JPS5815524A - Production of solid phenol/melamine co-condensation resin - Google Patents
Production of solid phenol/melamine co-condensation resinInfo
- Publication number
- JPS5815524A JPS5815524A JP11305281A JP11305281A JPS5815524A JP S5815524 A JPS5815524 A JP S5815524A JP 11305281 A JP11305281 A JP 11305281A JP 11305281 A JP11305281 A JP 11305281A JP S5815524 A JPS5815524 A JP S5815524A
- Authority
- JP
- Japan
- Prior art keywords
- melamine
- resin
- phenol
- reaction
- initial condensate
- 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.)
- Granted
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、自己硬化性の固形状フェノール・メラミン共
縮合樹脂の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a self-curing solid phenol-melamine cocondensation resin.
メラミン樹脂とフェノール樹脂とはいずれも古くから知
られ、かつ実用に用いられている樹脂であるが、メラミ
ン樹脂は耐トラッキング性、耐アーク性、耐燃性等に優
れている一方、硬度が高すぎるため耐衝撃性、耐クラッ
ク性2機械加工性。Melamine resin and phenolic resin are both resins that have been known for a long time and have been used in practice.While melamine resin has excellent tracking resistance, arc resistance, flame resistance, etc., it has too high hardness. Due to its impact resistance, crack resistance and machinability.
成形性等が劣ることが問題とされておシ、またフェノー
ル樹脂は耐熱性2機椋加工性等については優れているが
、耐トラッキング性、耐アーク性。Poor moldability has been a problem, and phenolic resins are excellent in terms of heat resistance, machining properties, etc., but tracking resistance and arc resistance are poor.
耐候性が劣ることが問題とされていた。従って。The problem was that it had poor weather resistance. Therefore.
これらの両者の樹脂の長所を生かし、欠点を改良する目
的で各種のフェノール・メラミン共縮合樹脂の開発も行
なわれてきた。Various phenol/melamine cocondensation resins have been developed to take advantage of the advantages of both of these resins and improve their disadvantages.
従来よシ開発されてきたフェノール・メラミン共縮合樹
脂の代表的な製造法としては次に記す方法を挙げること
ができる。Typical methods for producing phenol-melamine cocondensation resins that have been developed in the past include the following methods.
(1) メラミン、フェノールそしてホルムアルデヒ
ドの混合物を塩基性触媒の存在下で共縮合反応させる方
法。(1) A method in which a mixture of melamine, phenol and formaldehyde is subjected to a co-condensation reaction in the presence of a basic catalyst.
(2) フェノールとホルムアルデヒドを塩M 性触
媒の存在下で縮合させて自己硬化性フェノール樹脂初期
縮金物を得た後、これにメラミンを加えて共縮合反応さ
せる方法。(2) A method in which phenol and formaldehyde are condensed in the presence of a salt catalyst to obtain a self-curing phenol resin initial condensate, and then melamine is added thereto to carry out a co-condensation reaction.
これらの方法により得られる樹脂はいずれも液状樹脂で
あるため、成形材料として用いる場合に充填剤(基材)
に含浸して乾燥および粉砕処理を必要とする湿式1法を
利用することになる。従って、製造工程が複雑となり、
生産性が低いとの欠点がある。The resins obtained by these methods are all liquid resins, so when used as molding materials, fillers (base materials) are used.
Wet method 1, which requires impregnation, drying and pulverization, will be used. Therefore, the manufacturing process becomes complicated,
The disadvantage is that productivity is low.
一方、固形状フェノール樹脂と固形状メラミン樹脂とを
混合した後に充填剤を加えて混合することからなる乾式
1法も知られているが、この方法により得られた樹脂混
合物は成形性に乏しく、かつ成形物の耐クラツク性が充
分でないとの欠点がある。On the other hand, a dry method 1 is also known, which consists of mixing a solid phenol resin and a solid melamine resin and then adding a filler, but the resin mixture obtained by this method has poor moldability. Another drawback is that the crack resistance of the molded product is not sufficient.
