JP5224739B2 - Method for producing water-soluble resol resin - Google Patents
Method for producing water-soluble resol resin Download PDFInfo
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- JP5224739B2 JP5224739B2 JP2007176992A JP2007176992A JP5224739B2 JP 5224739 B2 JP5224739 B2 JP 5224739B2 JP 2007176992 A JP2007176992 A JP 2007176992A JP 2007176992 A JP2007176992 A JP 2007176992A JP 5224739 B2 JP5224739 B2 JP 5224739B2
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- soluble resol
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- 229920005989 resin Polymers 0.000 title claims description 55
- 239000011347 resin Substances 0.000 title claims description 55
- 229920003987 resole Polymers 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 22
- 150000002989 phenols Chemical class 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 7
- -1 organic ester compound Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 5
- 150000001299 aldehydes Chemical class 0.000 description 39
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000011230 binding agent Substances 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Description
本発明は水溶性レゾール樹脂の製造方法に関し、更に詳しくは未反応フェノール類モノマー及び未反応アルデヒド含有量が少なく、水希釈性に優れた水溶性レゾール樹脂の製造方法に関する。
本発明の水溶性レゾール樹脂は研磨布紙、木材または紙等の含浸、鋳物、ＦＲＰ及び発泡等に用いることができる、硬化性及び機械強度等に優れる未反応モノマー及び未反応アルデヒド含有量の少ない水溶性レゾール樹脂である。
The present invention relates to a method for producing a water-soluble resol resin, and more particularly to a method for producing a water-soluble resol resin having a low content of unreacted phenol monomers and unreacted aldehyde and excellent water dilutability.
The water-soluble resol resin of the present invention can be used for impregnation of abrasive cloth paper, wood or paper, castings, FRP, foaming, etc., and has low unreacted monomer and unreacted aldehyde content with excellent curability and mechanical strength. It is a water-soluble resol resin.
水溶性レゾール樹脂は、通常、フェノール類1モルに対しアルデヒド類を１〜３モルとして、触媒に水酸化ナトリウム、水酸化カリウム等のアルカリ金属、水酸化バリウム、水酸化カルシウム等のアルカリ土類金属またはアンモニア、トリエチルアミン、トリエタノールアミン等のアミン類を用いて反応することで得られる。しかしながら、このような条件で反応させた場合、反応終了後に未反応のフェノール類やアルデヒド類が残存する。未反応フェノール類が多いと、水溶性レゾール樹脂を使用した際に、異臭が発生し作業環境を悪化させる。さらに、硬化させた場合には硬化物の機械強度が低下するといった問題も生じる。また、未反応アルデヒド類が多いと、これもまた異臭を発生し作業環境上好ましくない。 The water-soluble resol resin usually contains 1 to 3 moles of aldehyde per mole of phenol, and the catalyst is an alkali metal such as sodium hydroxide or potassium hydroxide, or an alkaline earth metal such as barium hydroxide or calcium hydroxide. Or it can obtain by reacting using amines, such as ammonia, a triethylamine, a triethanolamine. However, when the reaction is performed under such conditions, unreacted phenols and aldehydes remain after completion of the reaction. When there are many unreacted phenols, when using a water-soluble resol resin, a strange odor is generated and the working environment is deteriorated. Furthermore, when it hardens | cures, the problem that the mechanical strength of hardened | cured material falls will also arise. Moreover, when there are many unreacted aldehydes, this will also generate a strange odor and is unpreferable on a working environment.
従って、水溶性レゾール樹脂は、未反応のフェノール類及びアルデヒド類の含有量が少ない事が要求される。未反応のフェノール類及びアルデヒド類を少なくする方法としては、フェノール類1モルに対しアルデヒド類を１．５モル以下の低モル比で反応させて未反応のフェノール類を除去する方法と、フェノール類１モルに対しアルデヒド類を１．８モル以上の高モルで反応させて未反応のアルデヒド類を除去する方法がある。
未反応のフェノール類を除去する方法としては、水蒸気蒸留法が一般的に知られている。しかし、水蒸気蒸留法は、５０℃以上の温度が必要であり、かつ長時間行わないと効果が少ない欠点がある。水溶性レゾール樹脂の水希釈性は、分子量の影響を強く受けることより、５０℃のような高温で長時間保持する事はできない。また、未反応のアルデヒド類除去方法としては、尿素、水加ヒドラジン等のアルデヒドキャッチャー剤を添加することによって除去が可能であるが、多くのアルデヒドキャッチャー剤は添加することで水溶性レゾール樹脂の水希釈性が低下する問題があった。
Therefore, the water-soluble resol resin is required to have a low content of unreacted phenols and aldehydes. As a method of reducing unreacted phenols and aldehydes, a method of removing unreacted phenols by reacting aldehydes at a low molar ratio of 1.5 mol or less with respect to 1 mol of phenols, and phenols There is a method of removing unreacted aldehydes by reacting aldehydes with a high mole of 1.8 moles or more per mole.
