JP2536593B2 - Method for producing phenolic resin foam - Google Patents
Method for producing phenolic resin foamInfo
- Publication number
- JP2536593B2 JP2536593B2 JP12998788A JP12998788A JP2536593B2 JP 2536593 B2 JP2536593 B2 JP 2536593B2 JP 12998788 A JP12998788 A JP 12998788A JP 12998788 A JP12998788 A JP 12998788A JP 2536593 B2 JP2536593 B2 JP 2536593B2
- Authority
- JP
- Japan
- Prior art keywords
- foam
- resin
- molecular weight
- resole
- resol
- 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.)
- Expired - Lifetime
Links
- 239000006260 foam Substances 0.000 title claims description 58
- 239000005011 phenolic resin Substances 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title description 16
- 229920001568 phenolic resin Polymers 0.000 title description 16
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 3
- 229920003987 resole Polymers 0.000 description 36
- 239000011134 resol-type phenolic resin Substances 0.000 description 13
- 238000005187 foaming Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 methylol group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229920005546 furfural resin Polymers 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- UGCSPKPEHQEOSR-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1,2-difluoroethane Chemical compound FC(Cl)(Cl)C(F)(Cl)Cl UGCSPKPEHQEOSR-UHFFFAOYSA-N 0.000 description 1
- BAMUEXIPKSRTBS-UHFFFAOYSA-N 1,1-dichloro-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Cl)Cl BAMUEXIPKSRTBS-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 1
- FJSRPVWDOJSWBX-UHFFFAOYSA-N 1-chloro-4-[1-(4-chlorophenyl)-2,2,2-trifluoroethyl]benzene Chemical compound C=1C=C(Cl)C=CC=1C(C(F)(F)F)C1=CC=C(Cl)C=C1 FJSRPVWDOJSWBX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 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
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、建築構造物や温，冷水配管、浴槽タンク等
の断熱材、鉄道車輌等の断熱や気密性保持を目的とした
床下地材などとして好適に利用されるフェノール樹脂発
泡体の製造方法に関し、特に現場スプレー発泡施工に有
用なレゾール系フェノール樹脂発泡体の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a building structure, a heat insulating material for hot and cold water pipes, a bath tank, etc., a floor base material for the purpose of heat insulating and maintaining airtightness of railway vehicles, etc. The present invention relates to a method for producing a phenol resin foam that is preferably used, and particularly to a method for producing a resol-based phenol resin foam that is useful for on-site spray foaming.
従来の技術及び発明が解決しようとする課題 周知のように、レゾール系フェノール樹脂発泡体は、
液状のレゾール型フェノール樹脂に発泡剤、整泡剤及び
酸性硬化剤を加えて攪拌混合し、樹脂化反応の進行と同
時に発泡させることにより製造される。As is well known, the prior art and the problems to be solved by the invention are resol-based phenol resin foams,
It is produced by adding a foaming agent, a foam stabilizer and an acidic curing agent to a liquid resol-type phenol resin, stirring and mixing, and foaming at the same time as the progress of the resinification reaction.
しかしながら、一般にレゾール系フェノール樹脂発泡
体は、重縮合反応を利用して製造されるため、発泡硬化
に長時間を要するという問題点がある。更に、従来のレ
ゾール型フェノール樹脂発泡体は固くて脆いという性質
を有しており、得られる発泡体は合板、クラフト紙、石
膏ボード等の各種面材やコンクリート等の躯体などに対
する接着性が悪いという欠点を有している。However, since a resol-based phenol resin foam is generally produced by using a polycondensation reaction, there is a problem that it takes a long time to foam and cure. Furthermore, conventional resole type phenolic resin foams have the property of being hard and brittle, and the resulting foams have poor adhesion to various face materials such as plywood, kraft paper, gypsum board, etc. It has the drawback of
このため、レゾール系フェノール樹脂発泡体は、特
に、従来より硬質ウレタン樹脂発泡体を用いている現場
スプレー発泡施工において、硬質ウレタン樹脂発泡体の
代用として利用することは極めて困難であり、実用性に
劣るものであった。Therefore, the resole phenolic resin foam is extremely difficult to use as a substitute for the rigid urethane resin foam, especially in the field spray foaming construction where the rigid urethane resin foam is conventionally used. It was inferior.