マタ、フェノールとホルムアルデヒドをまず酸性触媒の
存在下で反応させノボラック型初期縮合物をつくり、こ
れに塩基性触媒を加えてメチロール化して自己硬化型ノ
ボラック樹脂とした後、メラミンを加えて共縮合を行な
い、自己硬化性フェノールメラミン共縮合樹脂を製造す
る方法も公知であるが、耐l・ラッキング性および耐ア
ーク性が劣る欠点がある。First, phenol and formaldehyde are reacted in the presence of an acidic catalyst to create a novolak-type initial condensate, and a basic catalyst is added to this to methylolize it to form a self-curing novolac resin. Melamine is then added to perform co-condensation. A method for producing a self-curing phenol-melamine cocondensation resin is also known, but it has the disadvantage of poor l/racking resistance and arc resistance.
本発明は上記のような従来のフェノール・メラミン共縮
合樹脂、及びフェノール樹脂とメラミン樹脂との混合物
の各々の欠点を持たないフェノール・メラミン共縮合樹
脂を提供することを目的とするものであシ1本発明は、
塩基性触媒の存在下でメラミンとホルムアルデヒドを1
:1.5〜3.0のモル比にて反応させることにより得
た液状メラミン樹脂初期縮合物(5)と、酸性触媒の存
在下でフェノールとホルムアルデヒドをx:0.t〜o
、45のモル比にて反応させることによシ得たノボラッ
ク型の液状フェノール樹脂初期縮合物(B) 、!:を
、(A)100重量部に対して(B)6〜56重量部の
割合で混合し、この混合物を一17〜100条件下で共
縮合反応にかけ2次いで減圧下で水を留去させることを
特徴とする自己硬化性の固形状フェノール・メラミン共
縮合樹脂の製造法からなるものである。The object of the present invention is to provide a phenol-melamine co-condensed resin that does not have the disadvantages of the conventional phenol-melamine co-condensed resins and mixtures of phenol resins and melamine resins as described above. 1 The present invention is
Melamine and formaldehyde in the presence of a basic catalyst
: A liquid melamine resin initial condensate (5) obtained by reacting at a molar ratio of x:1.5 to 3.0, and phenol and formaldehyde in the presence of an acidic catalyst are mixed with x:0. t~o
, a novolac type liquid phenolic resin initial condensate (B) obtained by reacting at a molar ratio of 45,! : are mixed in a ratio of 6 to 56 parts by weight of (B) to 100 parts by weight of (A), and this mixture is subjected to a cocondensation reaction under conditions of -17 to 100 °C, and then water is distilled off under reduced pressure. This method consists of a method for producing a self-curing solid phenol-melamine cocondensation resin characterized by the following.
次に本発明の構成を詳しく説明する。Next, the configuration of the present invention will be explained in detail.
本発明は、先ず第一に、メラミンとホルムアル(4)
デヒドとの初期縮合物(Nとフェノールとホルムアルデ
ヒドとのノボラック型初期縮合物(B)を別々に調製し
た後に2両者を共縮合反応にかけ1次いで脱水処理を行
なうことを特徴としている。本発明は更に各初期縮合物
の調製に際して用いる各原料の量の相対比を特定した点
、そして共縮合反応の原料として用いる各初期縮合物の
混合比及び共縮合反応の反応条件を特定した点もまたそ
の特徴としている。The present invention first involves separately preparing an initial condensate of melamine and formal(4)dehyde (a novolak-type initial condensate (B) of N, phenol, and formaldehyde, and then subjecting the two to a co-condensation reaction. The present invention is further characterized in that the relative ratio of the amounts of each raw material used in the preparation of each initial condensate is specified, and the mixing of each initial condensate used as a raw material for the co-condensation reaction. Another characteristic of this method is that the ratio and reaction conditions of the cocondensation reaction were specified.
本発明においてメラミンとホルムアルデヒドとの初期縮
合物(菊は、塩基性触媒の存在下でメラミンとホルムア
ルデヒドを1:1.5〜3.00モル比(メラミン:ホ
ルムアルデヒド)、好ましくはl:1.6〜2.2のモ
ル比(同)にて反応させることによシ調製する。この反
応に使用する塩基性触媒は通常のメラミン樹脂の製造用
に用いられる塩基性触媒から任意に選ぶことができ、そ
のような触媒の例としては水酸化ナトリウム、水酸化カ
リウムそして炭酸ナトリウムを挙げることができる。In the present invention, the initial condensation product of melamine and formaldehyde (chrysanthemum) is a mixture of melamine and formaldehyde in the presence of a basic catalyst in a molar ratio of 1:1.5 to 3.00 (melamine:formaldehyde), preferably l:1.6. It is prepared by reacting at a molar ratio of ~2.2 (same).The basic catalyst used in this reaction can be arbitrarily selected from the basic catalysts used for the production of ordinary melamine resins. Examples of such catalysts include sodium hydroxide, potassium hydroxide and sodium carbonate.
