JPH0242100B2 - - Google Patents
Info
- Publication number
- JPH0242100B2 JPH0242100B2 JP57133750A JP13375082A JPH0242100B2 JP H0242100 B2 JPH0242100 B2 JP H0242100B2 JP 57133750 A JP57133750 A JP 57133750A JP 13375082 A JP13375082 A JP 13375082A JP H0242100 B2 JPH0242100 B2 JP H0242100B2
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- boric acid
- flame
- acid
- agent
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【発明の詳細な説明】
本発明は難燃性フエノール樹脂発泡体の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing flame retardant phenolic resin foam.
フエノール樹脂発泡体は、幾多の有機発泡体の
中でも特に耐燃性、耐熱性、寸法安定性、耐溶剤
性、極低温特性に優れるため各種建設資材として
利用され始めている。特に近年は省エネルギーの
面や経済性の面から住宅用の天井材や壁材として
注目を浴びているが、このような用途には更に厳
しい耐燃性や耐熱性が要求され、そのため難燃剤
を添加して対処することが行われる。難燃剤には
常温で固体又は液体のものがあるが、固体状のも
のは定量的に供給することが難しいという問題が
ある。本発明の製造方法は、固体の難燃剤を用い
ても定量的にかつ連続的に発泡原液に供給混合で
きる方法に関し、その要旨は酸性硬化剤及び発泡
剤から選ばれる一部の原料によつて、ホウ酸と比
重が近似する分散媒を形成し、この分散媒とホウ
酸とを予備混合したのち、予備混合液を酸性硬化
剤及び発泡剤の残部並びにレゾール型フエノール
樹脂と混合撹拌して発泡硬化反応を行わせること
を特徴とする難燃性フエノール樹脂発泡体の製造
方法である。 Among many organic foams, phenolic resin foams are beginning to be used as various construction materials because they are particularly excellent in flame resistance, heat resistance, dimensional stability, solvent resistance, and cryogenic properties. Particularly in recent years, it has attracted attention as a material for ceilings and walls in residential buildings due to its energy saving and economical properties.However, these applications require even stricter flame resistance and heat resistance, so flame retardants are added. Measures will be taken to deal with the situation. Some flame retardants are solid or liquid at room temperature, but there is a problem in that it is difficult to quantitatively supply solid flame retardants. The manufacturing method of the present invention relates to a method in which a solid flame retardant can be quantitatively and continuously mixed into a foaming stock solution. , a dispersion medium having a specific gravity similar to that of boric acid is formed, and this dispersion medium and boric acid are premixed, and then the premixed liquid is mixed and stirred with the remainder of the acidic curing agent and the foaming agent as well as the resol type phenolic resin to form foam. This is a method for producing a flame-retardant phenolic resin foam, which is characterized by carrying out a curing reaction.
本発明で用いる難燃剤は、通常フエノール樹脂
に添加される難燃剤のうち、常温で固体のホウ酸
であり、レゾール型フエノール樹脂に用いた場
合、少量の添加量で発泡に阻害を与えずに難燃性
を向上することができる。ホウ酸の使用量はレゾ
ール型フエノール樹脂100重量部に対して１乃至
50重量部、好適には３乃至20重量部である。 The flame retardant used in the present invention is boric acid, which is solid at room temperature among the flame retardants usually added to phenolic resins, and when used in resol type phenolic resins, it can be used in small amounts without inhibiting foaming. Flame retardancy can be improved. The amount of boric acid used is 1 to 100 parts by weight of resol type phenolic resin.
50 parts by weight, preferably 3 to 20 parts by weight.
酸性硬化剤は、通常レゾール型フエノール樹脂
の硬化剤として用いられるものなら如何なるもの
でもよく、たとえば塩酸、硫酸、リン酸、ポリリ
ン酸、ピロリン酸等の無機酸、ベンゼンスルフオ
ン酸、トルエンスルフオン酸、メタクレゾールス
ルフオン酸、レゾルシノールスルフオン酸、ブチ
ルスルフオン酸、プロピルスルフオン酸等の有機
酸あるいはこれらの混合酸を用いることができ
る。これらの酸性硬化剤のうちでは、比較的広範
囲に比重調整のできる硫酸が好適である。酸性硬
化剤の使用量は、レゾール型フエノール樹脂100
重量部に対して概ね３乃至30重量部である。 The acidic curing agent may be any curing agent that is normally used as a curing agent for resol-type phenolic resins, such as inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, and pyrophosphoric acid, benzenesulfonic acid, and toluenesulfonic acid. , metacresol sulfonic acid, resorcinol sulfonic acid, butyl sulfonic acid, propyl sulfonic acid, or a mixed acid thereof can be used. Among these acidic curing agents, sulfuric acid whose specific gravity can be adjusted over a relatively wide range is preferred. The amount of acidic curing agent used is 100% of resol type phenolic resin.
It is approximately 3 to 30 parts by weight.