As a method for removing unreacted phenols, a steam distillation method is generally known. However, the steam distillation method has a drawback that it requires a temperature of 50 ° C. or more and is less effective unless it is performed for a long time. The water-dilutability of the water-soluble resol resin is strongly influenced by the molecular weight, and cannot be held at a high temperature such as 50 ° C. for a long time. In addition, as a method for removing unreacted aldehydes, it can be removed by adding an aldehyde catcher agent such as urea or hydrazine hydrate, but by adding many aldehyde catcher agents, water of a water-soluble resol resin can be obtained. There was a problem that the dilutability decreased.
フェノール類とアルデヒド類をアルカリ性触媒の下で反応させ、次いで上記生成物に尿素化合物を付加重合させることでホルムアルデヒド臭気の発生が少ない鋳物砂粘結剤の製造方法があるが、尿素化合物を添加する主目的はコストダウンと刺激臭ガスの発生を少なくすることであり（特許文献１参照）、樹脂の水希釈性に関する記載はなく、この系では溶剤を含まずに水希釈性１００％以上を有する水溶性レゾール樹脂は得られない。特許文献１には尿素化合物としてエチレン尿素の記載もあるが、これらの添加量はフェノール類１モルに対し、０．５〜３．５モルであり、０．５モル未満では硬化速度が遅くなるとされている（特許文献１の第２頁左下欄）。ここでも水希釈性については触れられていない。 There is a method of producing a foundry sand binder that generates less formaldehyde odor by reacting phenols and aldehydes in the presence of an alkaline catalyst, and then addition polymerization of the urea compound to the above product, but the urea compound is added. The main purpose is to reduce the cost and reduce the generation of irritating odor gas (see Patent Document 1). There is no description about the water dilutability of the resin, and this system has a water dilutability of 100% or more without containing a solvent. A water-soluble resol resin cannot be obtained. Patent Document 1 also describes ethylene urea as a urea compound, but the amount of these added is 0.5 to 3.5 moles with respect to 1 mole of phenols. (Patent Document 1, page 2, lower left column). Again, water dilution is not mentioned.
これ以外にもノボラック樹脂とアルデヒド類とをアルカリ性触媒を用いてレゾール化することで、未反応のフェノール類を低減したレゾール樹脂を得ることができることが知られている（特許文献２〜４参照）。しかし、この方法では溶剤を含まずに水希釈性１００％以上を有する水溶性レゾール樹脂は得られない。
本発明は、水希釈性に優れた、未反応のフェノール類及びアルデヒド類の含有率が低く、環境負荷の低減と硬化性や機械的強度に優れた特性を有し、好ましくは溶剤を含まない水溶性レゾール樹脂を提供するものである。 The present invention is excellent in water reducibility, has a low content of unreacted phenols and aldehydes, has a characteristic of reducing environmental burden and excellent curability and mechanical strength, and preferably contains no solvent. A water-soluble resol resin is provided.
本発明者等は前記目的を達成するために誠意研究を重ねた結果、フェノール類にアルデヒド類を反応させて得られる水溶性レゾール樹脂中の未反応アルデヒド類とエチレン尿素とを特定の割合で反応させることで、水希釈性を低下させることなく、レゾール樹脂中の未反応アルデヒド類の含有量を低減することを見出し本発明を完成するに至った。
即ち、本発明は以下の通りである。
（１）アルデヒド類とフェノール類を反応させて水溶性レゾール樹脂を得、次いで有機エステル化合物の不存在下に、未反応アルデヒド１モルに対し、エチレン尿素を０．１モル以上０．５モル未満添加し、未反応アルデヒドとエチレン尿素とを反応させてアルデヒド類を低減することを特徴とする水希釈性（２５℃で樹脂に対し白濁する水含有量の割合）が１００質量％以上である水溶性レゾール樹脂の製造方法。
As a result of repeated sincere studies to achieve the above object, the present inventors have reacted unreacted aldehydes and ethylene urea in a water-soluble resol resin obtained by reacting phenols with aldehydes at a specific ratio. As a result, the present inventors have found that the content of unreacted aldehydes in the resole resin can be reduced without lowering the water dilutability, thereby completing the present invention.