この反応は8例えば所定のモル化の範囲内のメラ(5)
ミンとホルムアルデヒドとの混合溶液に塩基性触媒を加
えることによシ、その混合溶液の−1を8〜10に調整
し2次いで加温することによシメラミンをその混合溶液
中に溶解せしめ、更にこのメラミンの溶解の時点から約
5〜120分間、70℃から還流温度の範囲内の温度に
溶液を維持することにより行なう。This reaction can be carried out by adding a basic catalyst to a mixed solution of mela(5)mine and formaldehyde within a predetermined molarization range, adjusting the -1 of the mixed solution to 8 to 10, and then This is done by dissolving the simelamine in the mixed solution by heating and maintaining the solution at a temperature within the range of 70 DEG C. to reflux for about 5 to 120 minutes from the time of dissolution of the melamine.
初期縮合物(4)の調製に際して、メラミン1モルに対
してホルムアルデヒドを1.5モルより少なくすると生
成する初期縮合物(N中に未反応メラミンが残るため2
次の共縮合反応が不均一な反応になりやすく好ましくな
い。一方、メラミン1モルに対してホルムアルデヒドを
3.0モルより多くすると生成物中にメチロール基及び
ジメチレンエーテル基が多量含有されるようになりゲル
化を起こしやすくなるため、また更に次の共縮合反応に
よシ得られる樹脂の成形時の硬化反応の際に縮合水。When preparing the initial condensate (4), the initial condensate (4) produced when formaldehyde is less than 1.5 mol per 1 mol of melamine (2
The subsequent cocondensation reaction tends to be non-uniform, which is undesirable. On the other hand, if the amount of formaldehyde is more than 3.0 mol per 1 mol of melamine, the product will contain a large amount of methylol groups and dimethylene ether groups, which will easily cause gelation. Condensed water during the curing reaction during molding of the resin obtained by the reaction.
ホルムアルデヒドなどの発生ガス量が増加し2作業環境
の悪化や耐クラック性2機械的強度、電気絶縁性の劣化
および成形品の外観不良の原因とな/al\
るため好壕しぐない。This is not desirable because the amount of gases such as formaldehyde generated will increase, resulting in deterioration of the working environment, deterioration of crack resistance, deterioration of electrical insulation, and poor appearance of molded products.
本発明は上記のような条件により得られるメラミンとホ
ルムアルデヒドの液状の初期縮合物(6)を一方の原料
として用いる。In the present invention, the liquid initial condensate (6) of melamine and formaldehyde obtained under the above conditions is used as one of the raw materials.
フェノールとホルムアルデヒドとの初期縮合物(B)は
、酸性触媒の存在下でフェノールとホルムアルデヒドを
1 : O,1〜0450モル比(フェノール:ホルム
アルデヒド)、好ましくは1:0.2〜0.40のモル
比(同)にて反応させることによシ調製するもので、ノ
ボラック型を形成している。The initial condensate (B) of phenol and formaldehyde is prepared by combining phenol and formaldehyde in the presence of an acidic catalyst in a molar ratio of 1:0, 1 to 0,450 (phenol:formaldehyde), preferably 1:0.2 to 0.40. It is prepared by reacting at the same molar ratio and forms a novolac type.
この反応に使用する酸性触媒は通常のノボラック型フェ
ノール樹脂の製造用に用いられる酸性触媒から任意に選
ぶことができ、そのような触媒の例としては塩酸そして
シュウ酸を添げることができる。この反応は2例えば所
定のモル比の範囲内のフェノールとホルムアルデヒドそ
して酸性触媒力らなる混合溶液を80℃〜還流温度の範
囲内の温度に10〜120分間、好ましくは30〜90
分間維持することにより行ない、ホルムアルデヒドの転
化率を999c以上とした生成物を得る。このようにし
て得られるフェノールとホルムアルデヒドとの初期縮合
物(B)は液状で、平均分子量約140〜250を有す
るものである。The acidic catalyst used in this reaction can be arbitrarily selected from acidic catalysts commonly used for producing novolac type phenolic resins, and examples of such catalysts include hydrochloric acid and oxalic acid. This reaction is carried out by heating a mixed solution of 2, for example, phenol and formaldehyde in a predetermined molar ratio range and an acidic catalyst to a temperature in the range of 80°C to reflux temperature for 10 to 120 minutes, preferably 30 to 90 minutes.
