JP3381042B2 - Method for producing phenolic resin form - Google Patents
Method for producing phenolic resin formInfo
- Publication number
- JP3381042B2 JP3381042B2 JP34465693A JP34465693A JP3381042B2 JP 3381042 B2 JP3381042 B2 JP 3381042B2 JP 34465693 A JP34465693 A JP 34465693A JP 34465693 A JP34465693 A JP 34465693A JP 3381042 B2 JP3381042 B2 JP 3381042B2
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- foaming agent
- resin form
- acid
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Biological Depolymerization Polymers (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明はフェノ−ル樹脂フォ−ム
に関するものであり、特に本発明は発泡剤として１，３
−ジオキソランを使用してフォ−ムの充填性、圧縮強度
及び断熱性が優れ、且つ極めて均一微細なセル構造を有
するフェノ−ル樹脂フォ−ムの製造法に関するものであ
る。
【０００２】
【従来の技術】一般にフェノ−ル樹脂フォ−ムはその発
泡剤として、断熱特性及び難燃性に極めて優れたトリク
ロロフルオロメタン(通称ＣＦＣ−１１)、トリクロロト
リフルオロエタン(通称フロン１１３)を使用しており、
それによって得られたフェノ−ル樹脂フォ−ムは耐熱性
が高く、耐防火性、耐防煙性、断熱性に優れるため、建
材用途をはじめ各種断熱材用途へ開発が進められてい
る。又フェノ−ル樹脂フォ−ムは価格、熱安定性、耐火
性、耐湿性、耐薬品性、寸法安定性、発煙性、電気的性
質および現場発泡の適合性においてポリウレタン樹脂フ
ォ−ムのような他の発泡樹脂より有利であり、種々の用
途用のフェノ−ル樹脂フォ−ムを製造することが望まれ
ている。しかし、性能上多くの利点があり又経済的にも
好ましいにもかかわらず、フェノ−ル樹脂フォ−ムは絶
縁材市場に浸透していない。これはフェノ−ル樹脂フォ
−ムが破壊されたセル壁および発泡塊の中心の裂け目お
よび(あるいは)ボイドを有し、且つブロ−ホ−ル又はチ
ャンネルによって生ずるキャビテ−ションを受けやすい
という今日のフェノ−ル樹脂フォ−ムが抱えている問題
の結果によるものである。
【０００３】
【発明が解決しようとする課題】近年地球オゾン層保護
のためクロロフルオロカ−ボン類の規制が実施されてい
る。この規制対象には今までフェノ−ル樹脂フォ−ムの
発泡剤として用いられてきたＣＦＣ−１１、ＣＦＣ−１
１３も含まれている。その為ＣＦＣ−１１、ＣＦＣ−１
１３に替わるフェノ−ル樹脂フォ−ム用発泡剤の開発が
義務となっている。現在ＣＦＣ−１１、−１１３に替わ
るハロゲンを含まない発泡剤として、例えばシクロペン
タン等の炭化水素化合物が提案されている。しかし、こ
れらの化合物は引火点が極めて低いこと及び既存のフェ
ノ−ル樹脂との相溶性が悪いためフェノ−ル樹脂フォ−
ムを得る為に設備的な工夫などが必要となり、均一なセ
ル構造が得られにくいという欠点を有している。
【０００４】
【課題を解決するための手段】本発明者らは、上記問題
点を克服するための鋭意努力した結果フェノ−ル樹脂フ
ォ−ム用発泡剤として１，３−ジオキソランを使用する
ことによって優れたフォ−ムの充填性、圧縮強度及び断
熱性を有し、且つ裂け目又はボイドがほとんどない均一
微細なセル構造を有するフェノ−ルフォ−ムを製造する
ことを見出し、本発明に達した。その為本発明で使用さ
れるレゾ−ル型フェノ−ル樹脂は、一般にフェノ−ルに
ホルムアルデヒドを過剰に用いてアルカリ性で反応して
得られるが、好適なフェノ−ル樹脂フォ−ムを得るため
のフェノ−ル−ホルムアルデヒドのモル比は一般に１：
１〜１：２.０であるが、好ましくは１：１.３〜１：
１.６である。通常これらフェノ−ル樹脂の硬化物は硬
くて、脆い性質を有しているが、この欠点を改良する
為、例えばフェノ−ル樹脂を粘弾性の高いポリマ−とグ
ラフトすることや又は脂肪族低級ポリオ−ルのジ又はト
リグリシジルエ−テル化合物等で変性したフェノ−ル樹
脂等を使用することもできる。発泡剤としての１，３−
ジオキソランは適量使用するが、好ましくは５〜２０％
である。又、本発明で使用される酸性触媒は特に限定す
るものではなく、パラトルエンスルホン酸、フェノ−ル
スルホン酸、キシレンスルホン酸、レゾ−ルスルホン
酸、メタキシレンスルホン酸、ベンゼンスルホン酸等の
有機スルホン酸、リン酸、硫酸、シュウ酸、カルボン酸
等が使用される。その使用量は特に限定しないが、正常
１０〜２０％である。又、整泡剤としては従来公知の有
機ケイ素化合物であり、その使用量は特に限定しないが
０.１〜１０％が適当である。その他界面活性剤、助
剤、安定剤、着色剤など必要に応じて添加することがで
きる。以下に本発明をより具体的に説明するため実施例
をあげて説明するが、本発明は実施例に限定されるもの
ではない。
【０００５】
【実施例】
【実施例 １】２５℃における粘度が５,０００ｃｐｓ
であり、固形分含量が３２％であるレゾ−ル型フェノ−
ル樹脂１００部に整泡剤としてのシリコン界面活性剤、
約２部および発泡剤として１，３−ジオキソラン１０部
を加えて撹拌混合して安定なエマルジョンを生成させ
た。次いで得られたエマルジョン１００部に対してフェ
ノ−ルスルホン酸の６５％溶液１０部を充分撹拌混合し
発泡させ、フォ−ムを形成させた。そのフォ−ムの硬化
時間は５.５分であり、仕上り生成物の密度は０.０３８
であり、圧縮強度は１.１１Ｋｇ／ｃｍ2であった。