That is, the present invention is as follows.
(1) reacting aldehydes with phenols to give a water-soluble resol resin, then in the absence of an organic ester compound, relative to unreacted aldehyde 1 mol, 0.5 mol less than 0.1 mol or more of ethylene urea Addition and reaction of unreacted aldehyde and ethylene urea to reduce aldehydes, water dilution (water content ratio of white turbidity to resin at 25 ° C.) is 100% by mass or more For producing a functional resol resin.
（２）フェノール類１モルに対し、アルデヒド類１．５〜３．５モルを反応させることを特徴とする上記（１）に記載の水溶性レゾール樹脂の製造方法。
（３）前記水溶性レゾール樹脂の樹脂成分が５０質量％以上であり、樹脂中の未反応アルデヒド量が１質量％以下でかつ未反応モノマー量が５質量％以下であることを特徴とする上記（１）または（２）に記載の水溶性レゾール樹脂の製造方法。
（４）前記水溶性レゾール樹脂中に溶剤を含まないことを特徴とする上記（１）〜（３）のいずれかに記載の水溶性レゾール樹脂の製造方法。
(2) The method for producing a water-soluble resol resin according to the above (1), wherein 1.5 to 3.5 mol of aldehyde is reacted with 1 mol of phenol.
(3) The resin component of the water-soluble resol resin is 50% by mass or more, the amount of unreacted aldehyde in the resin is 1% by mass or less, and the amount of unreacted monomer is 5% by mass or less. (1) The manufacturing method of the water-soluble resol resin as described in (2).
(4) The method for producing a water-soluble resol resin according to any one of the above (1) to (3), wherein the water-soluble resol resin does not contain a solvent.
本発明は、アルデヒドキャッチャー剤としてエチレン尿素を必須成分とした未反応モノマー及び未反応アルデヒド含有量が少ない水溶性レゾール樹脂の製造方法あって、環境負荷の低減と硬化性や機械的強度、水希釈性に優れた特性を得ることができ、更に好ましくは溶剤を含有しない水溶性レゾール樹脂を提供することができる。 The present invention relates to a method for producing an unreacted monomer having ethylene urea as an essential component as an aldehyde catcher agent and a water-soluble resol resin having a low content of unreacted aldehyde, which reduces environmental burden, curability, mechanical strength, water dilution Thus, it is possible to provide a water-soluble resol resin that does not contain a solvent.
本発明に用いられるフェノール類としては、例えばフェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、レゾルシン、ビスフェノールＡ等が挙げられる。また、これらを単独または２種以上組み合わせて使用しても良い。
アルデヒド類としては、例えばホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド等が挙げられる。また、これらを単独または２種以上組み合わせて使用しても良い。
前記フェノール類と前記アルデヒド類の反応時のモル比（後者／前者）は、１．５〜３．５が好ましく、特に１．８〜３．０が好ましい。反応時のモル比が１．５未満であると、未反応のフェノール類が多くなる場合があり、３．５を超えると、レゾール樹脂の架橋密度が向上するため、硬化物が硬くなり機械強度が低下する場合がある。
Examples of the phenols used in the present invention include phenol, o-cresol, m-cresol, p-cresol, resorcin, and bisphenol A. Moreover, you may use these individually or in combination of 2 or more types.
Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Moreover, you may use these individually or in combination of 2 or more types.
The molar ratio (the latter / the former) during the reaction of the phenols and the aldehydes is preferably 1.5 to 3.5, and particularly preferably 1.8 to 3.0. If the molar ratio at the time of reaction is less than 1.5, unreacted phenols may increase, and if it exceeds 3.5, the crosslink density of the resole resin is improved, so that the cured product becomes hard and mechanical strength is increased. May decrease.
反応にはアルカリ性触媒が用いられるが、アルカリ性触媒としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属、水酸化バリウム、水酸化カルシウム等のアルカリ土類金属またはアンモニア、トリエチルアミン、トリエタノールアミン等のアミン類とが挙げられる。また、これらを単独または２種以上組み合わせて使用しても良い。
フェノール類と前記アルデヒド類の反応は通常５０〜１００℃の温度で行われる。
前記エチレン尿素の添加量は、レゾール樹脂中の未反応アルデヒド類1モルに対してエチレン尿素０．１モル以上０．５モル未満である。特に０．３モル以上〜０．５モル未満が好ましい。エチレン尿素の添加量が０．１モル未満であると、未反応のアルデヒド類が多くなる場合があり、０．５モル以上ではエチレン尿素が過剰となり、硬化物の機械強度が低下する場合がある。
An alkaline catalyst is used for the reaction. Examples of the alkaline catalyst include alkali metals such as sodium hydroxide and potassium hydroxide, alkaline earth metals such as barium hydroxide and calcium hydroxide, or ammonia, triethylamine, triethanolamine and the like. And amines. Moreover, you may use these individually or in combination of 2 or more types.