A product with a formaldehyde conversion of 999 c or more is obtained. The initial condensate (B) of phenol and formaldehyde thus obtained is liquid and has an average molecular weight of about 140 to 250.
初期縮合物(B)の調製に際して、フェノール1モルに
対してホルムアルデヒドを0.45モルよりも多くする
と反応の進展によシ反応液の粘性が高くなり水が分離し
て不均一系となりやすく、このため作業性が悪くなり好
ましくない。一方、フェノール1モルに対シてホルムア
ルデヒドヲ0.1モルより少なくすると未反応フェノー
ルが多く残存するようになるため1次の共縮合反応後に
得られる樹脂の硬化性、耐クラック性、電気絶縁性に悪
い影響を与え、好ましくない。When preparing the initial condensate (B), if the amount of formaldehyde is more than 0.45 mol per 1 mol of phenol, the viscosity of the reaction liquid increases due to the progress of the reaction, and water tends to separate and become a heterogeneous system. For this reason, workability deteriorates, which is not preferable. On the other hand, if the amount of formaldehyde is less than 0.1 mol per 1 mol of phenol, a large amount of unreacted phenol will remain, resulting in poor curing, crack resistance, and electrical insulation properties of the resin obtained after the primary cocondensation reaction. It has a bad influence on the people and is not desirable.
液状メラミン樹脂初期縮合物(A)とノボラック型液状
フェノール樹脂初期縮合物(B)とは100:6〜56
の割合(A:Bの重量比)に混合して共縮合反応にかけ
る。共縮合反応は、この混合溶液に水酸化ナトリウム、
水酸化カリウム、炭酸すトリウムなどのような塩基性化
合物を加えることにより溶液の−1を7〜1.0に調整
し9次いで例えば60℃〜還流温度の範囲内の温度で9
0分間以内、好ましくは60分間以内にこの溶液を維持
することによυ行々う3.このようにして得られた共縮
合反応液を2次いで減圧下、60〜115℃で水を除去
することにより固形状生成物、すなわち自己硬化性の固
形状フェノール・メラミン共縮合樹脂を得る。なお上記
の共縮合反応と脱水処理を一操作で行なうこと、すなわ
ち減圧下にて共縮合反応を行々うことも可能である。Liquid melamine resin initial condensate (A) and novolac type liquid phenol resin initial condensate (B) are 100:6 to 56
(weight ratio of A:B) and subjected to a cocondensation reaction. In the cocondensation reaction, sodium hydroxide and
The −1 of the solution is adjusted to 7 to 1.0 by adding basic compounds such as potassium hydroxide, sodium carbonate, etc., and then heated at a temperature in the range of e.g. 60° C. to reflux temperature.
3. By maintaining this solution for no more than 0 minutes, preferably no more than 60 minutes. The cocondensation reaction solution thus obtained is then subjected to water removal under reduced pressure at 60 to 115°C to obtain a solid product, that is, a self-curing solid phenol-melamine cocondensation resin. Note that it is also possible to carry out the above-mentioned cocondensation reaction and dehydration treatment in one operation, that is, to carry out the cocondensation reaction under reduced pressure.
本発明の共縮合反応の実施に際してメラミン樹脂初期縮
合物(A) 100重量部に対してフェノール樹脂初期
縮合物(B)を6重量部よりも少なくすると。When carrying out the co-condensation reaction of the present invention, the amount of the phenol resin initial condensate (B) is less than 6 parts by weight relative to 100 parts by weight of the melamine resin initial condensate (A).
生成する樹脂が従来のメラミン樹脂と類似の特性を示す
ようになシ、耐衝撃性および耐クラツク性が劣る樹脂と
なる。一方、メラミン樹脂初期縮合物(A) 100重
量部に対してフェノール樹脂初期縮金物申)を56重量
部よりも多くした場合には未反応フェノールが共縮合反
応後の樹脂に多く残るようになり、そのような樹脂は耐
トラツキング性。The resulting resin exhibits properties similar to conventional melamine resins, but has poor impact and crack resistance. On the other hand, if the amount of phenol resin initial condensate (A) is greater than 56 parts by weight per 100 parts by weight of melamine resin initial condensate (A), a large amount of unreacted phenol will remain in the resin after the co-condensation reaction. , such resins are tracking resistant.
