JPH0549702B2 - - Google Patents
Info
- Publication number
- JPH0549702B2 JPH0549702B2 JP24412089A JP24412089A JPH0549702B2 JP H0549702 B2 JPH0549702 B2 JP H0549702B2 JP 24412089 A JP24412089 A JP 24412089A JP 24412089 A JP24412089 A JP 24412089A JP H0549702 B2 JPH0549702 B2 JP H0549702B2
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- foam
- volume
- carbon dioxide
- liquefied carbon
- 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 claims description 30
- 239000005011 phenolic resin Substances 0.000 claims description 30
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 28
- 229920001568 phenolic resin Polymers 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000004604 Blowing Agent Substances 0.000 claims description 11
- 238000005187 foaming Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 4
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 4
- 229940044654 phenolsulfonic acid Drugs 0.000 description 4
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- -1 but among these Chemical compound 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 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 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000004619 high density foam Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
［産業上の利用分野］
本発明は、建材用として壁材、天井材、また家
具等の材料として有用な耐熱性、断熱性、難燃
性、耐水性を有し、機械的強度に優れたフエノー
ル樹脂発泡体の製造法に関する。
［従来の技術］
フエノール樹脂発泡体は、軽量で熱可塑性樹脂
製発泡体に比し、難燃性、耐熱性、機械的強度に
優れ、建材分野、家具等の材料として広く用いら
れる。
製造法としては、レゾール樹脂を原料とし、発
泡剤としてトリクロルモノフルオロメタン（フロ
ン−11）、トリクロルトリフルオロエタン（フロ
ン−113）、ペンタン等が主として用いられてい
た。
しかし、フロン−11やフロン−113は発泡剤と
して極めて優れた性質を有し、人体に対し無害
で、引火性、着火性もなく、工程的には安全な発
泡剤ではあるが、このフロン類が地球を取り巻く
オゾン層を破壊し、地球の環境破壊を促進するこ
とが分かり、使用量の減少、更には使用禁止の必
要性が叫ばれつつある。
また、ペンタンはフロンと異なり地球の環境破
壊の問題はないとしても、可燃性の炭化水素ガス
であつて、漏洩すれば爆発や火災の危険の極めて
大きい物質であり、またその爆発範囲もペンタン
が少量であつてもその範囲に入ること、空気より
比重が重いため低所に溜り易く安全上問題のある
ガスであることはよく知られているところであ
る。
他の発泡剤としては加熱により窒素ガスを放出
するアゾ系化合物の使用が行なわれてきたが、化
合物が高価であること、発泡倍率を高くするには
多量の使用が必要となること、発泡させるには化
合物の分解温度以上の温度に長時間保持すること
が必要であること等の点から主として低発泡倍率
の発泡体に利用されてきた。
［発明が解決しようとする課題］
本発明は比較的高倍率の発泡体を、大気汚染の
原因となるフロン類を使用せず、また可燃性で爆
発性のあるペンタン等を使用しないで安全な操業
可能な発泡剤を使用し、フエノール発泡体の有す
る耐熱性、難燃性、断熱性、軽量性等の優れた特
徴を持つたフエノール発泡体を製造する方法の開
発を目的とする。
［課題を解決するための手段］
本発明は、上記目的を達成するために種々検討
した結果、レゾール型フエノール樹脂、発泡剤、
整泡剤、酸硬化剤を混合、硬化して、フエノール
樹脂発泡体を製造するに当り、発泡剤の出発原料
として液化二酸化炭素をフエノール樹脂１容量部
に対し0.3〜15容量部使用して、フエノール樹脂
発泡体を製造することを開発した。
特に、整泡剤を含有したレゾール型フエノール
樹脂、酸硬化剤及びフエノール樹脂１容量部に対
し0.3〜15容量部の液化二酸化炭素をそれぞれ
別々に連続的にフエノール樹脂発泡機に供給する
と共に急速に均一に混合しながらフエノール樹脂
発泡混合物を吐出させ、ついでモールド中で硬化
させることにより安全で、大気汚染の全くないフ
エノール樹脂発泡体を製造できることを見出し
た。
ここで、レゾール型フエノール樹脂に使用でき
るフエノール類としては、通常フエノール樹脂の
製造原料として用いられるフエノール、クレゾー
ル、キシレノール等が挙げられるが、これらの中
でも反応性、硬化性の点でフエノール、メタクレ
ゾールが特に好ましい。これらフエノール類は単
独のみならず、これら同士の混合、更にはｏ−ク
レゾール、ｐ−クレゾールまたはビスフエノール
等を併用しても良い。
アルデヒド類としては、ホルムアルデヒド、パ
ラホルムアルデヒド、ポリオキシメチレン、トリ
オキサン等が使用できる。
この両者を塩基性触媒の存在下に反応させ、脱
水濃縮させてレゾール型フエノール樹脂を得る。
樹脂固形物としては60〜90％、粘度1500〜
8000cps／25℃位が使用するのに便利であり、も
し濃縮度が高いときは少量の水、アルコール、ア
セトン、エステル、可塑剤等で適宜希釈して濃
度、粘度を調整する。
本発明に使用する整泡剤としては、フロン発泡
剤使用の際に使用されていたものとほとんど同じ
ものが用いられる。シリコーン系：エチレンオキ
サイド−プロピレンオキサイド共重合体：ソルビ
タン、アルキルフエノールまたはヒマシ油等のポ
リオキシアルキレン付加物系等の界面活性剤が使
用できる。
これらは単独又は混合して使用されるが、使用
量はフエノール樹脂100重量部に対し、0.5〜10重
量部である。
酸硬化剤もレゾール発泡剤使用の際に使用され
ていたものと同じであつて、例えばパラトルエン
スルフオン酸、フエノールスルホン酸等の強酸を
使用する。添加量はフエノール樹脂100重量部当
り５〜40部が好ましい。
発泡剤の出発原料として使用する液化二酸化炭
素は、フエノール樹脂１容量部に対し0.3〜15容
