solved by the invention] Chlorinated fluorinated hydrocarbons that are extremely stable in the atmosphere, such as R-11 and R-12, which have been widely used in the past, reach the ozone layer above the atmospheric layer without being decomposed. Therefore, it was thought that it would be decomposed by the effects of ultraviolet rays, etc., and that the decomposed products could destroy the ozone layer. Chlorinated fluorinated hydrocarbons such as those mentioned above used as blowing agents,
Because some of it leaks into the atmosphere, there are concerns that its use could be part of the cause of ozone layer depletion. Therefore, in place of R-11 and R-12, it is desired to develop a blowing agent that is less likely to cause ozone layer depletion.
[課題を解決するための手段]
本発明は前述の問題点を解決すべくなされた下記の発明
を提供するものである。[Means for Solving the Problems] The present invention provides the following inventions that have been made to solve the above-mentioned problems.
インシアネート基と反応しつる活性水素含有官能基を2
以上有する活性水素化合物とポリイソシアネート化合物
とを低沸点有機化合物発泡剤の存在下に反応させて発泡
合成樹脂を製造する方法において、低沸点有機化合物系
発泡剤として窒素原子を含むポリフルオロ化合物を使用
することを特徴とする発泡合成樹脂の製造方法。2 active hydrogen-containing functional groups that react with incyanate groups
In a method for producing a foamed synthetic resin by reacting an active hydrogen compound having the above and a polyisocyanate compound in the presence of a low-boiling organic compound blowing agent, a polyfluoro compound containing a nitrogen atom is used as the low-boiling organic compound blowing agent. A method for producing a foamed synthetic resin characterized by:
本発明における窒素原子を含むポリフルオロ化合物とし
ては、次式によって表されるアルキルアミン類を挙げる
ことができる。Examples of the polyfluoro compound containing a nitrogen atom in the present invention include alkylamines represented by the following formula.
具体例として、 (CFa)、N (b、p、−6℃)
、(CFs)JCtF−(b、p、−21”C)、(C
Js)aN (b、p。As a specific example, (CFa), N (b, p, -6℃)
, (CFs)JCtF-(b,p,-21"C), (C
Js) aN (b, p.
70℃)などがあげられる。70℃).
その他は下記の式で表されるポリフルオロアゾ化合物類
も使用できる。In addition, polyfluoroazo compounds represented by the following formulas can also be used.
C+F+an+tlN”:’NCa1Fl*s*t+
n、m=1〜5具体例として、CFsN=NCFs、
CIFsN=NC,F。C+F+an+tlN":'NCa1Fl*s*t+
n, m=1 to 5 As a specific example, CFsN=NCFs,
CIFsN=NC,F.
などがあげられる。etc.
本発明における発泡剤である前記含フツ素化合物は塩素
原子を持たない化合物であることにより、前記オゾン層
破壊のおそれは少ないと考えられる。さらにその沸点が
R−11に近いのでそれに代る発泡剤として使用できる
ものである。Since the fluorine-containing compound that is the blowing agent in the present invention is a compound that does not have a chlorine atom, it is thought that there is little risk of the ozone layer being destroyed. Furthermore, since its boiling point is close to that of R-11, it can be used as a blowing agent in place of R-11.