本発明は上記事情に鑑みなされたもので、短時間で発
泡硬化し、かつ各種面材やコンクリート躯体等との接着
性に優れた現場スプレー発泡施工可能なレゾール系フェ
ノール樹脂発泡体の製造方法を提供することを目的とす
る。The present invention has been made in view of the above circumstances, a method for producing a resol-based phenolic resin foam capable of foaming and curing in a short time, and having excellent adhesiveness with various face materials and concrete frames, etc., which can be subjected to on-site spray foaming construction. The purpose is to provide.
課題を解決するための手段及び作用 本発明者らは上記目的を達成するため鋭意検討を重ね
た結果、レゾール型フェノール樹脂、発泡剤、硬化剤を
配合してなる発泡体原料を用いてレゾール系フェノール
樹脂発泡体を製造するにあたり、レゾール型フェノール
樹脂として数平均分子量200未満の低分子量レゾール型
フェノール樹脂と数平均分子量200以上の高分子量レゾ
ール型フェノール樹脂とを重量比で5/95〜80/20、好ま
しくは10/90〜60/40の割合で混合して使用した場合、発
泡硬化時間が短く、かつ優れた接着性を有するレゾール
系フェノール樹脂発泡体を製造することができることを
見い出した。Means and Actions for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a resole-type phenol resin, a foaming agent, and a resol-based foam raw material prepared by blending a curing agent are used. In producing a phenolic resin foam, a low-molecular-weight resol-type phenolic resin having a number-average molecular weight of less than 200 and a high-molecular-weight resol-type phenolic resin having a number-average molecular weight of 200 or more as a resole-type phenolic resin are contained in a weight ratio of 5/95 to 80 /. It has been found that when mixed and used in a ratio of 20, preferably 10/90 to 60/40, a resole phenolic resin foam having a short foaming and curing time and excellent adhesiveness can be produced.
即ち、本発明者らは、レゾール系フェノール樹脂発泡
体の原料として高分子量のレゾール型フェノール樹脂を
使用すると、得られる発泡体の接着性が大幅に向上する
ものの、活性メチロール基濃度が低下して発泡硬化時間
が極めて長くなるが、レゾール型フェノール樹脂として
数平均分子量が200未満の低分子量樹脂と数平均分子量
が200以上の高分子量樹脂とを組合せ、かつ両樹脂を上
記特定割合で混合して使用することにより、発泡体の接
着性に対して高分子量樹脂が比較的独立的因子となって
作用すると共に、低分子量樹脂が硬化助触媒的な効果を
発揮して、各種面材、コンクリート躯体等との接着性に
優れている上、短時間で発泡硬化し得、現場スプレー発
泡施工においても有効に利用できる実用性の高いレゾー
ル系フェノール樹脂発泡体を製造できることを知見し、
本発明をなすに至ったものである。That is, the present inventors, when using a high molecular weight resol type phenolic resin as a raw material of the resole type phenolic resin foam, the adhesiveness of the resulting foam is significantly improved, but the active methylol group concentration decreases. Although the foaming curing time becomes extremely long, the number average molecular weight as a resole type phenol resin is a low molecular weight resin of less than 200 and a number average molecular weight of 200 or more and a high molecular weight resin in combination, and both resins are mixed in the above specific ratio. By using it, the high molecular weight resin acts as a relatively independent factor for the adhesiveness of the foam, and the low molecular weight resin exerts a curing co-catalyst effect, making it possible to use various surface materials and concrete frames. Resol-based phenolic resin foam, which has excellent adhesiveness with other materials, can be foam-cured in a short time, and can be effectively used in on-site spray foaming construction. And knowledge that can be produced,
The present invention has been completed.