量部が適当である。この範囲外では良好な発泡体
が得られない。
フエノール樹脂発泡体の製造は、フロンを用い
た時とほぼ同一の方法を採用できる。
すなわち、整泡剤を含有する樹脂固形分及び粘
度を調整したレゾール型フエノール樹脂、酸硬化
剤および液化二酸化炭素をそれぞれフエノール樹
脂発泡機に付属する定量ポンプで混合機（ミキシ
ングヘツド）に供給する。ミキシングヘツドのス
クリユーは1000〜10000rpmの高速回転されてお
り、これら原料は瞬時に均一に混合され、発泡機
から押し出される。
本発明のフエノール樹脂発泡体はそのままで使
用する場合よりも、木材、金属、他の合成樹脂等
と複合材として使用することが多い。
したがつて、発泡体の発泡率も目的、複合され
る相手の材質や強度により変化し、比較的低発泡
率（比重0.1位）から高発泡率（0.005位）まで変
化する。この発泡率の調整は液化二酸化炭素の注
入量によつて行なう。
この発泡混合物は常温〜100℃の温度で硬化さ
れ、硬化時間はだいたい５〜20分である。
［実施例］
（実施例 １）
四ツ口フラスコにフエノール２Kg、37％ホルム
アルデヒド2.93Kg（ホルムアルデヒド／フエノー
ル：モル比1.7モル）及び触媒として20％カ性ソ
ーダ60ｇを仕込み、80℃で３時間反応した後、15
％硫酸でPHを7.0に中和し、減圧脱水により樹脂
中の水分を５％以下にした。
得られたレゾール型フエノール樹脂は樹脂固形
分80％、粘度2500cps／25℃、重量平均分子量430
であつた。
このレゾール型フエノール樹脂100重量部に対
してトウイーンNo.40（ポリオキシエチレンソルビ
タンモノパルミテート）２重量部を混合し、発泡
用フエノール樹脂とした。
発泡用フエノール樹脂1.6／minに対して、
65％フエノールスルホン酸0.12／minをフエノ
ール樹脂発泡機の定量ポンプより混合機（ミキシ
ングヘツド）に供給し、スクリユー回転数
6000rpmの下で液化二酸化炭素２／minを別ラ
インより混合機に注入し、フエノール樹脂、フエ
ノールスルホン酸及び二酸化炭素を瞬時に均一に
混合し、混合機底口より吐き出し、幅50cm、長さ
25cm、高さ４cmの鉄枠中に一定量流し込み、これ
を40℃オーブン中で５分間放置し、発泡硬化を完
了してフエノール樹脂発泡体を得た。
得られたフエノール樹脂発泡体の物性は密度20
Kg／m3、吸水量4.5ｇ／100cm2、熱伝導率
0.027Kcal／mh℃であり、外観上も全体的に均一
であつた。
（実施例２〜６、比較例１〜２、参考例１）
実施例１で得た整泡剤添加済のレゾール型発泡
用フエノール樹脂を1.6／min、65％フエノー
ルスルホン酸0.12／minの割合で供給すると共
に、液化二酸化炭素供給量、ミキシングヘツドの
スクリユーの回転数を変えて実施した結果を第１
表に示す。
なお、参考のためフロン−113を使用し、本発
明の実施例とほぼ同一の製品を得る条件を参考例
１として示す。
[Industrial Field of Application] The present invention is a material that has heat resistance, heat insulation, flame retardancy, water resistance, and excellent mechanical strength and is useful as a building material for wall materials, ceiling materials, furniture, etc. The present invention relates to a method for producing a phenolic resin foam. [Prior Art] Phenol resin foams are lightweight and have excellent flame retardancy, heat resistance, and mechanical strength compared to thermoplastic resin foams, and are widely used in the field of building materials and as materials for furniture and the like. As for the manufacturing method, resol resin was used as a raw material, and trichloromonofluoromethane (Freon-11), trichlorotrifluoroethane (Freon-113), pentane, etc. were mainly used as blowing agents. However, although Freon-11 and Freon-113 have extremely excellent properties as blowing agents, are harmless to the human body, are neither flammable nor ignitable, and are safe from a process standpoint. It has been found that the ozone layer that surrounds the earth is destroyed and the earth's environment is being destroyed, and calls are being made for the need to reduce or even ban its use. Furthermore, although pentane does not cause environmental damage to the earth unlike fluorocarbons, it is a flammable hydrocarbon gas that poses an extremely high risk of explosion or fire if it leaks, and pentane has an explosive range. It is well known that even a small amount of gas falls within this range, and that it is a gas that tends to accumulate in low places because it has a higher specific gravity than air, which poses a safety problem. As other foaming agents, azo compounds that release nitrogen gas when heated have been used, but these compounds are expensive, require large amounts to increase the foaming ratio, and are difficult to foam. Since it is necessary to maintain the temperature at a temperature higher than the decomposition temperature of the