発泡剤には、炭酸アルカル金属塩、炭酸アルカ
リ土類金属塩、低級パラフイン、アルコール、エ
ーテル、塩化フツ化炭化水素等通常フエノール樹
脂発泡体の製造に用いられる公知の発泡剤が用い
られる。発泡剤の使用量は、レゾール型フエノー
ル樹脂100重量部に対して概ね３乃至30重量部で
ある。 As the blowing agent, known blowing agents commonly used in the production of phenolic resin foams may be used, such as alkali metal carbonates, alkaline earth metal carbonates, lower paraffins, alcohols, ethers, and chlorofluorinated hydrocarbons. The amount of blowing agent used is approximately 3 to 30 parts by weight per 100 parts by weight of the resol type phenolic resin.
これらの酸性硬化剤及び発泡剤から選ばれる一
部の原料によつて、ホウ酸と比重が近似する分散
媒を形成し、この分散媒とホウ酸とを予備混合す
る。このとき酸性硬化剤及び発泡剤のいずれか一
方がホウ酸と比重が近似する場合は、その比重が
近似するもののみによつて分散媒を形成すること
ができるが、それぞれの比重がホウ酸の比重と異
なる場合には、両者の一部を組合せてホウ酸の比
重と近似するように調整し、分散媒を形成する。 A dispersion medium having a specific gravity similar to that of boric acid is formed using some raw materials selected from these acidic curing agents and blowing agents, and this dispersion medium and boric acid are premixed. At this time, if either the acidic curing agent or the blowing agent has a specific gravity similar to that of boric acid, a dispersion medium can be formed only with those having similar specific gravity; If the specific gravity is different from that of boric acid, a portion of both is combined to adjust the specific gravity to approximate that of boric acid to form a dispersion medium.
たとえば難燃剤にホウ酸を用い、酸性硬化剤と
して硫酸を利用した場合は、ホウ酸の比重が1.43
であるので、硫酸濃度を概ね53乃至60％に調整し
て、使用する硫酸の比重を1.40乃至1.60程度に調
整する。また発泡剤として塩化フツ化炭化水素
（通称フレオン）を用いた場合には、フレオン
R11、フレオンR112、フレオンR113を用いると
ホウ酸の比重に近いため、ホウ酸と予備混合する
ことができる。この場合、フレオン各種は単独ま
たは混合して用いてもよい。このほかホウ酸とレ
ゾール型フエノール樹脂とを予備混合することも
考えられるが、ホウ酸は酸性硬化剤としても働く
ため好ましくない。 For example, when boric acid is used as a flame retardant and sulfuric acid is used as an acidic curing agent, the specific gravity of boric acid is 1.43.
Therefore, the sulfuric acid concentration is adjusted to about 53 to 60%, and the specific gravity of the sulfuric acid used is adjusted to about 1.40 to 1.60. In addition, when chlorinated fluorinated hydrocarbons (commonly known as Freon) are used as a blowing agent, Freon
When R11, Freon R112, and Freon R113 are used, their specific gravity is close to that of boric acid, so they can be premixed with boric acid. In this case, various types of freon may be used alone or in combination. In addition, it is possible to premix boric acid and a resol type phenolic resin, but this is not preferable because boric acid also works as an acidic curing agent.
予備混合によつて固体の難燃剤としてのホウ酸
は、沈澱することなく均一に、酸性硬化剤及び発
泡剤の一部からなる分散媒中に分散されるので、
予備混合液はホウ酸の沈澱や目詰り等の障害なし
に、レゾール型フエノール樹脂への添加を定量的
にかつ連続的に行うことができる。 By premixing, boric acid as a solid flame retardant is uniformly dispersed in a dispersion medium consisting of an acidic curing agent and a part of a blowing agent without precipitation.
The premixed liquid can be quantitatively and continuously added to the resol type phenolic resin without problems such as boric acid precipitation or clogging.
このようにして予備混合された予備混合液は、
最後に酸性硬化剤及び発泡剤の残部並びにレゾー
ル型フエノール樹脂と混合撹拌されて発泡硬化反
応を生じ、難燃性フエノール樹脂発泡体が製造さ
れる。尚この時整泡剤、充填剤等他の添加剤を加
えてもよい。 The premixed liquid premixed in this way is
Finally, it is mixed and stirred with the rest of the acidic curing agent, the foaming agent, and the resol type phenolic resin to cause a foaming and curing reaction, producing a flame-retardant phenolic resin foam. At this time, other additives such as foam stabilizers and fillers may be added.