従って、本発明はレゾール型フェノール樹脂、発泡
剤、硬化剤を配合してなる発泡体原料を用いてレゾール
系フェノール樹脂発泡体を製造するにあたり、レゾール
型フェノール樹脂として数平均分子量200未満の低分子
量レゾール型フェノール樹脂と数平均分子量200以上の
高分子量レゾール型フェノール樹脂とを重量比で5/95〜
80/20の割合で混合して使用することを特徴とするレゾ
ール系フェノール樹脂発泡体の製造方法を提供する。Therefore, in the present invention, in producing a resole-based phenol resin foam using a foam raw material prepared by blending a resole-type phenol resin, a foaming agent, and a curing agent, a low-molecular weight of less than 200 as a resole-type phenol resin is used. Resol type phenolic resin and high molecular weight resol type phenolic resin with number average molecular weight of 200 or more in weight ratio 5/95 ~
Provided is a method for producing a resole-based phenol resin foam, which is used by mixing at a ratio of 80/20.
以下、本発明につき更に詳述する。 Hereinafter, the present invention will be described in more detail.
本発明のレゾール系フェノール樹脂発泡体の製造方法
では、レゾール型フェノール樹脂、発泡剤、硬化剤を配
合した発泡体原料を用いる。In the method for producing a resole-based phenol resin foam of the present invention, a foam raw material containing a resole-type phenol resin, a foaming agent, and a curing agent is used.
この場合、レゾール型フェノール樹脂は、フェノー
ル，クレゾール等とホルムアルデヒド，フルフラール等
とをアルカリ性触媒の存在下で反応させることにより得
られるフェノールホルムアルデヒド樹脂，フェノールフ
ルフラール樹脂，クレゾールホルムアルデヒド樹脂，ク
レゾールフルフラール樹脂などのメチロール基に富んだ
液状のフェノール樹脂であり、本発明においては、フェ
ノール樹脂合成の分野及び目的に適したものであれば、
種々のレゾール型フェノール樹脂を用いることができ、
また、一種を単独で用いても、二種以上を組合せて用い
てもよい。In this case, the resol type phenol resin is a methylol such as phenol formaldehyde resin, phenol furfural resin, cresol formaldehyde resin or cresol furfural resin obtained by reacting phenol, cresol etc. with formaldehyde, furfural etc. in the presence of an alkaline catalyst. A liquid phenol resin rich in groups, in the present invention, if suitable for the field and purpose of phenol resin synthesis,
Various resol type phenolic resins can be used,
In addition, one kind may be used alone, or two or more kinds may be used in combination.
なお、各種レゾール型フェノール樹脂のうち、特にフ
ェノールホルムアルデヒド樹脂は、フェノールとホルム
アルデヒドとの反応速度が速く、合成時間短縮という経
済的有利性から多用されており、本発明においてもこの
フェノールホルムアルデヒド樹脂が好適に使用される。Among various resol-type phenolic resins, particularly phenol-formaldehyde resin is frequently used because of its fast reaction rate between phenol and formaldehyde and economical advantage of shortening synthesis time. The phenol-formaldehyde resin is also suitable for the present invention. Used for.
また、レゾール型フェノール樹脂の粘度は、別に制限
されないが、2000〜20000センチポイズ程度が好適であ
る。The viscosity of the resol-type phenol resin is not particularly limited, but is preferably about 2000 to 20000 centipoise.