compound for a long time, it has been mainly used for foams with a low expansion ratio. [Problems to be Solved by the Invention] The present invention is capable of producing a relatively high-density foam in a safe manner without using fluorocarbons, which cause air pollution, and without using pentane, which is flammable and explosive. The purpose of this project is to develop a method for producing phenolic foam that has the excellent characteristics of phenolic foam, such as heat resistance, flame retardance, heat insulation, and lightness, using a blowing agent that can be operated. [Means for Solving the Problems] As a result of various studies to achieve the above object, the present invention has been developed by using a resol type phenolic resin, a blowing agent,
When mixing and curing a foam stabilizer and an acid curing agent to produce a phenolic resin foam, use 0.3 to 15 parts by volume of liquefied carbon dioxide as a starting material for the foaming agent per 1 part by volume of the phenolic resin. Developed to produce phenolic resin foam. In particular, 0.3 to 15 parts by volume of liquefied carbon dioxide are separately and continuously supplied to a phenolic resin foaming machine for each part by volume of a resol-type phenolic resin containing a foam stabilizer, an acid curing agent, and a phenolic resin. It has been found that by discharging a phenolic resin foam mixture while uniformly mixing it and then curing it in a mold, it is possible to produce a phenolic resin foam that is safe and completely free from air pollution. Here, phenols that can be used in resol type phenolic resin include phenol, cresol, xylenol, etc., which are usually used as raw materials for manufacturing phenolic resin, but among these, phenol, meta-cresol, etc. are preferred in terms of reactivity and curability. is particularly preferred. These phenols may be used not only alone, but also in combination with each other, or in combination with o-cresol, p-cresol, bisphenol, or the like. As aldehydes, formaldehyde, paraformaldehyde, polyoxymethylene, trioxane, etc. can be used. Both are reacted in the presence of a basic catalyst and dehydrated and concentrated to obtain a resol type phenolic resin. Resin solids: 60-90%, viscosity 1500-
It is convenient to use around 8000cps/25℃, and if it is highly concentrated, dilute it with a small amount of water, alcohol, acetone, ester, plasticizer, etc. to adjust the concentration and viscosity. The foam stabilizer used in the present invention is almost the same as that used in the case of using chlorofluorocarbon foaming agents. Silicone-based: Ethylene oxide-propylene oxide copolymer: Surfactants such as sorbitan, alkylphenol, or polyoxyalkylene adducts such as castor oil can be used. These may be used alone or in combination, and the amount used is 0.5 to 10 parts by weight per 100 parts by weight of the phenolic resin. The acid curing agent is also the same as that used when using the resol blowing agent, and for example, a strong acid such as para-toluenesulfonic acid or phenolsulfonic acid is used. The amount added is preferably 5 to 40 parts per 100 parts by weight of the phenolic resin. The appropriate amount of liquefied carbon dioxide used as a starting material for the blowing agent is 