JPH07215902A - Production of naphthol aldehyde condensate - Google Patents
Production of naphthol aldehyde condensateInfo
- Publication number
- JPH07215902A JPH07215902A JP2880394A JP2880394A JPH07215902A JP H07215902 A JPH07215902 A JP H07215902A JP 2880394 A JP2880394 A JP 2880394A JP 2880394 A JP2880394 A JP 2880394A JP H07215902 A JPH07215902 A JP H07215902A
- Authority
- JP
- Japan
- Prior art keywords
- naphthol
- amount
- weight
- unreacted
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- -1 naphthol aldehyde Chemical class 0.000 title claims description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 135
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 abstract description 18
- 230000008018 melting Effects 0.000 abstract description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 abstract description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008096 xylene Substances 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 2
- 229950011260 betanaphthol Drugs 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 229930040373 Paraformaldehyde Natural products 0.000 description 15
- 229920002866 paraformaldehyde Polymers 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 14
- 239000000155 melt Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000539 dimer Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 150000003833 nucleoside derivatives Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はエポキシ樹脂の硬化剤や
エポキシ樹脂の前駆体として有用な、ナフタレン核体数
が２個である縮合物を多く含んだナフトールアルデヒド
縮合物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a naphthol aldehyde condensate containing a large amount of a condensate having two naphthalene nuclides, which is useful as a curing agent for epoxy resins and a precursor for epoxy resins.
【０００２】[0002]
【従来の技術】従来、半導体素子を外部環境から保護す
るため、エポキシ樹脂組成物で封止する方法が広く採用
されている。前記組成物は、通常、エポキシ樹脂，硬化
剤，硬化促進剤，充填剤，及びその他の添加剤で構成さ
れている。前記エポキシ樹脂としては、フェノール類と
ホルムアルデヒドとの反応により得られたノボラック樹
脂をエポキシ化した樹脂、特にオルトクレゾールノボラ
ックエポキシ樹脂が広く用いられ、硬化剤としては、フ
ェノールホルムアルデヒドノボラック樹脂が採用されて
いる。また、高性能な硬化剤としてα−ナフトールとホ
ルマリン水とを酸触媒を用いて反応させたノボラック樹
脂が紹介されている。2. Description of the Related Art Conventionally, a method of encapsulating with a epoxy resin composition has been widely adopted in order to protect a semiconductor element from the external environment. The composition is usually composed of an epoxy resin, a curing agent, a curing accelerator, a filler, and other additives. As the epoxy resin, a resin obtained by epoxidizing a novolak resin obtained by the reaction of phenols and formaldehyde, particularly an orthocresol novolac epoxy resin is widely used, and a phenol-formaldehyde novolac resin is used as a curing agent. . In addition, a novolak resin obtained by reacting α-naphthol and formalin water with an acid catalyst is introduced as a high-performance curing agent.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記硬
化剤のフェノールホルムアルデヒドノボラック樹脂にお
いては、エポキシ樹脂との硬化後、耐熱性に劣り、かつ
吸湿性が高いためクラックが発生し、クレームが多発し
ている。又、α−ナフトールとホルマリン水とを酸触媒
を用いて反応させたノボラック樹脂においては、耐熱
性，吸湿性等の性能は満足できるものの、ホルマリンの
反応モル比が、α−ナフトール１モルに対して０．５モ
ル以上であるため、多核体が多量に生成し、そのため縮
合物の融点と溶融粘度が高く（通常、融点１２５℃程
度、１５０℃における溶融粘度７０００ｃｐ程度）、成
型等の作業性に劣るため実用化されていないのが現状で
ある。このように公知の縮合方法では前記縮合物の融点
及び溶融粘度は低くならず、所望する低い融点及び溶融
粘度を持った作業性能の優れた縮合物の製造方法は確立