本発明においては、レゾール型フェノール樹脂として
低分子量のレゾール型フェノール樹脂と高分子量のレゾ
ール型フェノール樹脂とを組合せて使用するもので、低
分子量樹脂としては、その数平均分子量が200未満、好
ましくは150以上180以下のレゾール型フェノール樹脂を
使用し、高分子量樹脂としては、その数平均分子量が20
0以上、好ましくは250以上450以下のレゾール型フェノ
ール樹脂を使用する。本発明においては、レゾール型フ
ェノール樹脂として、それぞれの数平均分子量が上記範
囲の低分子量樹脂と高分子量樹脂とを組合せて使用する
ことにより、本発明の目的を達成し得るものであり、低
分子量樹脂のみを使用したり、高分子量樹脂のみを使用
した場合、発泡体の接着性が低下したり、発泡硬化時間
が長くなって、いずれも本発明の目的を達成することが
できない。In the present invention, a low molecular weight resol type phenolic resin and a high molecular weight resol type phenolic resin are used in combination as the resol type phenolic resin, and the low molecular weight resin has a number average molecular weight of less than 200, preferably Uses a resol type phenolic resin of 150 or more and 180 or less, and the number average molecular weight is 20
A resol-type phenolic resin having 0 or more, preferably 250 or more and 450 or less is used. In the present invention, as the resol type phenolic resin, each number average molecular weight is a combination of a low molecular weight resin and a high molecular weight resin in the above range, which can achieve the object of the present invention. When only the resin is used or only the high molecular weight resin is used, the adhesiveness of the foam is deteriorated and the foam curing time becomes long, so that neither of the objects of the present invention can be achieved.
更に、上記低分子量樹脂と高分子量樹脂とは、重量比
で5/95〜80/20、好ましくは10/90〜60/40の割合で混合
する。両樹脂の混合比が5/95より小さいと、レゾール型
フェノール樹脂混合物の粘度が高くなり、取扱い難く、
かつ得られる発泡体の面材や躯体等との接着性は良好で
あるものの発泡硬化反応が遅くなり、また、混合比が80
/20を超えると、発泡硬化反応時間は短いものの接着性
が悪くなり、いずれの場合も発泡体の実用性が劣る。Further, the low molecular weight resin and the high molecular weight resin are mixed in a weight ratio of 5/95 to 80/20, preferably 10/90 to 60/40. If the mixing ratio of both resins is less than 5/95, the viscosity of the resol-type phenol resin mixture will be high, making it difficult to handle,
And, although the obtained foam has good adhesion to the face material and the body, the foam-hardening reaction is slow, and the mixing ratio is 80.
If it exceeds / 20, the foam hardening reaction time will be short, but the adhesiveness will be poor, and in any case, the practicality of the foam will be poor.
次いで、発泡剤としては、通常フェノール樹脂発泡体
原料として用いられるものであれば特に制限はなく、例
えばクロロホルム、塩化メチレンなどの塩素化炭化水
素、トリクロロフルオロメタン、1,1,2−トリクロロ−
1,2,2−トリフルオロエタン、モノクロロジフルオロメ
タン、ジクロロジフルオロメタン、1,1−ジクロロ−1,
2,2,2−テトラフルオロエタン、1,2−ジクロロ−1,1,2,
2−テトラフルオロエタン、1,1,1−トリクロロ−2,2,2
−トリフルオロエタン、1,2−ジフルオロエタン、1,1,
2,2−テトラクロロ−1,2−ジフルオロエタン、1,1,1,2
−テトラクロロ−2,2−ジフルオロエタンなどの塩素弗
素置換炭化水素化合物などの一種又は二種以上を通常の
配合量で使用することができる。Next, the foaming agent is not particularly limited as long as it is usually used as a phenol resin foam raw material, for example, chloroform, chlorinated hydrocarbons such as methylene chloride, trichlorofluoromethane, 1,1,2-trichloro-.
1,2,2-trifluoroethane, monochlorodifluoromethane, dichlorodifluoromethane, 1,1-dichloro-1,
2,2,2-tetrafluoroethane, 1,2-dichloro-1,1,2,
2-tetrafluoroethane, 1,1,1-trichloro-2,2,2
-Trifluoroethane, 1,2-difluoroethane, 1,1,
2,2-Tetrachloro-1,2-difluoroethane, 1,1,1,2
One or more of chlorine-fluorine-substituted hydrocarbon compounds such as tetrachloro-2,2-difluoroethane can be used in a usual amount.