0.3 to 15 parts by volume per part by volume of phenolic resin. A good foam cannot be obtained outside this range. The phenolic resin foam can be produced using almost the same method as when using fluorocarbons. That is, a resol type phenolic resin containing a foam stabilizer with adjusted resin solid content and viscosity, an acid curing agent, and liquefied carbon dioxide are each supplied to a mixer (mixing head) by a metering pump attached to a phenolic resin foaming machine. The screw in the mixing head is rotated at a high speed of 1,000 to 10,000 rpm, and these raw materials are instantly and uniformly mixed and extruded from the foaming machine. The phenolic resin foam of the present invention is more often used as a composite material with wood, metal, other synthetic resins, etc. than when used as it is. Therefore, the expansion rate of the foam also changes depending on the purpose, the material and strength of the composite material, and varies from a relatively low expansion rate (specific gravity around 0.1) to a high expansion rate (around 0.005). This foaming rate is adjusted by adjusting the amount of liquefied carbon dioxide injected. This foamed mixture is cured at a temperature of room temperature to 100°C, and the curing time is approximately 5 to 20 minutes. [Example] (Example 1) A four-necked flask was charged with 2 kg of phenol, 2.93 kg of 37% formaldehyde (formaldehyde/phenol: molar ratio 1.7 mol), and 60 g of 20% caustic soda as a catalyst, and reacted at 80°C for 3 hours. After that, 15
% sulfuric acid to 7.0, and reduced the water content in the resin to 5% or less by dehydration under reduced pressure. The obtained resol type phenolic resin has a resin solid content of 80%, a viscosity of 2500 cps/25°C, and a weight average molecular weight of 430.
It was hot. 2 parts by weight of Tween No. 40 (polyoxyethylene sorbitan monopalmitate) was mixed with 100 parts by weight of this resol type phenolic resin to obtain a foaming phenolic resin. For foaming phenolic resin 1.6/min,
65% phenolsulfonic acid 0.12/min was supplied to the mixer (mixing head) from the metering pump of the phenolic resin foaming machine, and the screw rotation speed was
At 6000 rpm, liquefied carbon dioxide 2/min is injected into the mixer from a separate line, and the phenol resin, phenolsulfonic acid, and carbon dioxide are instantly and uniformly mixed, and then discharged from the bottom of the mixer. Width: 50 cm, length:
A certain amount of the mixture was poured into a 25 cm x 4 cm high iron frame and left in an oven at 40°C for 5 minutes to complete foam curing and obtain a phenolic resin foam. The physical properties of the obtained phenolic resin foam have a density of 20
Kg/m 3 , water absorption 4.5g/100cm 2 , thermal conductivity
The temperature was 0.027 Kcal/mh°C, and the appearance was uniform throughout. (Examples 2 to 6, Comparative Examples 1 to 2, Reference Example 1) The resol type foaming phenolic resin obtained in Example 1 with added foam stabilizer was added at a rate of 1.6/min and 65% phenolsulfonic acid at a rate of 0.12/min. The first results were obtained by supplying liquefied carbon dioxide by changing the amount of liquefied carbon dioxide supplied and the number of revolutions of the mixing head screw.