耐アーク性そして硬化性が劣るため実用上好ましくない
。It is not preferred in practice because of poor arc resistance and hardenability.
前述のようにして得られるフェノール樹脂初期縮合物(
B)は−0,8〜1.2の酸性を示し、この!1まの状
態でメラミン樹脂初期縮合物(B)との共縮合反応を行
なうと共縮合の反応系の…は5〜6.8と酸性となり、
目的の共縮合反応よシもむしろメラミン樹脂中のメチロ
ールメラミン相互の縮合反応が優先して発生することに
なシ、また反応液もゲル化しやすくなる。従って、共縮
合反応及び/又は減圧脱水操作の際の−は7〜10に維
持されるように管理する必要がある。共縮合反応を−7
よシ低いか、あるいは−110よシも高い条件下で行な
った場合には反応の途中でゲル化が発生し、目的とする
樹脂を得ることができない。なお共縮合反応の反応液の
声を7〜10に管理するためには2例えばフェノール樹
脂初期縮合物ω)の−を該縮合物の製造直後に上記の範
囲内となるように調整するか、あるいはメラミン樹脂初
期縮合物(6)と混合した後に−の調整を行なうなどの
方法を採用することができる。Phenol resin initial condensate obtained as described above (
B) shows an acidity of -0.8 to 1.2, and this! When the cocondensation reaction with the melamine resin initial condensate (B) is carried out in the state of 1, the cocondensation reaction system becomes acidic with a value of 5 to 6.8,
Rather than the desired co-condensation reaction, the condensation reaction between the methylolmelamine in the melamine resin occurs preferentially, and the reaction solution also tends to gel. Therefore, it is necessary to manage the cocondensation reaction and/or vacuum dehydration operation so that - is maintained at 7 to 10. Cocondensation reaction -7
If the reaction is carried out under conditions that are too low or as high as -110, gelation will occur during the reaction, making it impossible to obtain the desired resin. In addition, in order to control the voice of the reaction solution in the cocondensation reaction to 7 to 10, for example, adjust the - of the phenol resin initial condensate ω) to be within the above range immediately after producing the condensate, or Alternatively, it is possible to adopt a method in which - is adjusted after mixing with the melamine resin initial condensate (6).
フェノール・メラミン共縮合樹脂を得るために本発明の
方法を用いた場合には、各段階の反応の制御が容易でゲ
ル化、不均一反応などが起こシにくいため作業性が高い
との特徴を有する。When the method of the present invention is used to obtain a phenol-melamine cocondensation resin, it is characterized by high workability because the reactions at each stage can be easily controlled and gelation and heterogeneous reactions are less likely to occur. have
一方2本発明によシ得られるフェノール・メラミン共縮
合樹脂は自己硬化型で固形状として取り出されるため、
そのまま充填剤、離型剤などと混練した後、生産性の高
い乾式1法によシ耐トラッキング性、耐アーク性、耐ク
ラック性、耐熱性および成形性の優れた成形体を製造す
ることができる。On the other hand, the phenol-melamine cocondensation resin obtained according to the present invention is self-curing and can be taken out as a solid.
After kneading it as it is with fillers, mold release agents, etc., it is possible to produce molded products with excellent tracking resistance, arc resistance, crack resistance, heat resistance, and moldability using the highly productive dry method 1. can.
次に実施例により本発明を更に詳しく説明する。Next, the present invention will be explained in more detail with reference to Examples.
なお実施例中の1部」は「重量部」を意味する。Note that "1 part" in the examples means "part by weight."
〔実施例1〕
(1) ノボラック型フェノール樹脂初期縮合物の調
製
フェノール3299(3,5モル)と36%ホルマリン
s7.5r(x、o5モル)との混合物にシュウ酸1.
6fを加え、還流下で60分間反応させた後、30℃に
冷却し、10%水酸化ナトリウム水溶液を加えて反応液
の−を8.8に調整してノボラック型フェノール樹脂初
期縮合物425.1 tを得た。[Example 1] (1) Preparation of novolak type phenolic resin initial condensate A mixture of phenol 3299 (3.5 mol) and 36% formalin S7.5r (x, o 5 mol) was mixed with 1.0 oxalic acid.