されていなかった。However, in the phenol-formaldehyde novolac resin as the above-mentioned curing agent, after curing with the epoxy resin, the heat resistance is poor and the hygroscopicity is high, so that cracks occur and many claims are made. There is. Further, in the novolak resin obtained by reacting α-naphthol and formalin water using an acid catalyst, although the performances such as heat resistance and hygroscopicity are satisfactory, the reaction molar ratio of formalin is relative to 1 mol of α-naphthol. Since it is 0.5 mol or more, a large amount of polynuclear body is generated, and therefore the melting point and melt viscosity of the condensate are high (usually, melting point is about 125 ° C, melt viscosity at 150 ° C is about 7,000 cp), and workability of molding, etc. The current situation is that it has not been put to practical use because it is inferior to Thus, the known condensation method does not lower the melting point and melt viscosity of the condensate, and a method for producing a condensate having a desired low melting point and melt viscosity and excellent workability has not been established.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記目的
を達成するため鋭意検討の結果、ナフタレン核体数２の
縮合物の含有量を多くする、すなわち２核体の量（重量
％）を３核体の量又は４以上の核体の量のいずれよりも
多くし、かつ未反応ナフトールを除去して未反応ナフト
ールの含有量を少なくしたナフトール・アルデヒド縮合
物（以下「２量体リッチなナフトールアルデヒド縮合
物」という）とすることで、所望する低い融点及び溶融
粘度（融点４５〜１１０℃、１５０℃における溶融粘度
１０〜２００ｃｐ）をもった作業性能の優れた縮合物が
得られ、そのためには、特定の条件のもとでの縮合反応
と未反応ナフトールの除去が必要であることを見い出し
本発明を完成した。Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have increased the content of condensate having 2 naphthalene nuclides, that is, the amount of dinuclear compounds (% by weight). ) Is greater than either the amount of trinuclear body or the amount of 4 or more nuclear body, and unreacted naphthol is removed to reduce the content of unreacted naphthol (hereinafter referred to as “dimer”). "Rich naphthol aldehyde condensate") provides a condensate having a desired low melting point and melt viscosity (melting point 45 to 110 ° C, melt viscosity 10 to 200 cp at 150 ° C) and excellent workability. Therefore, they have found that it is necessary to carry out a condensation reaction and removal of unreacted naphthol under specific conditions, and completed the present invention.
【０００５】すなわち、本発明はナフトールとアルデヒ
ド化合物の縮合反応において、ナフトール１モルに対し
てモノアルデヒドを０．５モル未満として反応し、一部
未反応ナフトールを残存させた後、未反応ナフトールを
除去することからなる２量体リッチなナフトール・アル
デヒド縮合物の製造方法を提供するものである。That is, according to the present invention, in the condensation reaction of naphthol and an aldehyde compound, monoaldehyde is reacted in an amount of less than 0.5 mol with respect to 1 mol of naphthol, and the unreacted naphthol is partially left unreacted. Disclosed is a method for producing a dimer-rich naphthol / aldehyde condensate.
【０００６】又、前記縮合反応において、反応における
触媒を用いず、ナフトール１モルに対してモノアルデヒ
ドを０．２５〜０．４５モルで反応させる２量体リッチ
なナフトールアルデヒド縮合物の製造方法を提供するも
のである。Further, in the condensation reaction, a method for producing a dimer-rich naphthol aldehyde condensate in which a monoaldehyde is reacted in an amount of 0.25 to 0.45 mol with respect to 1 mol of naphthol without using a catalyst in the reaction. It is provided.
【０００７】さらに、前記縮合反応において、沸点が８
０℃以上の水に不溶又は難溶性の溶剤を用い、かつ反応
温度が８０〜１５０℃である２量体リッチなナフトール
アルデヒド縮合物の製造方法を提供するものである。さ
らに前記ナフトールが、α−ナフトール又はα−ナフト
ールとβ−ナフトールであることを特徴とする２量体リ
ッチなナフトールアルデヒド縮合物の製造方法を提供す
るものである。Further, in the condensation reaction, the boiling point is 8
It is intended to provide a method for producing a dimer-rich naphtholaldehyde condensate having a reaction temperature of 80 to 150 ° C using a solvent insoluble or hardly soluble in water at 0 ° C or higher. Further, the present invention provides a method for producing a dimer-rich naphthol aldehyde condensate, wherein the naphthol is α-naphthol or α-naphthol and β-naphthol.
