JPH11279248A - Melamine/phenol co-condensation resin and its production - Google Patents
Melamine/phenol co-condensation resin and its productionInfo
- Publication number
- JPH11279248A JPH11279248A JP8452898A JP8452898A JPH11279248A JP H11279248 A JPH11279248 A JP H11279248A JP 8452898 A JP8452898 A JP 8452898A JP 8452898 A JP8452898 A JP 8452898A JP H11279248 A JPH11279248 A JP H11279248A
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- Japan
- Prior art keywords
- phenol
- melamine
- condensation resin
- resin
- mol
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、強度、難
燃性等に優れる成形材料、摩擦材、塗料、コーティング
材、接着剤封止材、積層板、ＦＲＰ及び炭素製品原料に
好適なメラミン・フェノール共縮合樹脂及びその製造法
に関する。The present invention relates to a molding material, a friction material, a paint, a coating material, an adhesive sealing material, a laminate, an FRP, and a carbon material raw material which are excellent in heat resistance, strength, flame retardancy and the like. The present invention relates to a melamine-phenol co-condensation resin and a method for producing the same.
【０００２】[0002]
【従来の技術】フェノール樹脂及びメラミン樹脂は、耐
熱性、耐薬品性、強度等に優れていることから、成形
材、摩擦材、積層板、ＦＲＰ及び炭素製品のバインダー
として使用されている。加熱硬化型のフェノール樹脂、
メラミン樹脂は、エポキシ樹脂等の高価な硬化剤を加え
なくても樹脂単独で加熱硬化することから、成形材の製
造における、材料コストが安価になり、硬化剤の混合工
程を必要としない。加熱硬化型のフェノール樹脂は耐熱
性及び耐水性に優れているものの、メラミン樹脂に比べ
て劣っている。一方、加熱硬化型のメラミン樹脂はフェ
ノール樹脂に比べて難燃性に優れているものの、耐水性
に劣っている。そこで、両者の長所である耐熱性、耐水
性、難燃性に優れた樹脂組成物を得るために、フェノー
ル類とメラミン類の混合物及びその反応物が検討されて
いる。しかし、これまで検討された両者の混合物及びそ
の反応物は、窒素含有量を多くすると、軟化点が高くな
るという欠点がある。2. Description of the Related Art Phenol resins and melamine resins have been used as binders for molding materials, friction materials, laminates, FRP and carbon products because of their excellent heat resistance, chemical resistance, strength and the like. Heat-curable phenolic resin,
The melamine resin is cured by heating alone without adding an expensive curing agent such as an epoxy resin. Therefore, the material cost in the production of a molding material is reduced, and the step of mixing the curing agent is not required. Heat-curable phenolic resins are excellent in heat resistance and water resistance, but inferior to melamine resins. On the other hand, a heat-curable melamine resin is superior in flame retardancy to a phenol resin, but is inferior in water resistance. Therefore, a mixture of phenols and melamines and a reaction product thereof have been studied in order to obtain a resin composition having excellent heat resistance, water resistance, and flame retardancy, which are advantages of both. However, the mixture and the reaction product thereof, which have been studied so far, have a disadvantage that when the nitrogen content is increased, the softening point is increased.
【０００３】[0003]
【発明が解決しようとする課題】請求項１記載の発明
は、耐熱性、耐水性、難燃性及び強度に優れたメラミン
・フェノール共縮合樹脂を提供するものである。請求項
２記載の発明は、耐熱性、耐水性、難燃性及び強度に優
れたメラミン・フェノール共縮合樹脂を生産性よく製造
可能なメラミン・フェノール共縮合樹脂の製造法を提供
するものである。The object of the present invention is to provide a melamine-phenol co-condensation resin excellent in heat resistance, water resistance, flame retardancy and strength. The invention according to claim 2 provides a method for producing a melamine-phenol co-condensation resin capable of producing a melamine-phenol co-condensation resin excellent in heat resistance, water resistance, flame retardancy and strength with high productivity. .