The reaction between phenols and the aldehydes is usually performed at a temperature of 50 to 100 ° C.
The added amount of ethylene urea is 0.1 mol or more and less than 0.5 mol of ethylene urea with respect to 1 mol of unreacted aldehydes in the resole resin. Particularly preferred is 0.3 mol or more and less than 0.5 mol. If the addition amount of ethylene urea is less than 0.1 mol, unreacted aldehydes may increase, and if it is 0.5 mol or more, ethylene urea becomes excessive and the mechanical strength of the cured product may decrease. .
未反応アルデヒド類とエチレン尿素との反応は４０〜５０℃の温度範囲で行うのがよい。
水希釈性について、エチレン尿素が有効な理由としてはエチレン尿素は未反応のアルデヒドと優先的に反応し、その反応物が高い水希釈性を示す為に、レゾール樹脂の水希釈性を低下させないのに対し、尿素等のアルデヒドキャッチャー剤の多くは、未反応のアルデヒド類との反応物の水希釈性が悪い。もしくは、レゾール樹脂中のメチロール基とも反応することで、レゾール樹脂の水希釈性を低下させることが推測される。
本発明のレゾール樹脂の水希釈性は２５℃で１００質量％以上である。水希釈性は樹脂に水を加えた場合、ある水の量までは白濁しないが、それ以上水を加えると白濁する。水希釈性が１００質量％以上とはレゾール樹脂中の樹脂固形分１００質量部に対し、水を１００質量部以上含めても白濁しないことを意味する。
本発明において、好ましくは水溶性レゾール樹脂の樹脂成分が５０質量％以上であり、樹脂中の未反応アルデヒド量が１質量％以下でかつ未反応のフェノール類モノマー量が５質量％以下である。
The reaction between unreacted aldehydes and ethylene urea is preferably carried out in a temperature range of 40 to 50 ° C.
Regarding water dilutability, ethylene urea is effective because ethylene urea reacts preferentially with unreacted aldehyde, and the reaction product exhibits high water dilutability, so it does not reduce the water dilutability of the resole resin. On the other hand, many aldehyde catcher agents such as urea have poor water dilutability of the reaction product with unreacted aldehydes. Or it is estimated that the water reducibility of a resole resin is reduced by reacting with the methylol group in a resole resin.
The water reducibility of the resol resin of the present invention is 100% by mass or more at 25 ° C. When water is added to the resin, water dilution does not become cloudy up to a certain amount of water, but becomes cloudy when more water is added. The water dilutability of 100% by mass or more means that even if 100 parts by mass or more of water is included with respect to 100 parts by mass of the resin solid content in the resole resin, it does not become cloudy.
In the present invention, the resin component of the water-soluble resol resin is preferably 50% by mass or more, the amount of unreacted aldehyde in the resin is 1% by mass or less, and the amount of unreacted phenolic monomer is 5% by mass or less.
以下、実施例により詳細に説明するが、本発明はこれに限定されるものではない。なお、ここに記載する「部」及び「％」は全て「質量部」及び「質量％」を示す。
また、残留フェノール類の測定はガスクロマトグラフィーで測定し、残留アルデヒド類の測定は亜硫酸ソーダ法を用いて測定した。
Hereinafter, although an example explains in detail, the present invention is not limited to this. Note that “parts” and “%” described here all indicate “parts by mass” and “% by mass”.
Residual phenols were measured by gas chromatography, and residual aldehydes were measured using a sodium sulfite method.
実施例1
２リットルのセパラブルフラスコに攪拌機、温度計をセットしフェノール６００ｇと３７％ホルマリン水溶液１２９３ｇとを仕込み２５％水酸化ナトリウム水溶液６０gを添加し、８０℃まで昇温した後、２時間保った後、真空下で水を４００ｇ除去した。除去後の未反応ホルマリンの濃度は３．２％であった。
その後純度９０％エチレン尿素８２ｇ（未反応ホルマリン１モルに対し、０．４モルに相当）を加え、４０℃で２０分間保持後室温まで冷却し樹脂Ａを得た。
Example 1
After setting a stirrer and a thermometer in a 2 liter separable flask, adding 600 g of phenol and 1293 g of 37% formalin aqueous solution, adding 60 g of 25% aqueous sodium hydroxide solution, raising the temperature to 80 ° C., and maintaining for 2 hours, 400 g of water was removed under vacuum. The concentration of unreacted formalin after removal was 3.2%.