本発明における前記含フツ素化合物系発泡剤はそれらの
み使用することは勿論、他の発泡剤と併用することがで
きる。特に水は多くの場合前記含フツ素化合物系発泡剤
と併用される。水辺外の他の併用しつる発泡剤としては
、たとえば現行の発泡剤であるR−11やR−12、そ
の他の低沸点ハロゲン化炭化水素、低沸点炭化水素、不
活性ガスなどがある。R−11やR−12はそれ自身は
オゾン層破壊の原因となるおそれはあるものの、本発明
における発泡剤との併用によりその使用量を減らすこと
ができる。その他の低沸点ハロゲン化炭化水素としては
、塩化メチレンなどのフッ素原子を含まないハロゲン化
炭化水素や前記以外の含フツ素ハロゲン化炭化水素があ
る。低沸点炭化水素としてはブタンやヘキサンが、不活
性ガスとしては空気や窒素などがある。The fluorine-containing compound blowing agents in the present invention may be used alone or in combination with other blowing agents. In particular, water is often used in combination with the fluorine-containing compound blowing agent. Examples of other blowing agents that can be used in combination with other than waterside blowing agents include current blowing agents R-11 and R-12, other low-boiling halogenated hydrocarbons, low-boiling hydrocarbons, and inert gases. Although R-11 and R-12 themselves may cause ozone layer destruction, their usage can be reduced by using them in combination with the blowing agent in the present invention. Other low-boiling halogenated hydrocarbons include halogenated hydrocarbons that do not contain fluorine atoms, such as methylene chloride, and fluorine-containing halogenated hydrocarbons other than those mentioned above. Low-boiling hydrocarbons include butane and hexane, and inert gases include air and nitrogen.
イソシアネート基と反応しつる活性水素含有官能基を2
以上有する活性水素化合物としては、水酸基やアミノ基
などの活性水素含有官能基を2以上有する化合物、ある
いはその化合物の2種以上の混合物である。特に、2以
上の水酸基を有する化合物やその混合物、またはそれを
主成分としさらにポリアミンなどを含む混合物が好まし
い。2以上の水酸基を有する化合物としては、広(使用
されているポリオールが好ましいが、2以上のフェノー
ル性水酸基を有する化合物(たとえばフェノール樹脂初
期縮合物)なども使用できる。ポリオールとしては、ポ
リエーテル系ポリオール、ポリエステル系ポリ叶−ル、
多価アルコール、水酸基含有ジエチレン系ポリマーなど
がある。特にポリエーテル系ポリオールの1種以上のみ
からなるか、それを主成分としてポリエステル系ポリオ
ール、多価アルコール、ポリアミン、アルカノールアミ
ン、その他の活性水素化合物との併用が好ましい。ポリ
エーテル系ポリオールとしては、多価アルコール、糖類
、アルカノールアミン、その他のイニシェークーに環状
エーテル、特にプロピレンオキシドやエチレンオキシド
などのアルキレンオキシドを付加して得られるポリエー
テル系ポリオールが好ましい。また、ポリオールとして
ポリマーポリオールあるいはグラフトポリオールと呼ば
れる主にポリエーテル系ポリオール中にビニルポリマー
の微粒子が分散したポリオール組成物を使用することも
できる。ポリエステル系ポリオールとしては、多価アル
コール−多価カルボン酸縮合系のポリオールや環状エス
テル開環重合体系のポリオールがあり、多価アルコール
としてはエチレングリコール、プロピレングリコール、
ジエチレングリコール、ジプロピレングリコール、グリ
セリン、トリメチロールプロパン、ペンタエリスリトー
ル、ジェタノールアミン、トリエタノールアミンなどが
ある。2以上のフェノール性水酸基を有する化合物とし
ては、フェノール類をアルカリ触媒の存在下で過剰のホ
ルムアルデヒド類と縮合結合させたレゾール型初期縮合
物、レゾール型初期縮合物を合成する際、非水系で反応
させたベンジリック型初期縮合物、過剰のフェノール類
を酸触媒の存在下でホルムアルデヒド類を反応させたノ
ボラック型初期縮合物等がある。これらの初期縮合物の
分子量は200〜10000のものが好ましい。ここで
フェノール類のはベンゼン環を形成する骨格の一個以上
の炭素原子が直接水酸基と結合したものを意味しその同
一構造内に他の置換結合基を有するものも含まれる。代
表的なものとしてはフェノール、クレゾール、ビスフェ
ノールA、レゾルシノール等がある。また、ホルムアル
デヒド類は特に限定しないがホルマリン、バラホルムア
ルデヒドが好ましい。ポリオールあるいは活性水素化合
物水素の混合物の水酸基価は約20〜1000のものか
ら目的に応じて選択されることが多い。2 active hydrogen-containing functional groups that react with isocyanate groups.