【０００８】（手段を構成する要件）作業性のよい低い
融点及び溶融粘度をもった縮合物を得るには、ナフタレ
ン核体数２の縮合物の含有量を多くする、すなわち、２
核体の量（重量％）を３核体の量又は４以上の核体の量
のいずれよりも多くし、未反応ナフトールの含有量を極
力少なくする必要がある。このためには特定の条件のも
とでの縮合反応と未反応ナフトールの除去が必要で、下
記の３つの条件が必要である。(Requirements for Means) In order to obtain a condensate having a low workability and a low melting point and a melt viscosity, the content of the condensate having 2 naphthalene nuclides is increased, that is, 2
It is necessary to increase the amount (% by weight) of the nuclide to be larger than the amount of the trinucleus or the amount of the nuclei of 4 or more to minimize the content of unreacted naphthol. For this purpose, a condensation reaction under specific conditions and removal of unreacted naphthol are required, and the following three conditions are required.
【０００９】（イ）ナフトール１モルに対してモノアル
デヒドを０．５モル未満とする。 （ロ）縮合反応は、未反応ナフトールを残存させた状態
で終了させる。 （ハ）未反応ナフトールは除去し、その含有量を低減す
る。(A) Monoaldehyde is less than 0.5 mol per mol of naphthol. (B) The condensation reaction is terminated with the unreacted naphthol remaining. (C) Unreacted naphthol is removed to reduce its content.
【００１０】さらに、以下の４つの条件のいずれか又は
全部をつけ加えると好ましい２量体リッチなナフトール
アルデヒド縮合物が得られる。 （ニ）触媒を用いずに加熱反応する。 （ホ）沸点８０℃以上の水に不溶又は難溶性の溶剤を用
い、かつ反応温度を８０〜１５０℃にする。 （ヘ）ナフトールとしてα−ナフトール又はα−ナフト
ールとβ−ナフトールを用いる。 （ト）モノアルデヒドとして、ホルマリン水、パラホル
ムアルデヒド，ベンズアルデヒド，ヒドロキシベンズア
ルデヒド及びサリチルアルデヒドの内の少なくとも１つ
を使用する。Further, by adding any or all of the following four conditions, a preferable dimer-rich naphtholaldehyde condensate can be obtained. (D) Heat reaction without using a catalyst. (E) A solvent insoluble or hardly soluble in water having a boiling point of 80 ° C or higher is used, and the reaction temperature is set to 80 to 150 ° C. (F) As naphthol, α-naphthol or α-naphthol and β-naphthol is used. As (g) monoaldehyde, at least one of formalin water, paraformaldehyde, benzaldehyde, hydroxybenzaldehyde and salicylaldehyde is used.
【００１１】次に前記（イ）〜（ト）について説明す
る。 （ｉ）（イ）について 従来のナフトール・アルデヒド縮合物の反応は、ナフト
ール１モルに対してアルデヒドを０．５〜１．２モルの
範囲で、範囲内でも比較的多くの量を用い、しかも酸性
触媒を加えて反応し、極力未反応ナフトールを残存させ
ないことが主眼とされてきた。Next, the above (a) to (g) will be described. Regarding (i) and (a), in the conventional reaction of a naphthol-aldehyde condensate, an aldehyde is used in the range of 0.5 to 1.2 mol with respect to 1 mol of naphthol, and a relatively large amount is used within the range. It has been the main objective to react by adding an acidic catalyst so that unreacted naphthol does not remain as much as possible.
【００１２】又エポキシの硬化剤等として用いるために
は、硬化反応いいかえると橋かけ反応をさせる必要があ
り、分子内に２個以上のフェノール性水酸基を有するナ
フタレン化合物が有用で、未反応ナフトールは極力少な
いことが望まれる。In order to use it as a curing agent for epoxies, it is necessary to carry out a crosslinking reaction, that is, a crosslinking reaction. A naphthalene compound having two or more phenolic hydroxyl groups in the molecule is useful, and unreacted naphthol is It is desired to be as small as possible.