【０００４】[0004]
【課題を解決するための手段】本発明は、メラミン類、
アルデヒド類及びフェノール類を反応させてなる、軟化
点が８０度以下でかつ窒素含有量が１０重量％以上であ
るメラミン・フェノール共縮合樹脂に関する。また、本
発明は、メラミン類、アルデヒド類及びフェノール類
を、アルデヒド類の仕込量がメラミン類及びフェノール
類の合計仕込量に対してモル比で０．０５〜１となるよ
うにして、反応させることを特徴とする軟化点が８０度
以下でかつ窒素含有量が１０重量％以上であるメラミン
・フェノール共縮合樹脂の製造法に関する。SUMMARY OF THE INVENTION The present invention provides a melamine,
The present invention relates to a melamine-phenol co-condensation resin obtained by reacting an aldehyde and a phenol and having a softening point of 80 degrees or less and a nitrogen content of 10% by weight or more. Further, in the present invention, melamines, aldehydes and phenols are reacted in such a manner that the charged amount of the aldehydes becomes 0.05 to 1 in a molar ratio with respect to the total charged amount of the melamines and phenols. A method for producing a melamine-phenol co-condensation resin having a softening point of not more than 80 degrees and a nitrogen content of not less than 10% by weight.
【０００５】[0005]
【発明の実施の形態】本発明で用いられるメラミン類
は、分子中にトリアジン核を有する化合物であり、例え
ば、メラミン、ベンゾグアナミン、アセトグアナミン等
のグアナミン誘導体、メチルシアヌレート等のシアヌル
酸誘導体などが挙げられ、この中でもメラミン、ベンゾ
グアナミン、アセトグアナミン等のグアナミン誘導体が
好ましい。本発明で用いられるアルデヒド類としては、
例えば、ホルマリン、パラホルムアルデヒド等が挙げら
れる。BEST MODE FOR CARRYING OUT THE INVENTION Melamines used in the present invention are compounds having a triazine nucleus in the molecule. Examples thereof include guanamine derivatives such as melamine, benzoguanamine and acetoguanamine, and cyanuric acid derivatives such as methyl cyanurate. Among them, guanamine derivatives such as melamine, benzoguanamine and acetoguanamine are preferred. Aldehydes used in the present invention include:
For example, formalin, paraformaldehyde and the like can be mentioned.
【０００６】本発明で用いられるフェノール類として
は、例えば、フェノール、クレゾール、キシレノール、
エチルフェノール、ブチルフェノール、ノニルフェノー
ル、オクチルフェノール等のアルキルフェノール類、ビ
スフェノールＡ、ビスフェノールＦ、ビスフェノール
Ｓ、レゾルシン、カテコール等の多価フェノール、ハロ
ゲン化フェノール、フェニルフェノール、アミノフェノ
ール等が挙げられる。The phenols used in the present invention include, for example, phenol, cresol, xylenol,
Examples include alkylphenols such as ethylphenol, butylphenol, nonylphenol, and octylphenol, polyphenols such as bisphenol A, bisphenol F, bisphenol S, resorcinol, catechol, halogenated phenol, phenylphenol, and aminophenol.
【０００７】本発明のメラミン・フェノール共縮合樹脂
は軟化点が８０度以下でかつ窒素含有量が１０重量％以
上である。軟化点が８０度を超えると他の成分との混合
性、成形性が劣る。窒素含有量が１０重量％未満である
と難燃性が劣る。The melamine-phenol co-condensation resin of the present invention has a softening point of not more than 80 degrees and a nitrogen content of not less than 10% by weight. If the softening point exceeds 80 degrees, mixability with other components and moldability will be poor. When the nitrogen content is less than 10% by weight, the flame retardancy is poor.
【０００８】本発明のメラミン・フェノール共縮合樹脂
は、未反応ホルムアルデヒドを含まず、メチロール基を
有さないものであることが、エポキシ樹脂用硬化剤とし
て使用する場合の安定性の点から好ましい。本発明のメ
ラミン・フェノール共縮合樹脂に含まれる未反応フェノ
ール類は、１重量％以下であることが安全衛生性、臭気
の点から好ましい。The melamine-phenol co-condensation resin of the present invention preferably contains no unreacted formaldehyde and has no methylol group from the viewpoint of stability when used as a curing agent for epoxy resins. The unreacted phenol contained in the melamine-phenol co-condensation resin of the present invention is preferably 1% by weight or less from the viewpoint of safety and health and odor.
【０００９】本発明のメラミン・フェノール共縮合樹脂
は、例えば、メラミン類、アルデヒド類及びフェノール
類を、アルデヒド類の仕込量がメラミン類及びフェノー
ル類の合計仕込量に対してモル比で０．０５〜１となる
ようにして、反応させることにより製造できる。上記モ
ル数の比が０．０５未満であると得られるメラミン・フ
ェノール共縮合樹脂の窒素含有量が１０％未満となる。
また、１を超えると、得られるメラミン・フェノール共
縮合樹脂の軟化点が８０℃以上なる。上記モル比は０．
０５〜０．５であることが好ましい。The melamine-phenol co-condensation resin of the present invention comprises, for example, melamines, aldehydes and phenols in a molar ratio of 0.05 to the total charge of melamines and phenols. To 1 to produce a reaction. If the molar ratio is less than 0.05, the melamine-phenol co-condensation resin obtained has a nitrogen content of less than 10%.