The active hydrogen compound having the above is a compound having two or more active hydrogen-containing functional groups such as a hydroxyl group or an amino group, or a mixture of two or more such compounds. Particularly preferred are compounds having two or more hydroxyl groups, mixtures thereof, or mixtures containing the same as the main component and further containing polyamine or the like. As the compound having two or more hydroxyl groups, polyols used in Hiroshima are preferred, but compounds having two or more phenolic hydroxyl groups (for example, phenol resin initial condensates) can also be used.As the polyols, polyether-based Polyol, polyester polyol,
Examples include polyhydric alcohols and diethylene polymers containing hydroxyl groups. In particular, it is preferable to use only one or more types of polyether polyols, or to use them as a main component in combination with polyester polyols, polyhydric alcohols, polyamines, alkanolamines, and other active hydrogen compounds. The polyether polyol is preferably a polyether polyol obtained by adding a cyclic ether, particularly an alkylene oxide such as propylene oxide or ethylene oxide, to a polyhydric alcohol, saccharide, alkanolamine, or other initiator. Further, as the polyol, it is also possible to use a polyol composition called a polymer polyol or a graft polyol, in which fine particles of a vinyl polymer are dispersed in a mainly polyether polyol. Polyester polyols include polyhydric alcohol-polycarboxylic acid condensation polyols and cyclic ester ring-opening polymer polyols, and polyhydric alcohols include ethylene glycol, propylene glycol,
These include diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, jetanolamine, and triethanolamine. Compounds having two or more phenolic hydroxyl groups include resol-type initial condensates in which phenols are condensed and bonded with excess formaldehyde in the presence of an alkali catalyst; There are benzylic-type precondensates made by reacting excess phenols with formaldehyde in the presence of an acid catalyst, and novolac-type precondensates. The molecular weight of these initial condensates is preferably 200 to 10,000. Here, phenols mean those in which one or more carbon atoms of the skeleton forming a benzene ring are directly bonded to a hydroxyl group, and also include those having other substituent bonding groups within the same structure. Typical examples include phenol, cresol, bisphenol A, and resorcinol. Further, the formaldehyde is not particularly limited, but formalin and formaldehyde are preferable. The hydroxyl value of the polyol or the mixture of active hydrogen compound hydrogen is often selected from about 20 to 1000 depending on the purpose.
ポリイソシアネート化合物としてはイソシアネート基を
2以上有する芳喬族系、脂環族系、あるいは脂肪族系の
ポリイソシアネート、それら2種以上の混合物、および
それらを変性して得られる変性ポリイソシアネートがあ
る。具体的には、たとえば、トリレンジイソシアネート
、ジフェニルメタンジイソシアネート、ポリメチレンポ
リフェニルイソシアネート(通称:クルードMDI)キ
シリレンジイソシアネート、イソホロンジイソシアネー
ト、ヘキサメチレンジイソシアネートなどのポリイソシ
アネートやそれらのプレポリマー型変性体、ヌレート変
性体、ウレア変性体などがある。Examples of the polyisocyanate compound include aromatic, alicyclic, or aliphatic polyisocyanates having two or more isocyanate groups, mixtures of two or more thereof, and modified polyisocyanates obtained by modifying them. Specifically, for example, polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate (commonly known as crude MDI), xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, prepolymer type modified products thereof, and nurate modified products. body, urea denatured body, etc.