【００１３】従来の方法によるナフトールアルデヒド縮
合物は、融点と溶融粘度が高く、高沸点（２８０℃前
後）の未反応ナフトールを工業的有利に除去すること
は、きわめて困難であり、通常０．５〜３重量％程度残
存する。このため、前記の反応率を向上させ、未反応ナ
フトールの残存量の低減に努力してきたきらいがある。The naphthol aldehyde condensate obtained by the conventional method has a high melting point and a high melt viscosity, and it is extremely difficult to industrially remove unreacted naphthol having a high boiling point (around 280 ° C.), and it is usually 0.5 About 3% by weight remains. Therefore, there is a desire to improve the above-mentioned reaction rate and make an effort to reduce the residual amount of unreacted naphthol.
【００１４】本発明では、ナフトール１モルに対してモ
ノアルデヒドを０．５モル未満、好しくは０．２５〜
０．４５モルときわめて少量にする。これにより縮合物
中の２核体の量が急増し、同時に未反応ナフトールがか
なり残存することを見い出した。ここでα−ナフトール
とパラホルムアルデヒドの反応におけるアルデヒド仕込
比と縮合物中の２核体量の関係を図１に示す。In the present invention, the monoaldehyde is less than 0.5 mol, preferably 0.25 to 1 mol, relative to 1 mol of naphthol.
Very small amount of 0.45 mol. As a result, it was found that the amount of binuclear compounds in the condensate rapidly increased, and at the same time, unreacted naphthol remained considerably. Here, the relationship between the aldehyde charge ratio and the amount of binuclear compounds in the condensate in the reaction of α-naphthol and paraformaldehyde is shown in FIG.
【００１５】０．５モル以上では２核体量が減少し３核
体以上の量が増加するため、低粘度縮合物が得られず、
又好ましい範囲の下限である０．２５モル未満では、未
反応ナフトールの増加により２核体量が減少するため、
除去すべきナフトール量がふえることで工業的に不利と
なる。この条件により、２核体の縮合物の含有量を３核
体又は４以上の核体の含有量のいずれよりも多くでき、
すなわち少なくとも３４重量％以上の２核体の含有量が
可能であり、更にモノアルデヒドを０．２５〜０．４５
モルとした時、４０重量％以上が可能となる。When the amount is 0.5 mol or more, the amount of the binuclear body decreases and the amount of the trinuclear body increases, so that a low-viscosity condensate cannot be obtained.
If the amount is less than 0.25 mol, which is the lower limit of the preferable range, the amount of unreacted naphthol increases and the amount of binuclear compounds decreases.
Increasing the amount of naphthol to be removed is industrially disadvantageous. By this condition, the content of the condensate of the binuclear body can be made higher than the content of the trinuclear body or the content of 4 or more cores,
That is, a binuclear content of at least 34% by weight or more is possible, and monoaldehyde is added in an amount of 0.25 to 0.45.
When the amount is mol, 40% by weight or more is possible.
【００１６】（ｉｉ）（ロ）について 前記（イ）記載のとおり、あえて、未反応ナフトールを
残存、（５重量％以上、好ましくは１０〜５０重量％）
させて反応を終了させることが第２の必須要件であり、
これは（イ）の条件によって達成される。(Ii) (b) As described in (a) above, the unreacted naphthol remains intentionally (5% by weight or more, preferably 10 to 50% by weight).
To complete the reaction is the second essential requirement,
This is achieved by the condition (a).