If it exceeds 1, the softening point of the obtained melamine-phenol co-condensation resin will be 80 ° C or higher. The above molar ratio is 0.
It is preferably from 0.5 to 0.5.
【００１０】また、メラミン類の仕込量は、メラミン
類、アルデヒド類及びフェノール類の合計仕込量に対し
てモル比で０．０１〜０．９となるようにすることが好
ましく、０．０１〜０．５となるようにすることがより
好ましい。このモル比が０．０１未満であると、得られ
るメラミン・フェノール共縮合樹脂の窒素含有量が１０
％未満になる場合があり、０．９を超えると得られるメ
ラミン・フェノール共縮合樹脂の軟化点が８０℃を超え
る場合がある。The amount of melamine to be charged is preferably 0.01 to 0.9 in a molar ratio with respect to the total amount of melamine, aldehyde and phenol. More preferably, it is set to 0.5. When this molar ratio is less than 0.01, the nitrogen content of the obtained melamine-phenol co-condensation resin is 10
%, And if it exceeds 0.9, the softening point of the melamine-phenol co-condensation resin obtained may exceed 80 ° C.
【００１１】反応時のpHは９以下が好ましく、pH３〜９
がより好ましく、pH４〜８が特に好ましい。pHが９より
高いと、メラミン類、フェノール類及びアルデヒド類の
共縮合が起こりにくくなり、窒素含有量が１０％未満に
なる場合があり、３未満では反応中にゲル化し易くな
る。The pH during the reaction is preferably 9 or less, and the pH is 3-9.
Is more preferable, and pH 4 to 8 is particularly preferable. If the pH is higher than 9, co-condensation of melamines, phenols and aldehydes is less likely to occur, and the nitrogen content may be less than 10%. If the pH is less than 3, gelation tends to occur during the reaction.
【００１２】反応温度、反応時間には特に制限が無いが
６０℃〜２５０℃、１〜２４時間程度とされる。反応終
了後、常圧又は減圧下での蒸留、水洗等で、未反応のフ
ェノール類及び未反応アルデヒド類を除去できる。この
除去を蒸留で行う場合、温度を１００℃以上として行う
ことによりメチロール基を消失させることができ、得ら
れるメラミン・フェノール共縮合樹脂をメチロール基を
有さないものとすることができる。There are no particular restrictions on the reaction temperature and the reaction time, but the reaction is carried out at 60 ° C. to 250 ° C. for about 1 to 24 hours. After completion of the reaction, unreacted phenols and unreacted aldehydes can be removed by distillation under normal pressure or reduced pressure, washing with water, or the like. When the removal is carried out by distillation, the methylol group can be eliminated by setting the temperature to 100 ° C. or higher, and the melamine-phenol co-condensation resin obtained can have no methylol group.
【００１３】このようにして得られるメラミン・フェノ
ール共縮合樹脂の分子量に、特に制限はないが、重量平
均分子量（Ｍｗ）は３５０〜６００程度であることが好
ましい。なお、Ｍｗは、ゲルパーミエーションクロマト
グラフで測定し、標準ポリスチレン換算した値である。The molecular weight of the melamine-phenol co-condensation resin thus obtained is not particularly limited, but the weight average molecular weight (Mw) is preferably about 350 to 600. Here, Mw is a value measured by gel permeation chromatography and converted to standard polystyrene.
【００１４】[0014]
【実施例】以下に、実施例により本発明を説明する 実施例１ 撹拌機、還流冷却器及び温度計を備えたフラスコにメラ
ミン１２６ｇ（１モル）、３７重量％ホルマリン水２４
３ｇ（３モル）及びフェノール３７６０ｇ（４０モル）
を仕込み、還流脱水させながら２００℃まで４時間で昇
温させ、次いで２００℃で８時間反応させた。その後、
１８０℃にて減圧下で未反応フェノールを除去しメラミ
ン・フェノール共縮合樹脂を得た。The present invention will be described below by way of examples. Example 1 In a flask equipped with a stirrer, a reflux condenser and a thermometer, 126 g (1 mol) of melamine, 37% by weight formalin water 24
3 g (3 mol) and phenol 3760 g (40 mol)
And heated to 200 ° C. for 4 hours while refluxing and dehydrating, and then reacted at 200 ° C. for 8 hours. afterwards,
Unreacted phenol was removed at 180 ° C. under reduced pressure to obtain a melamine-phenol co-condensation resin.