活性水素化合物とポリイソシアネート化合物を反応させ
る際、通常触媒の使用が必要とされる。触媒としては、
活性水素含有基とインシアネート基の反応を促進させる
有機スズ化合物などの金属化合物系触媒やトリエチレン
ジアミンなどの3級アミン触媒が使用される。また、カ
ルボン酸金属塩などのイソシアネート基同志を反応させ
る多量化触媒が目的に応じて使用される。さらに、良好
な気泡を形成するための整泡剤も多くの場合使用される
。整泡剤としては、たとえばシリコーン系整泡剤や含フ
ツ素化合物系整泡剤などがある。その他、任意に使用し
つる配合剤としては、たとえば充填剤、安定剤、着色剤
、難燃剤などがある。When reacting active hydrogen compounds and polyisocyanate compounds, the use of catalysts is usually required. As a catalyst,
Metal compound catalysts such as organotin compounds and tertiary amine catalysts such as triethylenediamine are used, which promote the reaction between active hydrogen-containing groups and incyanate groups. Further, a polymerization catalyst that causes isocyanate groups to react with each other, such as a carboxylic acid metal salt, is used depending on the purpose. Furthermore, foam stabilizers are often used to form good foam. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. Other optional additives include fillers, stabilizers, colorants, flame retardants, and the like.
これら原料を使用し、ポリウレタンフォーム、ウレタン
変性ポリイソシアネレートフォーム、マイクロセルラー
ポリウレタンエラストマー、マイクロセルラーポリウレ
タンウレアエラストマー、マイクロセルラーポリウレア
エラストマー、その他の発泡合成樹脂が得られる。Using these raw materials, polyurethane foam, urethane-modified polyisocyanate foam, microcellular polyurethane elastomer, microcellular polyurethane urea elastomer, microcellular polyurea elastomer, and other foamed synthetic resins can be obtained.
ポリウレタンフォームは大別して硬質ポリウレタンフオ
ーム、半硬質ポリウレタンフォーム、軟質ポリウレタン
フォームがある。本発明は、特にハロゲン化炭化水素系
発泡剤の使用量の多い分野である硬質ポリウレタンフォ
ーム、ウレタン変性ポリイソシアヌレートフオーム、そ
の他の硬質フオームの製造において特に有用である。そ
の内でも、水酸基価的200〜1000のポリオールあ
るいはポリオール混合物と芳香族系のポリイソシアネー
ト化合物を使用して得られる硬質ポリウレタンフォーム
の製造において特に有用である。これら硬質フオームを
製造する場合、本発明におけるハロゲン化炭化水素系発
泡剤の使用量は、活性水素化合物に対して、5〜150
重量%、特に20〜60重量%が適当である。また、そ
れとともに、水を活性水素化合物に対して0〜10童量
%、特に1〜5重量%使用することが好ましい。一方、
軟質ポリウレタンフォームや半硬質ポリウレタンフォー
ム、マイクロセルラーエラストマーの場合には、本発明
におけるハロゲン化炭化水素発泡剤は活性水素化合物に
対して5〜150重量%の使用が好ましい。軟質ウレタ
ンフオーム、半硬質ウレタンフオームの場合水を0〜1
0重量%、マイクロセルラーエラストマーの場合には水
を0〜5重量%併用することが好ましい。Polyurethane foam can be broadly divided into rigid polyurethane foam, semi-rigid polyurethane foam, and flexible polyurethane foam. The present invention is particularly useful in the production of rigid polyurethane foams, urethane-modified polyisocyanurate foams, and other rigid foams, which are fields in which halogenated hydrocarbon blowing agents are used in large quantities. Among these, it is particularly useful in the production of rigid polyurethane foam obtained by using a polyol or polyol mixture having a hydroxyl value of 200 to 1000 and an aromatic polyisocyanate compound. When producing these hard foams, the amount of halogenated hydrocarbon blowing agent used in the present invention is 5 to 150% based on the active hydrogen compound.
Weight percentages are suitable, especially 20 to 60 weight percent. In addition, it is preferable to use water in an amount of 0 to 10% by weight, particularly 1 to 5% by weight, based on the active hydrogen compound. on the other hand,
In the case of flexible polyurethane foam, semi-rigid polyurethane foam, and microcellular elastomer, the halogenated hydrocarbon blowing agent in the present invention is preferably used in an amount of 5 to 150% by weight based on the active hydrogen compound. For soft urethane foam and semi-hard urethane foam, add 0 to 1 of water.