Thereafter, 82 g of 90% purity ethylene urea (corresponding to 0.4 mol with respect to 1 mol of unreacted formalin) was added, kept at 40 ° C. for 20 minutes, and then cooled to room temperature to obtain Resin A.
実施例２
２リットルのセパラブルフラスコに攪拌機、温度計をセットしフェノール５００ｇと３７％ホルマリン水溶液１２９４ｇとを仕込み２５％水酸化ナトリウム水溶液５０gを添加し、８０℃まで昇温した後、２時間保った後、真空下で水を４５０ｇ除去した。除去後の未反応ホルマリンの濃度は３．２％であった。
その後純度９０％エチレン尿素６３ｇ（未反応ホルマリン１モルに対し、０．４５モルに相当）を加え、４０℃で２０分間保持後室温まで冷却し樹脂Ｂを得た。
Example 2
After setting a stirrer and a thermometer in a 2 liter separable flask, charging 500 g of phenol and 1294 g of 37% formalin aqueous solution, adding 50 g of 25% sodium hydroxide aqueous solution, raising the temperature to 80 ° C., and maintaining for 2 hours, 450 g of water was removed under vacuum. The concentration of unreacted formalin after removal was 3.2%.
Thereafter, 63 g of 90% pure ethylene urea (corresponding to 0.45 mol with respect to 1 mol of unreacted formalin) was added, kept at 40 ° C. for 20 minutes and then cooled to room temperature to obtain Resin B.
実施例３
触媒を２５％水酸化ナトリウム水溶液から水酸化バリウム３６ｇに変えた以外は実施例１と同様に行い樹脂Ｃをえた。
エチレン尿素を加える際の樹脂の未反応ホルマリン濃度は３．５％であり、この未反応ホルマリン１モルに対し、エチレン尿素を０．４８モルの割合で加えた。
Example 3
Resin C was obtained in the same manner as in Example 1 except that the catalyst was changed from 25% aqueous sodium hydroxide solution to 36 g of barium hydroxide.
The concentration of unreacted formalin in the resin when adding ethylene urea was 3.5%, and ethylene urea was added at a ratio of 0.48 mole per mole of unreacted formalin.
比較例１
エチレン尿素を除いた以外は実施例１と同様に行い樹脂Ｄを得た。
比較例２
エチレン尿素を尿素９０ｇに変更した以外は実施例１と同様に行い樹脂Ｅを得た。
Comparative Example 1
Resin D was obtained in the same manner as in Example 1 except that ethylene urea was omitted.
Comparative Example 2
Resin E was obtained in the same manner as in Example 1 except that ethylene urea was changed to 90 g of urea.
比較例３
エチレン尿素を除いた以外は実施例３と同様に行い樹脂Ｆを得た。
比較例４
エチレン尿素を６０％水加ヒドラジン１０９ｇに変更した以外は実施例１と同様に行い樹脂Ｇを得た。
以上のＡ〜Ｇ樹脂の特性を表１に示す。
Comparative Example 3
Resin F was obtained in the same manner as in Example 3 except that ethylene urea was omitted.
Comparative Example 4
Resin G was obtained in the same manner as in Example 1 except that ethylene urea was changed to 109 g of 60% hydrazine hydrate.
The characteristics of the above A to G resins are shown in Table 1.
本発明の水溶性レゾール樹脂は未反応モノマー及び未反応アルデヒド含有量が少なく、硬化性及び機械強度、水分散性等に優れているので、研磨布紙、木材または紙等の含浸、鋳物、ＦＲＰ及び発泡等に用いることができる。 The water-soluble resol resin of the present invention has a low content of unreacted monomers and unreacted aldehydes and is excellent in curability, mechanical strength, water dispersibility, etc., so impregnation of abrasive cloth paper, wood or paper, casting, FRP And can be used for foaming and the like.
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| JP2001114851A (en) * | 1999-10-20 | 2001-04-24 | Dainippon Ink & Chem Inc | Phenolic resin composition and method for producing the same |
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| JP2005186097A (en) * | 2003-12-25 | 2005-07-14 | Hodogaya Ashland Kk | Binder composition for making mold and composition for making mold, and method for making mold for casting |
| JP4424222B2 (en) * | 2005-02-25 | 2010-03-03 | Ｄｉｃ株式会社 | Method for producing resol-type solid alkylphenol resin |
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