After adding 6f and reacting for 60 minutes under reflux, it was cooled to 30°C, and a 10% aqueous sodium hydroxide solution was added to adjust the - of the reaction mixture to 8.8 to obtain a novolak type phenolic resin initial condensate 425. I got 1t.
(2) メラミン樹脂初期縮合物の調製36%ホルマ
リン3001F(3,6モル)と水20、2 Fの混合
物に10%水酸化す) IJウム水溶液を加えて混合物
の−Iを9.0に調整し、これにメラミン252f(2
,0モル)を加えた。この混合物を油浴で加温すること
により室温から90℃にまで1時間をかけて徐々に昇温
させ、その後90℃に10分間保つことによりメラミン
樹脂初期縮合物573vを得た。(2) Preparation of melamine resin initial condensate Add 10% hydroxide to a mixture of 36% formalin 3001F (3.6 mol) and water 20.2F) Add IJum aqueous solution to bring -I of the mixture to 9.0 Adjust and add melamine 252f (2
,0 mol) was added. This mixture was heated in an oil bath to gradually raise the temperature from room temperature to 90°C over 1 hour, and then kept at 90°C for 10 minutes to obtain 573v of a melamine resin initial condensate.
(3)固形状フェノール・メラミン共縮合樹脂の製造上
記の(2)によシ調製したメラミン樹脂初期縮合物の全
量に上記の(りによシ得られたフェノール樹脂初期縮合
物811Fを加え、80〜85℃で15分間共縮合反応
を行なった。次いで反応混合物の温度を60〜110℃
に保ち、同時に反応混合物系の圧力を480〜160
un Hy に減圧することにより脱水を行なった。(3) Production of solid phenol-melamine co-condensate resin Add the above-obtained phenol resin initial condensate 811F to the entire amount of the melamine resin initial condensate prepared in (2) above, The cocondensation reaction was carried out at 80-85°C for 15 minutes.Then, the temperature of the reaction mixture was increased to 60-110°C.
and simultaneously maintain the pressure of the reaction mixture system at 480 to 160
Dehydration was performed by reducing the pressure to un Hy.
脱水量が224fに達した時点で脱水操作を停止し、生
成した固形状樹脂を取シ出した。得られた固形状樹脂の
軟化点は85℃で、ゲル化時間120秒であった。When the amount of dehydration reached 224 f, the dehydration operation was stopped and the produced solid resin was taken out. The solid resin obtained had a softening point of 85° C. and a gelation time of 120 seconds.
この樹脂70部とバルブ17部、アスベスト30部に離
型剤を配合して混線、粉砕し成形材料を得た。A mold release agent was blended with 70 parts of this resin, 17 parts of a valve, and 30 parts of asbestos, mixed, and crushed to obtain a molding material.
〔実施例2〕
36%ホルマリン3oor(3,6モル)と水20、2
fの混合物に10%水酸化ナトリウム水溶液を加えて
混合物の−1を9.0に調整し、これにメラミン252
ft(2゜0モル)を加えた。この混合物を油浴で加温
することにより室温から90℃にまで1時間をかけて徐
々に昇温させ、その後90℃に10分間保つことにより
メラミン樹脂初期縮合物5731を得た。[Example 2] 36% formalin 3oor (3.6 mol) and water 20.2
A 10% aqueous sodium hydroxide solution was added to the mixture of f to adjust -1 of the mixture to 9.0, and melamine 252
ft (2°0 mol) was added. This mixture was heated in an oil bath to gradually raise the temperature from room temperature to 90°C over 1 hour, and then kept at 90°C for 10 minutes to obtain melamine resin initial condensate 5731.