In the case of a microcellular elastomer, it is preferable to use water in an amount of 0 to 5% by weight.
以下、実施例により本発明を具体的に説明するが、本発
明はこれら実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
[実施例]
下記のポリオールについて本発明におけるハロゲン化炭
化水素系発泡剤の発泡評価を行なった。[Example] Foaming evaluation of the halogenated hydrocarbon blowing agent in the present invention was conducted for the following polyols.
ポリオ−ルミ:グリセリンにプロピレンオキシドを反応
させた水酸基価420のポリエーテルポリオール
ボリオールb:シェークロースにプロピレンオシドとエ
チレンオキシドを反応させた水酸基価450のポリエー
テルポリオール
ポリオールc:トルエンジアミンにプロピレンキシドを
反応させた水酸基価440のポリエーテルポリオール
発泡評価は次の様に行なった。ポリオール100重量部
にに対し、シリコーン系整泡剤(信越化学■ 商品名
F−338)を2部、水1部、触媒としてN、N−ジメ
チルシクロヘキシルアミンをゲルタイム45秒とするた
めの必要量、下記に示す発泡剤適当量の混合液とポリメ
チレンポリフェニルイソシアネート(MD化成■ 商品
名PAP1135)を液温20’Cで混合し、200+
++mX 200mggX 200ma+の木製のボッ
クス内に投入、発泡させ評価した。Polyolumi: A polyether polyol with a hydroxyl value of 420 made by reacting glycerin with propylene oxide Polyol b: A polyether polyol with a hydroxyl value of 450 made by reacting propylene oxide with shaken rose and ethylene oxide Polyol C: Propylene oxide with toluene diamine The foaming evaluation of polyether polyol having a hydroxyl value of 440 was carried out as follows. For 100 parts by weight of polyol, silicone foam stabilizer (Shin-Etsu Chemical ■ trade name)
A mixture of 2 parts of F-338), 1 part of water, the necessary amount of N,N-dimethylcyclohexylamine as a catalyst to give a gel time of 45 seconds, an appropriate amount of the blowing agent shown below, and polymethylene polyphenylisocyanate (MD Chemical ■Product name PAP1135) was mixed at a liquid temperature of 20'C, and the mixture was heated to 200+
It was placed in a ++mX 200mgX 200ma+ wooden box and foamed for evaluation.
また、比較例としてR−11を同様に発泡し評価した。Further, as a comparative example, R-11 was similarly foamed and evaluated.
なお発泡剤の使用量は発泡体のコア密度が30±2 k
g/m”となるよう調整した。The amount of foaming agent used is determined when the core density of the foam is 30±2K.
g/m".
結果を表1に示す。The results are shown in Table 1.
判定の規準は次の通りである。The criteria for judgment are as follows.
0 : R−11と同等以上
△: R−11よりやや劣る
x : R−11より劣る
表 1
発泡剤; (CFs)JCaFs
表 2
発泡剤; (CaFs)sN
[発明の効果コ
本発明は、オゾン層破壊のおそれのあるR−11などの
塩素化フッ素化炭化水素を実質的に使用することな(良
好な発泡合成樹脂を製造することができるものである。0: Equivalent to or better than R-11 Δ: Slightly inferior to R-11 x: Inferior to R-11 Table 1 Foaming agent; (CFs) JCaFs Table 2 Foaming agent; It is possible to produce a good foamed synthetic resin without substantially using chlorinated fluorinated hydrocarbons such as R-11, which may cause ozone layer depletion.