【００１５】実施例２ 撹拌機、還流冷却器及び温度計を備えたフラスコにメラ
ミン１２６ｇ（１モル）、３７％ホルマリン水４８６ｇ
（６モル）及びフェノール３７６０ｇ（４０モル）を入
れ、４８重量％水酸化ナトリウム水溶液を用いpHを８．
０に調整後、還流脱水させながら２００℃まで４時間で
昇温させ、次いで２００℃で８時間反応させた。その
後、１８０℃にて減圧下で未反応フェノールを除去しメ
ラミン・フェノール共縮合樹脂を得た。Example 2 A flask equipped with a stirrer, reflux condenser and thermometer was charged with 126 g (1 mol) of melamine and 486 g of 37% formalin water.
(6 moles) and 3760 g (40 moles) of phenol, and adjusted to pH 8. using a 48% by weight aqueous sodium hydroxide solution.
After the temperature was adjusted to 0, the temperature was raised to 200 ° C. in 4 hours while refluxing and dehydrating, followed by a reaction at 200 ° C. for 8 hours. Thereafter, unreacted phenol was removed under reduced pressure at 180 ° C. to obtain a melamine-phenol co-condensation resin.
【００１６】実施例３ 撹拌機、還流冷却器及び温度計を備えたフラスコにベン
ゾグアナミン１８７ｇ（１モル）、３７重量％ホルマリ
ン水２４３ｇ（３モル）及びフェノール１８８０ｇ（２
０モル）を仕込み、還流脱水させながら２００℃まで４
時間で昇温させ、次いで２００℃で８時間反応させた。
その後、１８０℃にて減圧下で未反応フェノールを除去
しメラミン・フェノール共縮合樹脂を得た。Example 3 In a flask equipped with a stirrer, a reflux condenser and a thermometer, 187 g (1 mol) of benzoguanamine, 243 g (3 mol) of 37% by weight formalin water and 1880 g of phenol (2 mol)
0 mol), and refluxed to 200 ° C. while dehydrating.
Then, the reaction was carried out at 200 ° C. for 8 hours.
Thereafter, unreacted phenol was removed under reduced pressure at 180 ° C. to obtain a melamine-phenol co-condensation resin.
【００１７】実施例４ 撹拌機、還流冷却器及び温度計を備えたフラスコにベン
ゾグアナミン１８７ｇ（１モル）、３７重量％ホルマリ
ン水４８６ｇ（６モル）及びフェノール３７６０ｇ（４
０モル）を仕込み、４８％水酸化ナトリウム水溶液を用
いpHを８．０に調整後、還流脱水させながら２００℃ま
で４時間で昇温させ、次いで２００℃で８時間反応させ
た。その後、１８０℃にて減圧下で未反応フェノールを
除去しメラミン・フェノール共縮合樹脂を得た。Example 4 In a flask equipped with a stirrer, a reflux condenser and a thermometer, 187 g (1 mol) of benzoguanamine, 486 g (6 mol) of 37% by weight formalin water and 3760 g of phenol (4 mol)
0 mol), the pH was adjusted to 8.0 using a 48% aqueous sodium hydroxide solution, and the mixture was heated to 200 ° C. for 4 hours while refluxing and dehydrating, and then reacted at 200 ° C. for 8 hours. Thereafter, unreacted phenol was removed under reduced pressure at 180 ° C. to obtain a melamine-phenol co-condensation resin.
【００１８】比較例１ 撹拌機、還流冷却器及び温度計を備えたフラスコにメラ
ミン１８７ｇ（１モル）、３７重量％ホルマリン水９７
２ｇ（１２モル）及びフェノール４７０（５モル）を仕
込み、４８％水酸化ナトリウム水溶液を用いpHを８．０
に調整後、還流脱水させながら２００℃まで４時間で昇
温させ、次いで１００℃で２０時間反応させた。その
後、１８０℃にて減圧下で未反応フェノールを除去し樹
脂を得た。Comparative Example 1 A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 187 g (1 mol) of melamine and 97% by weight of 37% by weight formalin water.
2 g (12 mol) and phenol 470 (5 mol) were charged, and the pH was adjusted to 8.0 using a 48% aqueous sodium hydroxide solution.