【０００６】
【実施例２、３】発泡剤である１，３−ジオキソランの
添加量を変えて、実施例−１と同様の操作を行って得ら
れた結果を下表に示す。
【比較例】発泡剤として従来のフロン１１を使用した例
を比較例として実施例と共に下表に示した。
【０００７】
＊１：発泡剤として１,３ＤＯＬの代わりにフロン１１
を使用
【０００８】
【発明の効果】本発明は上記の説明から明らかな様に、
１，３−ジオキソランを発泡剤として使用することによ
り圧縮強度、断熱性などに優れ、特に微細なセル構造を
有するフェノ−ルフォ−ムを製造することが可能となっ
た。特にオゾン層破壊を引き起こすＣＦＣを使用しない
で地球環境を保護する極めて有用な発泡手段を推奨する
ことができる。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic resin form, and more particularly, to a phenol resin foam, which is used as a foaming agent.
The present invention relates to a process for producing a phenolic resin foam having excellent uniformity in filling, compressive strength and heat insulation, and having a very uniform and fine cell structure using dioxolan. 2. Description of the Related Art Generally, phenol resin foams are used as foaming agents for trichlorofluoromethane (commonly known as CFC-11) and trichlorotrifluoroethane (commonly known as Freon 113) which are extremely excellent in heat insulating properties and flame retardancy. ) Is used,
The phenolic resin foam obtained thereby has high heat resistance, and is excellent in fire resistance, smoke resistance, and heat insulation. Therefore, its development is being promoted for various heat insulation materials including building materials. Also, phenolic resin foams are similar to polyurethane resin foams in terms of price, thermal stability, fire resistance, moisture resistance, chemical resistance, dimensional stability, smoke generation, electrical properties and compatibility with in-situ foaming. It would be advantageous to produce phenolic resin forms that are more advantageous than other foamed resins and for various applications. However, despite the many performance advantages and economic benefits, phenolic resin foam has not penetrated the insulating market. This is because today's phenolic resin forms have broken cell walls and central cracks and / or voids in the foam mass and are susceptible to cavitation caused by blowholes or channels. This is a result of the problem with the phenolic resin form. [0003] Recently, chlorofluorocarbons have been regulated to protect the earth's ozone layer. This regulation covers CFC-11 and CFC-1 which have been used as foaming agents for phenol resin foams.
13 is also included. Therefore CFC-11, CFC-1
The development of a foaming agent for phenol resin foam replacing 13 is obligatory. Currently, hydrocarbon compounds such as cyclopentane have been proposed as halogen-free blowing agents replacing CFC-11 and -113. However, these compounds have extremely low flash points and poor compatibility with existing phenolic resins, so that phenolic resin foams are used.