Claims (1)
を2以上有する活性水素化合物とポリイソシアネート化
合物とを低沸点有機化合物発泡剤の存在下に反応させて
発泡合成樹脂を製造する方法において、低沸点有機化合
物系発泡剤として窒素原子を含むポリフルオロ化合物を
使用することを特徴とする発泡合成樹脂の製造方法。1. In a method for producing a foamed synthetic resin by reacting an active hydrogen compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group with a polyisocyanate compound in the presence of a low-boiling point organic compound blowing agent, A method for producing a foamed synthetic resin, characterized in that a polyfluoro compound containing a nitrogen atom is used as an organic compound foaming agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13460489A JPH03745A (en) | 1989-05-30 | 1989-05-30 | Preparation of foamed synthetic resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13460489A JPH03745A (en) | 1989-05-30 | 1989-05-30 | Preparation of foamed synthetic resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03745A true JPH03745A (en) | 1991-01-07 |
Family
ID=15132287
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13460489A Pending JPH03745A (en) | 1989-05-30 | 1989-05-30 | Preparation of foamed synthetic resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03745A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0518127A1 (en) * | 1991-06-13 | 1992-12-16 | BASF Aktiengesellschaft | Process for producing cellular synthetics using the polyisocyanate-polyaddition process and with an emulsion containing (per)fluorinated tertiary alkylamines as blowing agent |
US5240965A (en) * | 1991-04-03 | 1993-08-31 | Imperial Chemical Industries Plc | Manufacture of cellular polymers and compositions therefor |
US5391584A (en) * | 1991-04-03 | 1995-02-21 | Imperial Chemical Industries Plc | Manufacture of rigid foams and compositions therefor |
US5604265A (en) * | 1993-11-30 | 1997-02-18 | Imperial Chemical Industries Plc | Process for rigid polyurethane foams |
WO1999027802A1 (en) * | 1997-11-28 | 1999-06-10 | Han Kook Sin Yak Pharm. Co., Ltd. | HEALTH BEVERAGE CONTAINING THE EXTRACT OF $i(PHELLINUS LINTEUS) |
US6303686B1 (en) | 1996-09-25 | 2001-10-16 | Daikin Industries Ltd. | Resin composition having water and oil repellency |
WO2004051119A1 (en) * | 2002-11-29 | 2004-06-17 | Mahle Gmbh | Piston-pin boss of a piston for an internal combustion engine |
-
1989
- 1989-05-30 JP JP13460489A patent/JPH03745A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5240965A (en) * | 1991-04-03 | 1993-08-31 | Imperial Chemical Industries Plc | Manufacture of cellular polymers and compositions therefor |
US5368769A (en) * | 1991-04-03 | 1994-11-29 | Imperial Chemical Industries Plc | Manufacture of cellular polymers and compositions therefor |
US5391584A (en) * | 1991-04-03 | 1995-02-21 | Imperial Chemical Industries Plc | Manufacture of rigid foams and compositions therefor |
EP0518127A1 (en) * | 1991-06-13 | 1992-12-16 | BASF Aktiengesellschaft | Process for producing cellular synthetics using the polyisocyanate-polyaddition process and with an emulsion containing (per)fluorinated tertiary alkylamines as blowing agent |
US5604265A (en) * | 1993-11-30 | 1997-02-18 | Imperial Chemical Industries Plc | Process for rigid polyurethane foams |
US5698606A (en) * | 1993-11-30 | 1997-12-16 | Imperial Chemical Industries Plc | Process for rigid polyurethane foams |
US6303686B1 (en) | 1996-09-25 | 2001-10-16 | Daikin Industries Ltd. | Resin composition having water and oil repellency |
WO1999027802A1 (en) * | 1997-11-28 | 1999-06-10 | Han Kook Sin Yak Pharm. Co., Ltd. | HEALTH BEVERAGE CONTAINING THE EXTRACT OF $i(PHELLINUS LINTEUS) |
WO2004051119A1 (en) * | 2002-11-29 | 2004-06-17 | Mahle Gmbh | Piston-pin boss of a piston for an internal combustion engine |
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