また、硬化剤としては、フェノール樹脂重合に硬化剤
として一般的に用いられる鉱酸や有機酸が好適に使用し
得、具体的には硫酸，塩酸，リン酸等の鉱酸や、ｐ−ト
リエンスルホン酸，キシレンスルホン酸，フェノールス
ルホン酸等の有機酸が例示される。なお、硬化剤の配合
量についても何ら限定はなく、通常の配合量とすること
ができる。Further, as the curing agent, a mineral acid or an organic acid generally used as a curing agent for phenol resin polymerization can be preferably used, and specifically, a mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or p-triene can be used. Organic acids such as sulfonic acid, xylene sulfonic acid and phenol sulfonic acid are exemplified. The amount of the curing agent is not particularly limited, and may be a normal amount.
更に、本発明においては、発泡体原料として、整泡剤
を配合することが望ましく、整泡剤としては、例えばポ
リシロキサン系化合物，ヒマシ油エチレンオキサイド付
加物，ポリオキシエチレンソルビタン脂肪酸等が用いら
れる。Further, in the present invention, it is desirable to add a foam stabilizer as a foam raw material, and as the foam stabilizer, for example, a polysiloxane compound, castor oil ethylene oxide adduct, polyoxyethylene sorbitan fatty acid and the like are used. .
なおまた、発泡体原料として、上記整泡剤以外の任意
成分を本発明の目的を妨げない範囲で配合することは、
何ら差支えない。Further, as the foam raw material, blending any component other than the foam stabilizer within the range not hindering the object of the present invention,
No problem.
上記発泡体原料からレゾール系フェノール樹脂発泡体
を製造する際は、通常のフェノール樹脂発泡体と同様の
方法を採用することができ、例えば高分子量と低分子量
の両レゾール型フェノール樹脂混合物と整泡剤とを混合
し、次いで発泡剤を添加、混合した後、硬化剤を加えて
室温で激しく攪拌するなどの方法で発泡体を得ることが
できる。When producing a resole phenolic resin foam from the above foam raw material, a method similar to that of a normal phenol resin foam can be adopted, and for example, both high molecular weight and low molecular weight both resole type phenolic resin mixtures and foam stabilizers can be used. It is possible to obtain a foam by a method such as mixing the agent with the agent, then adding and mixing the foaming agent, adding the curing agent, and vigorously stirring at room temperature.
発明の効果 以上説明したように、本発明のレゾール系フェノール
樹脂発泡体の製造方法によれば、各種面材やコンクリー
ト躯体などとの接着性に優れている上、短時間で発泡硬
化し得るレゾール系フェノール樹脂発泡体を製造するこ
とができる。それ故、本発明の製造方法により得られる
レゾール系フェノール樹脂発泡体は、現場スプレー発泡
施工に利用することも可能であり、建築構造物や温、冷
水配管、浴槽タンク等の断熱材、鉄道車輌等の床下地材
などとして幅広く利用することのできる実用性の高いも
のである。Effects of the Invention As described above, according to the method for producing a resol-based phenolic resin foam of the present invention, the resol which has excellent adhesiveness to various face materials and concrete skeletons and which can be foam-cured in a short time A phenolic resin foam can be produced. Therefore, the resol-based phenol resin foam obtained by the production method of the present invention can also be used for on-site spray foaming construction, such as a building structure, heat insulation material for cold and cold water pipes, bath tanks, and railway vehicles. It is a highly practical material that can be widely used as a floor base material, etc.
以下、実施例及び比較例を挙げて本発明を具体的に説
明するが、本発明は下記実施例に制限されるものではな
い。Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
なお、以下の例において、部はいずれも重量部を示
す。In the following examples, all parts are parts by weight.