上記の操作によシ調製したメラミン樹脂初期縮合物の全
量に、実施例1の(1)で調製したフェノール樹脂初期
縮合物106゜8vを加え、80〜85℃で15分間共
縮合反応を行なった。次いで反応混合物の温度を60〜
105℃に保ち、同時に反応混合物系の圧力を480〜
160 smHy に減圧することによシ脱水を行な
った。脱水量が2162に達した時点で脱水操作を停止
し、生成した固形状樹脂を取シ出した。得られた固形状
樹脂の軟化点は87℃で、ゲル化時間は240秒であっ
た。To the entire amount of the melamine resin initial condensate prepared by the above procedure, 106°8v of the phenolic resin initial condensate prepared in Example 1 (1) was added, and a cocondensation reaction was carried out at 80 to 85°C for 15 minutes. Ta. The temperature of the reaction mixture was then adjusted to 60~
Maintain the temperature at 105°C, and at the same time increase the pressure of the reaction mixture system to 480~
Dehydration was carried out by reducing the pressure to 160 smHy. When the amount of dehydration reached 2162, the dehydration operation was stopped and the solid resin produced was taken out. The solid resin obtained had a softening point of 87° C. and a gelation time of 240 seconds.
この樹脂70部とバルブ17部、アスベスト30部に離
型剤を配合して混練、粉砕し成形材料を得た。A mold release agent was blended with 70 parts of this resin, 17 parts of the bulb, and 30 parts of asbestos, and the mixture was kneaded and crushed to obtain a molding material.
〔比較例1〕
メラミン樹脂(ダイマー型メチロールメラミン樹脂)4
9部とノボラック型フェノール樹脂(数平均分子量58
0)21部、バルブ17部、アスベスト30部に離型剤
を配合して混練、粉砕し成形材料を得た。[Comparative Example 1] Melamine resin (dimer type methylol melamine resin) 4
9 parts and novolak type phenolic resin (number average molecular weight 58
0), 17 parts of a valve, and 30 parts of asbestos were mixed with a mold release agent, kneaded, and pulverized to obtain a molding material.
〔比較例2〕
フェノール188r(2,0モル)と36%ホルマリン
166.7f(2,0モル)との混合液に3.65%塩
酸4CCを加え、80℃で70分間反応させノボラック
型初期縮合物をつクシ、次に36%ホルマリン33a、
3y(toモル)、509cトリエタノールアミン44
9を加えて一■7.8に調節した後。[Comparative Example 2] 4CC of 3.65% hydrochloric acid was added to a mixture of phenol 188r (2.0 mol) and 36% formalin 166.7f (2.0 mol), and the mixture was reacted at 80°C for 70 minutes to form a novolak-type initial stage. comb the condensate, then 36% formalin 33a,
3y (to mol), 509c triethanolamine 44
After adding 9 and adjusting to 7.8.
80℃で60分反応させてレゾールを得た。A resol was obtained by reacting at 80° C. for 60 minutes.
この樹脂液にメラミン2529 (2,0%ル) ト3
6%ホルマリy83.3 f (1,0モル)を加え。Add melamine 2529 (2.0%) to this resin solution.
Add 6% formali y83.3f (1.0 mol).
s o X )リエタノールアミンで−17.9に調節
し。s o X ) adjusted to −17.9 with reethanolamine.
80℃で60分共縮合反応を行なった。次いで実施例1
および2と同様の操作で減圧脱水し、脱水量4001に
達した時点で脱水操作を停止し、樹脂を取シ出した。得
られた固形状樹脂の軟化点は80℃で、ゲル化時間60
秒であった。A cocondensation reaction was carried out at 80°C for 60 minutes. Next, Example 1
Dehydration was carried out under reduced pressure in the same manner as in step 2. When the amount of dehydration reached 4001, the dehydration operation was stopped and the resin was taken out. The softening point of the obtained solid resin was 80°C, and the gelation time was 60°C.
It was seconds.
この樹脂70部とパルプ17部、アスベスト30部に離
型剤を配合して混線、粉砕し、成形材料を得た。A mold release agent was blended with 70 parts of this resin, 17 parts of pulp, and 30 parts of asbestos, mixed and crushed to obtain a molding material.
実施例1〜2及び比較例1〜2の成形材料の性能を比較
するために、各々の成形材料を成形加工して各種の試験
を行なった。試験項目及び試験結果を第1表に示す。In order to compare the performance of the molding materials of Examples 1 and 2 and Comparative Examples 1 and 2, each molding material was molded and various tests were conducted. Test items and test results are shown in Table 1.
第1表
なお、試験に用いた試験片は、耐トラツキング性と耐ク
ラツク性の試験については圧縮成形、それ以外の試験に
ついては移送成形により製造したものを用いた。Table 1 Note that the test pieces used in the tests were compression molded for the tracking resistance and crack resistance tests, and were manufactured by transfer molding for the other tests.