Shown in the table. For reference, conditions for obtaining almost the same product as in the examples of the present invention are shown as Reference Example 1 using Freon-113.
【表】
［効果］
従来、発泡剤として使用されていたトリクロル
モノフルオロメタン（フロン−11）、トリクロル
トリフルオロエタン（フロン−113）はオゾン層
を破壊し、地球の環境汚染をするとされて使用量
の制限、使用禁止の必要が叫ばれており、フロン
を使用しない製造法の開発が要望されていた。
一方、フロンを使用しないペンタンを発泡剤と
して使用する発泡体製造法もあるが、これは爆発
の危険があり、安全上問題があつた。
これに対し本発明は、発泡剤の出発原料として
液化二酸化炭素を使用することにより大気汚染を
なくし、また爆発の危険なく、安全にフエノール
樹脂発泡体の製造を可能とする技術を開発した。[Table] [Effects] Trichlormonofluoromethane (Freon-11) and trichlorotrifluoroethane (Freon-113), which were conventionally used as blowing agents, were discontinued because they were thought to destroy the ozone layer and pollute the earth's environment. There have been calls for the need to limit the amount and ban the use of chlorofluorocarbons, and there has been a demand for the development of a manufacturing method that does not use fluorocarbons. On the other hand, there is a foam production method that uses pentane as a blowing agent without using CFCs, but this poses a safety problem due to the risk of explosion. In contrast, the present invention has developed a technology that eliminates air pollution by using liquefied carbon dioxide as a starting material for a blowing agent, and also enables the safe production of phenolic resin foams without the risk of explosion.
Claims (1)
剤、酸硬化剤を混合、硬化して、フエノール樹脂
発泡体を製造するに当り、発泡剤の出発原料とし
て液化二酸化炭素をフエノール樹脂１容量部に対
し0.3〜15容量部使用することを特徴とするフエ
ノール樹脂発泡体の製造法。 ２ 整泡剤を含有したレゾール型フエノール樹
脂、酸硬化剤及びフエノール樹脂１容量部に対し
0.3〜15容量部の液化二酸化炭素をそれぞれ別々
に連続的にフエノール樹脂発泡機に供給すると共
に急速に均一に混合しながらフエノール樹脂発泡
混合物を吐出させ、ついでモールド中で硬化させ
ることを特徴とするフエノール樹脂発泡体の製造
法。[Claims] 1. When producing a phenolic resin foam by mixing and curing a resol type phenolic resin, a blowing agent, a foam stabilizer, and an acid curing agent, liquefied carbon dioxide is used as a starting material for the blowing agent. A method for producing a phenolic resin foam, characterized in that 0.3 to 15 parts by volume are used for 1 part by volume of resin. 2 For 1 part by volume of resol type phenolic resin containing foam stabilizer, acid curing agent and phenolic resin
The method is characterized in that 0.3 to 15 parts by volume of liquefied carbon dioxide are each separately and continuously supplied to a phenolic resin foaming machine, and the phenolic resin foaming mixture is discharged while rapidly and uniformly mixed, and then cured in a mold. Method for producing phenolic resin foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24412089A JPH03106947A (en) | 1989-09-20 | 1989-09-20 | Production of phenolic rein foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24412089A JPH03106947A (en) | 1989-09-20 | 1989-09-20 | Production of phenolic rein foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03106947A JPH03106947A (en) | 1991-05-07 |
| JPH0549702B2 true JPH0549702B2 (en) | 1993-07-27 |
Family
ID=17114059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24412089A Granted JPH03106947A (en) | 1989-09-20 | 1989-09-20 | Production of phenolic rein foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03106947A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4868653B2 (en) * | 2001-04-11 | 2012-02-01 | 旭化成建材株式会社 | Phenolic resin foam |
-
1989
- 1989-09-20 JP JP24412089A patent/JPH03106947A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03106947A (en) | 1991-05-07 |
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