Then, the mixture was heated to 200 ° C. in 4 hours while refluxing and dehydrating, and then reacted at 100 ° C. for 20 hours. Thereafter, unreacted phenol was removed at 180 ° C. under reduced pressure to obtain a resin.
【００１９】実施例１〜４及び比較例１における、原料
モル比、得られた樹脂の重量平均分子量（Ｍｗ）、軟化
点及び元素分析法から求めた窒素含有量の結果を表１に
示した。ここで、原料モル比＝アルデヒド類の仕込量
（モル）／〔メラミン類仕込量（モル）＋フェノール類
の仕込量（モル）〕である。また、実施例１〜４及び比
較例１で得られた樹脂をそれぞれガラス繊維に含浸さ
せ、１６０℃１０分間乾燥させた後、１７０℃、圧力４
０kgf/cm2にて１時間加熱した成形品の難燃性（ＵＬ−
９４に準じて評価）の結果を表１に示した。Table 1 shows the results of the molar ratios of the starting materials, the weight-average molecular weight (Mw) of the obtained resin, the softening point and the nitrogen content obtained by elemental analysis in Examples 1 to 4 and Comparative Example 1. . Here, the molar ratio of the raw materials = the charged amount of aldehydes (mol) / [the charged amount of melamines (mol) + the charged amount of phenols (mol)]. Further, the resins obtained in Examples 1 to 4 and Comparative Example 1 were each impregnated into glass fibers and dried at 160 ° C. for 10 minutes.
Flame retardancy of molded products heated at 0 kgf / cm 2 for 1 hour (UL-
Table 1 shows the results.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【発明の効果】請求項１記載のメラミン・フェノール共
縮合樹脂は、耐熱性、耐水性、難燃性及び強度に優れた
ものである。請求項２記載のメラミン・フェノール共縮
合樹脂の製造法は、耐熱性、耐水性、難燃性及び強度に
優れたメラミン・フェノール共縮合樹脂を生産性よく製
造可能なものである。The melamine-phenol co-condensation resin according to claim 1 is excellent in heat resistance, water resistance, flame retardancy and strength. The method for producing a melamine-phenol co-condensation resin according to the second aspect is capable of producing a melamine-phenol co-condensation resin excellent in heat resistance, water resistance, flame retardancy and strength with good productivity.
Claims (2)
ル類を反応させてなる、軟化点が８０度以下でかつ窒素
含有量が１０重量％以上であるメラミン・フェノール共
縮合樹脂。1. A melamine-phenol co-condensation resin obtained by reacting melamines, aldehydes and phenols, having a softening point of 80 ° C. or less and a nitrogen content of 10% by weight or more.
ル類を、アルデヒド類の仕込量がメラミン類及びフェノ
ール類の合計仕込量に対してモル比で０．０５〜１とな
るようにして、反応させることを特徴とする軟化点が８
０度以下でかつ窒素含有量が１０重量％以上であるメラ
ミン・フェノール共縮合樹脂の製造法。2. The reaction of melamines, aldehydes and phenols in such a manner that the amount of aldehyde charged is 0.05 to 1 in molar ratio with respect to the total amount of melamine and phenol. Has a softening point of 8
A method for producing a melamine-phenol co-condensation resin having a temperature of 0 ° or less and a nitrogen content of 10% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8452898A JPH11279248A (en) | 1998-03-30 | 1998-03-30 | Melamine/phenol co-condensation resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8452898A JPH11279248A (en) | 1998-03-30 | 1998-03-30 | Melamine/phenol co-condensation resin and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11279248A true JPH11279248A (en) | 1999-10-12 |
Family
ID=13833151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8452898A Pending JPH11279248A (en) | 1998-03-30 | 1998-03-30 | Melamine/phenol co-condensation resin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11279248A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010493A (en) * | 2010-10-14 | 2011-04-13 | 山东圣泉化工股份有限公司 | Method for preparing nitrogen-contained phenolic resin |
| US9249251B2 (en) | 2010-08-17 | 2016-02-02 | Hexion Inc. | Compositions and methods to produce triazine-arylhydroxy-aldehyde condensates with improved solubility |
-
1998
- 1998-03-30 JP JP8452898A patent/JPH11279248A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9249251B2 (en) | 2010-08-17 | 2016-02-02 | Hexion Inc. | Compositions and methods to produce triazine-arylhydroxy-aldehyde condensates with improved solubility |
| CN102010493A (en) * | 2010-10-14 | 2011-04-13 | 山东圣泉化工股份有限公司 | Method for preparing nitrogen-contained phenolic resin |
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