〔実施例１〜4,比較例１〜５〕 第１表に示す配合処方に従って、まず200ccの紙コッ
プに低分子量レゾール型フェノール樹脂と高分子量レゾ
ール型フェノール樹脂（以下、レゾール型フェノール樹
脂をレゾール樹脂と略す。）と整泡剤とを所定量加えて
よく混合し、更に所定量の発泡剤を添加混合した後、所
定量の硬化剤を加え、室温中でミキサーにより10秒間激
しく攪拌、混合した。次いで、この混合物をベニヤ板上
に注ぎ、室温にて反応、発泡させて発泡体（実施例１〜
４）を得た。[Examples 1 to 4, Comparative Examples 1 to 5] According to the formulation shown in Table 1, first, a low molecular weight resol type phenol resin and a high molecular weight resol type phenol resin (hereinafter, resole type phenol resin was used as a resole type resin) in a 200 cc paper cup. (Abbreviated as resin) and a foam stabilizer are added in a predetermined amount and mixed well, and then a predetermined amount of a foaming agent is added and mixed, then a predetermined amount of a curing agent is added, and the mixture is vigorously stirred and mixed for 10 seconds by a mixer at room temperature. did. Then, this mixture was poured onto a plywood plate, reacted at room temperature and allowed to foam to give a foam (Examples 1 to 1).
4) was obtained.
また、比較のため、レゾール樹脂として低分子量レゾ
ール樹脂を単独使用したもの（比較例１）、低分子量レ
ゾール樹脂２種の混合物を使用したもの（比較例２）、
高分子量レゾール樹脂を単独で使用したもの（比較例
３）、高分子量レゾール樹脂２種の混合物を使用したも
の（比較例４）及び低分子量レゾール樹脂と高分子量レ
ゾール樹脂とを重量比で90/10の割合で使用したもの
（比較例５）を上記実施例と同様の方法で作製し、発泡
体を得た。For comparison, a low molecular weight resole resin alone is used as a resole resin (Comparative Example 1), a mixture of two low molecular weight resole resins is used (Comparative Example 2),
A high molecular weight resole resin alone (Comparative Example 3), a mixture of two high molecular weight resole resins (Comparative Example 4), and a low molecular weight resole resin and a high molecular weight resole resin in a weight ratio of 90 / What was used in a ratio of 10 (Comparative Example 5) was produced in the same manner as in the above-mentioned Example to obtain a foam.
なお、上記工程において、各混合物の攪拌開始時から
発泡による見かけの体積増加が止まるまでに要した時間
を測定し、この時間を各発泡体の発泡硬化時間とした。
更に、発泡体の接着性の評価は、ベニヤ板と発泡体との
界面に剥離が観察された場合を×、剥離が観察されない
場合を○とし、フォーム密度はJIS A−9514により測定
した。以上の結果を第１表に併記する。In the above step, the time required from the start of stirring each mixture until the apparent volume increase due to foaming stopped was measured, and this time was taken as the foaming curing time of each foam.
Further, the evaluation of the adhesiveness of the foam was performed when the peeling was observed at the interface between the veneer plate and the foam, and when the peeling was not observed, the foam density was measured according to JIS A-9514. The above results are also shown in Table 1.
第１表の結果より、レゾール樹脂として低分子量レゾ
ール樹脂のみを配合した発泡体（比較例1,2）及び低分
子量レゾール樹脂と高分子量レゾール樹脂との混合比が
本発明範囲外の発泡体（比較例５）は、ベニヤ板との接
着性に劣り、高分子量レゾール樹脂のみを配合した発泡
体（比較例3,4）は、発泡硬化するのに長時間を要する
が、本発明の製造方法で得られた発泡体（実施例１〜
４）は、いずれも接着性が良好で、かつ短時間に発泡硬
化することが確認された。 From the results of Table 1, foams containing only low molecular weight resole resin as the resole resin (Comparative Examples 1 and 2) and foams in which the mixing ratio of the low molecular weight resole resin and the high molecular weight resole resin is outside the range of the present invention ( Comparative Example 5) is inferior in adhesiveness to a veneer board, and foams containing only high molecular weight resol resin (Comparative Examples 3 and 4) require a long time for foaming and curing, but with the production method of the present invention. The obtained foam (Examples 1 to 1
It was confirmed that all of 4) had good adhesiveness and foamed and cured in a short time.