In order to obtain such a system, it is necessary to devise equipment and the like, and it is difficult to obtain a uniform cell structure. SUMMARY OF THE INVENTION The present inventors have made intensive efforts to overcome the above-mentioned problems, and as a result, have found that 1,3-dioxolan is used as a foaming agent for phenol resin foam. The present invention has been found to produce a phenolic foam having excellent form filling, compressive strength and heat insulating properties, and having a uniform and fine cell structure with almost no cracks or voids. . Therefore, the resole type phenol resin used in the present invention is generally obtained by reacting phenol with an excess of formaldehyde in an alkaline manner. The phenol-formaldehyde molar ratio of
1-1: 2.0, preferably 1: 1.3-1:
1.6. Usually, the cured products of these phenolic resins are hard and brittle, but in order to remedy this drawback, for example, grafting the phenolic resin with a polymer having high viscoelasticity, A phenol resin modified with a polyol di- or triglycidyl ether compound or the like can also be used. 1,3- as foaming agent
Dioxolane is used in an appropriate amount, preferably 5 to 20%.
It is. The acidic catalyst used in the present invention is not particularly limited, and organic sulfonic acids such as paratoluenesulfonic acid, phenolsulfonic acid, xylenesulfonic acid, resolesulfonic acid, metaxylenesulfonic acid, and benzenesulfonic acid. , Phosphoric acid, sulfuric acid, oxalic acid, carboxylic acid and the like are used. The amount used is not particularly limited, but is normally 10 to 20%. The foam stabilizer is a conventionally known organosilicon compound, and its use amount is not particularly limited, but 0.1 to 10% is suitable. Other surfactants, auxiliaries, stabilizers, coloring agents, and the like can be added as necessary. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. EXAMPLES Example 1 A viscosity at 25 ° C. of 5,000 cps
A phenolic phenol having a solid content of 32%
Silicone surfactant as a foam stabilizer in 100 parts of resin
About 2 parts and 10 parts of 1,3-dioxolane as a foaming agent were added and stirred and mixed to form a stable emulsion. Then, 10 parts of a 65% solution of phenolsulfonic acid was sufficiently mixed with 100 parts of the obtained emulsion by stirring and foaming to form a foam. The cure time of the form is 5.5 minutes and the density of the finished product is 0.038.
And the compressive strength was 1.11 kg / cm 2 . Examples 2 and 3 The results obtained by performing the same operation as in Example 1 by changing the amount of 1,3-dioxolane as a foaming agent are shown in the following table. Comparative Example An example using conventional Freon 11 as a foaming agent is shown in the table below together with an example as a comparative example. [0007] * 1: Freon 11 instead of 1,3 DOL as a foaming agent
According to the present invention, as is apparent from the above description,
By using 1,3-dioxolane as a foaming agent, it became possible to produce a phenol form having excellent compressive strength and heat insulating properties, and particularly having a fine cell structure. In particular, extremely useful foaming means for protecting the global environment without using CFCs that cause ozone depletion can be recommended.
Claims (1)
泡剤等からフェノ−ル樹脂フォ−ムを製造する方法にお
いて、発泡剤として１，３−ジオキソランを用いること
を特徴とするフェノ−ル樹脂フォ−ムの製造方法。(57) [Claims 1] In a method for producing a phenolic resin form from a resole type phenolic resin, an acidic catalyst, a foaming agent, etc., 1,3-dimethylphenol is used as a foaming agent. A method for producing a phenolic resin form, comprising using dioxolan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34465693A JP3381042B2 (en) | 1993-12-21 | 1993-12-21 | Method for producing phenolic resin form |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34465693A JP3381042B2 (en) | 1993-12-21 | 1993-12-21 | Method for producing phenolic resin form |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07179644A JPH07179644A (en) | 1995-07-18 |
| JP3381042B2 true JP3381042B2 (en) | 2003-02-24 |
Family
ID=18370964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34465693A Expired - Fee Related JP3381042B2 (en) | 1993-12-21 | 1993-12-21 | Method for producing phenolic resin form |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3381042B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104237042B (en) * | 2014-09-30 | 2015-05-13 | 中国石油大学(华东) | Testing device for simulating organic coating washout environment |
-
1993
- 1993-12-21 JP JP34465693A patent/JP3381042B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07179644A (en) | 1995-07-18 |
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