本発明の製造方法によると、従来困難視されて
いた固体状難燃剤であるホウ酸の定量的供給を簡
単に行うことができ、更に連続発泡成形を行つて
も沈澱によつてホウ酸が発泡成形装置内の配管や
バルブ等に詰りを生じるトラブルを防止すること
ができ、工業上利用価値が非常に大きい。また無
水ホウ酸を用いると、水分との反応が起るため、
水分を含有する酸性硬化剤および発泡剤は分散媒
として使用できないが、ホウ酸を使用すると、こ
のような障害はなく、分散媒として水性のものを
使用することができ、比重の調整が容易であり、
発泡に対する障害もない。 According to the manufacturing method of the present invention, it is possible to easily quantitatively supply boric acid, which is a solid flame retardant, which has been considered difficult in the past, and furthermore, even when continuous foam molding is performed, boric acid foams due to precipitation. It is possible to prevent troubles such as clogging of piping and valves in the molding equipment, and has great industrial value. Also, when boric anhydride is used, it reacts with moisture, so
Acidic curing agents and blowing agents that contain water cannot be used as dispersion media, but when boric acid is used, this problem does not occur, and an aqueous dispersion medium can be used, making it easy to adjust the specific gravity. can be,
There are no obstacles to foaming.
実施例 １
難燃剤としてのホウ酸（H3BO3）を10重量部
及び発泡剤としてのフレオンR113を10重量部
混合槽で予備混合したのち最終混合槽へ供給し
た。該最終混合槽には別途レゾール型フエノール
樹脂100重量部、酸性硬化剤としてフエノールス
ルフオン酸10重量部が供給されており、これらを
混合撹拌したのち発泡金型内へ注入し、温度70℃
で15分間加熱し発泡硬化反応を行わせた。得られ
たフエノール樹脂発泡体の密度は45Kg／cm3であ
り、ASTM D2863による酸素指数は33％であつ
た。Example 1 10 parts by weight of boric acid (H 3 BO 3 ) as a flame retardant and 10 parts by weight of Freon R113 as a blowing agent were premixed in a mixing tank and then supplied to a final mixing tank. Separately, 100 parts by weight of resol-type phenolic resin and 10 parts by weight of phenolsulfonic acid as an acidic curing agent are supplied to the final mixing tank, and after mixing and stirring these, they are poured into a foaming mold and heated to a temperature of 70°C.
was heated for 15 minutes to cause a foaming hardening reaction. The density of the resulting phenolic resin foam was 45 Kg/cm 3 and the oxygen index according to ASTM D2863 was 33%.
Claims (1)
料によつて、ホウ酸と比重が近似する分散媒を形
成し、この分散媒とホウ酸とを予備混合したの
ち、予備混合液を酸性硬化剤及び発泡剤の残部並
びにレゾール型フエノール樹脂と混合撹拌して発
泡硬化反応を行わせることを特徴とする難燃性フ
エノール樹脂発泡体の製造方法。 ２ 酸性硬化剤が硫酸である特許請求の範囲第１
項記載の難燃性フエノール樹脂発泡体の製造方
法。 ３ 発泡剤が塩化フツ化炭化水素である特許請求
の範囲第１項または第２項いずれかに記載の難燃
性フエノール樹脂発泡体の製造方法。[Scope of Claims] 1. A dispersion medium having a specific gravity similar to that of boric acid is formed using some raw materials selected from acidic curing agents and blowing agents, and after premixing this dispersion medium and boric acid, A method for producing a flame-retardant phenolic resin foam, which comprises mixing and stirring a premixed liquid with an acidic hardening agent, the remainder of a blowing agent, and a resol type phenolic resin to cause a foaming and curing reaction. 2 Claim 1 in which the acidic curing agent is sulfuric acid
A method for producing a flame-retardant phenolic resin foam as described in 2. 3. The method for producing a flame-retardant phenolic resin foam according to claim 1 or 2, wherein the blowing agent is a chlorofluorinated hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13375082A JPS5924730A (en) | 1982-08-02 | 1982-08-02 | Production of flame-retarding phenolic resin foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13375082A JPS5924730A (en) | 1982-08-02 | 1982-08-02 | Production of flame-retarding phenolic resin foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5924730A JPS5924730A (en) | 1984-02-08 |
| JPH0242100B2 true JPH0242100B2 (en) | 1990-09-20 |
Family
ID=15112056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13375082A Granted JPS5924730A (en) | 1982-08-02 | 1982-08-02 | Production of flame-retarding phenolic resin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5924730A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6035032A (en) * | 1983-08-08 | 1985-02-22 | Showa Highpolymer Co Ltd | Production of flame-retarding phenolic resin foam |
| JPH0249037A (en) * | 1988-08-11 | 1990-02-19 | Toyo Tire & Rubber Co Ltd | Production of foam of flame-retardant phenolic resin |
| JP2002088186A (en) * | 2000-09-14 | 2002-03-27 | Showa Highpolymer Co Ltd | Method for producing flame-retardant phenolic resin foam |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5927772B2 (en) * | 1973-06-01 | 1984-07-07 | エツソ リサ−チ アンド エンジニアリング カンパニ− | Improved foamed phenolic resin board and its molding method |
-
1982
- 1982-08-02 JP JP13375082A patent/JPS5924730A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5924730A (en) | 1984-02-08 |
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