Claims (1)
剤を配合してなる発泡体原料を用いてレゾール系フェノ
ール樹脂発泡体を製造するにあたり、レゾール型フェノ
ール樹脂として数平均分子量200未満の低分子量レゾー
ル型フェノール樹脂と数平均分子量200以上の高分子量
レゾール型フェノール樹脂とを重量比で5/95〜80/20の
割合で混合して使用することを特徴とするレゾール系フ
ェノール樹脂発泡体の製造方法。1. A low-molecular weight resin having a number average molecular weight of less than 200 as a resole-type phenol resin when producing a resole-type phenol resin foam using a foam raw material containing a resole-type phenol resin, a foaming agent and a curing agent. Production of a resole-type phenol resin foam characterized by using a resol-type phenol resin and a high-molecular-weight resol-type phenol resin having a number average molecular weight of 200 or more in a weight ratio of 5/95 to 80/20. Method.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12998788A JP2536593B2 (en) | 1988-05-27 | 1988-05-27 | Method for producing phenolic resin foam |
| US07/356,945 US5008297A (en) | 1988-05-27 | 1989-05-25 | Method for producing phenol resin foams and method of making foamed laminates |
| DE8989305409T DE68903428T2 (en) | 1988-05-27 | 1989-05-30 | METHOD FOR PRODUCING PHENOLIC RESIN FOAMS AND ROLLED FOAMS. |
| EP89305409A EP0344022B1 (en) | 1988-05-27 | 1989-05-30 | Methods for producing phenol resin foams and foamed laminates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12998788A JP2536593B2 (en) | 1988-05-27 | 1988-05-27 | Method for producing phenolic resin foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01299841A JPH01299841A (en) | 1989-12-04 |
| JP2536593B2 true JP2536593B2 (en) | 1996-09-18 |
Family
ID=15023352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12998788A Expired - Lifetime JP2536593B2 (en) | 1988-05-27 | 1988-05-27 | Method for producing phenolic resin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2536593B2 (en) |
-
1988
- 1988-05-27 JP JP12998788A patent/JP2536593B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01299841A (en) | 1989-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3876620A (en) | Process of preparing phenolic-aldehyde polymer using o-cresol | |
| JPS6142549A (en) | Production of phenolic resin foam | |
| EP3992220A1 (en) | Resin composition for manufacturing phenolic foam, and phenolic foam and method for manufacturing same | |
| US3835208A (en) | Method for producing an integral skin phenolic foam | |
| US3968300A (en) | Phenolic polymer, related products and processes thereof | |
| JP5464863B2 (en) | Foamable resol-type phenol resin molding material, method for producing the same, and phenol resin foam | |
| JP4756683B2 (en) | Foamable resol-type phenolic resin molding material and phenolic resin foam | |
| US3953645A (en) | Phenolic polymer, related products and processes thereof | |
| EP0344022B1 (en) | Methods for producing phenol resin foams and foamed laminates | |
| JP2536593B2 (en) | Method for producing phenolic resin foam | |
| US4409361A (en) | Fire retardant polymer resin | |
| US4036793A (en) | Phenolic polymer, related products and processes thereof | |
| JP3962145B2 (en) | Phenol-modified polyurethane foam | |
| US3766100A (en) | Rigid phenolic foams suitable for use as non flammable insulating material | |
| US4471089A (en) | Fire retardant polymer resin | |
| JP4060694B2 (en) | Foamable resol-type phenolic resin composition and phenolic resin foam using the same | |
| JPH0853563A (en) | Method for producing phenolic resin foam | |
| JP2551481B2 (en) | Foaming phenolic resin composition | |
| JPH07188446A (en) | Production of phenol resin foam | |
| JP3313491B2 (en) | Method for producing phenolic resin foam | |
| JP3381042B2 (en) | Method for producing phenolic resin form | |
| JP2920928B2 (en) | In-situ foaming method for phenolic resin foam | |
| JPS6248978B2 (en) | ||
| EP0229877A2 (en) | Improved foaming system for phenolic foams | |
| JP4251469B2 (en) | Method for producing phenolic resole resin foam and foaming agent used therefor |