耐クラツク性は、内径42m、高さ10.0インサート
金具を入れた肉厚4mの試験片を用い。For crack resistance, a test piece with a wall thickness of 4 m and an inner diameter of 42 m and a height of 10.0 mm was inserted.
130℃、25分間加熱した後、冷水中で5分間冷却す
る工程を1サイクルとして測定した。その他の項目につ
いては JISK−6911に規定された試験法に従い
試験を行なった。One cycle was measured by heating at 130° C. for 25 minutes and then cooling in cold water for 5 minutes. For other items, tests were conducted in accordance with the test methods specified in JISK-6911.
第1表に示した試験結果により、実施例1〜2の成形材
料は射出成形操作における成形性が良好で、成形収縮率
が小さく、耐クラツク性に優れ。According to the test results shown in Table 1, the molding materials of Examples 1 and 2 had good moldability in injection molding operations, had low mold shrinkage, and had excellent crack resistance.
耐トラッキング性9機械的強度、電気絶縁性が良好であ
ることがわかる。また実施例1〜2の成形材料は成形時
におけるホルムアルデヒド臭が少なく作業性も良好であ
った。一方比較例1の成形材料は各種の項目の内では良
好な値を示す項目もあるが、特に成形収縮率2曲げ強さ
、衝撃強さ、電気絶縁性そして耐クラツク性については
実用的に充分な性能を示していない。また比較例2の成
形材料についてもいくつかの項目については実用的に充
分な性能を示していない。Tracking Resistance 9 It can be seen that the mechanical strength and electrical insulation properties are good. Further, the molding materials of Examples 1 and 2 had little formaldehyde odor during molding and had good workability. On the other hand, the molding material of Comparative Example 1 shows good values in some of the various items, but in particular, the molding shrinkage rate 2 bending strength, impact strength, electrical insulation property, and crack resistance are insufficient for practical use. It does not show good performance. Further, the molding material of Comparative Example 2 also did not exhibit sufficient performance for practical use in some items.
特許出願人 宇部興産株式会社 代理人 弁理士柳川泰男Patent applicant Ube Industries Co., Ltd. Agent: Patent attorney Yasuo Yanagawa
Claims (1)
:1.5〜3.0のモル比にて反応させることにより得
た液状メラミン樹脂初期縮合物(6)と。 酸性触媒の存在下でフェノールとホルムアルデヒドを1
:0.1〜0.45のモル比にて反応させることによシ
得たノボラック型の液状フェノール樹脂初期縮合物ω)
とを、(A)100重量部に対して(B)6〜56重量
部の割合で混合し、この混合物をpH7〜10の条件下
で共縮合反応にかけ1次いで減圧下で水を留去させるこ
とを特徴とする自己硬化性の固形状フェノール・メラミ
ン共縮合樹脂の製造法。[Claims] Melamine and formaldehyde are mixed together in the presence of a basic catalyst.
: with a liquid melamine resin initial condensate (6) obtained by reacting at a molar ratio of 1.5 to 3.0. phenol and formaldehyde in the presence of an acidic catalyst
: Novolak type liquid phenolic resin initial condensate obtained by reacting at a molar ratio of 0.1 to 0.45 ω)
are mixed in a ratio of 6 to 56 parts by weight of (B) to 100 parts by weight of (A), and this mixture is subjected to a cocondensation reaction under conditions of pH 7 to 10. Then, water is distilled off under reduced pressure. A method for producing a self-curing solid phenol-melamine co-condensation resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11305281A JPS6026491B2 (en) | 1981-07-21 | 1981-07-21 | Production method of solid phenol-melamine cocondensation resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11305281A JPS6026491B2 (en) | 1981-07-21 | 1981-07-21 | Production method of solid phenol-melamine cocondensation resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5815524A true JPS5815524A (en) | 1983-01-28 |
JPS6026491B2 JPS6026491B2 (en) | 1985-06-24 |
Family
ID=14602272
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11305281A Expired JPS6026491B2 (en) | 1981-07-21 | 1981-07-21 | Production method of solid phenol-melamine cocondensation resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6026491B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61203697U (en) * | 1985-06-12 | 1986-12-22 | ||
JPH0312799Y2 (en) * | 1986-03-14 | 1991-03-26 |
-
1981
- 1981-07-21 JP JP11305281A patent/JPS6026491B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS6026491B2 (en) | 1985-06-24 |
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