【００１７】従来の方法の未反応ナフトールを極力少な
くした条件下では、３核体以上の量が増加し、低粘度の
縮合体が得られず、これ以上の未反応ナフトールの除去
は困難であるが、本発明の方法では、未反応ナフトール
を５重量％以上、好しくは１０〜５０重量％残存させる
ことが肝要である。上限の５０重量％をこえると相対的
に２核体量が減少し、除去する必要のある未反応ナフト
ールが多くなるため経済的に不利である。α−ナフトー
ルとパラホルムアルデヒドの反応における未反応ナフト
ール量と２核体量の関係を図２に示す。この未反応ナフ
トールの存在量は、モノアルデヒドの仕込モル比によっ
て変化し、モノアルデヒドが少ないほど未反応ナフトー
ルが増加する。Under the conditions in which the amount of unreacted naphthol in the conventional method is minimized, the amount of trinuclear or more is increased and a low-viscosity condensate cannot be obtained, and further removal of unreacted naphthol is difficult. However, in the method of the present invention, it is important to leave unreacted naphthol in an amount of 5% by weight or more, preferably 10 to 50% by weight. If the upper limit of 50% by weight is exceeded, the amount of binuclear bodies is relatively decreased, and unreacted naphthol that needs to be removed is increased, which is economically disadvantageous. FIG. 2 shows the relationship between the amount of unreacted naphthol and the amount of binuclear bodies in the reaction of α-naphthol and paraformaldehyde. The amount of the unreacted naphthol present varies depending on the molar ratio of the monoaldehyde charged, and the unreacted naphthol increases as the monoaldehyde content decreases.
【００１８】（ｉｉｉ）（ハ）について （イ）と（ロ）の必須条件により反応した粗成物から、
残存させた未反応ナフトールを除去することが第３の必
須条件である。(Iii) (c) From the crude product reacted under the essential conditions of (a) and (b),
The third essential condition is to remove the remaining unreacted naphthol.
【００１９】（イ）と（ロ）の条件により反応した粗成
物は前記のとおり、２核体の量が多く必然的に３核体物
や４以上の核体物が少なく、縮合体自体の融点と溶融粘
度が低い。このため減圧脱気等の簡単な操作で、短時間
の内に未反応ナフトールを除去できることを見い出し
た。減圧脱気は１５０°〜３００℃で２０ｍｍＨｇ以下
好しくは１７０〜２３０℃で１５ｍｍＨｇ以下で行うと
未反応ナフトールを通常は１重量％以下にまで短時間で
除去できる。As described above, the crude product reacted under the conditions of (a) and (b) has a large amount of dinuclear bodies, and inevitably a small amount of trinuclear bodies or 4 or more nuclear bodies, and the condensate itself. Has a low melting point and melt viscosity. Therefore, it was found that unreacted naphthol can be removed within a short time by a simple operation such as degassing under reduced pressure. If the degassing under reduced pressure is carried out at 150 ° to 300 ° C. at 20 mmHg or less, preferably at 170 to 230 ° C. at 15 mmHg or less, unreacted naphthol can be usually removed in a short time to 1% by weight or less.
【００２０】高粘度縮合物（１５０℃の溶融粘度が５０
０ｃｐ以上とする）の場合、ほとんどナフトールの除去
が不可能で、１５０ｃｐ程度でも除去率は５０％程度で
ある。これに対して本発明に従えばほとんどの場合１０
０ｃｐ以下で良好な場合は１０〜３０ｃｐ品が得られる
ため除去がきわめて容易となった。High-viscosity condensate (melt viscosity at 150 ° C. of 50
In the case of 0 cp or more), it is almost impossible to remove naphthol, and the removal rate is about 50% even at about 150 cp. On the other hand, according to the present invention, in most cases 10
When 0 cp or less is good, a 10 to 30 cp product is obtained, and therefore removal is extremely easy.
【００２１】ナフトールアルデヒド縮合物は高温すなわ
ち２３０℃特に３００℃以上では分解が生じ不用のナフ
トールが急増するため、可能なかぎり低温での脱気が必
要で、しかも短時間内に終了することが求められ、この
ためからも低粘度縮合体にしておくことが必須となる。
α−ナフトール・パラホルムアルデヒド縮合物の溶融粘
度と減圧処理後の残存ナフトール量の関係を図３に示
す。The naphthol aldehyde condensate is decomposed at a high temperature, that is, at 230 ° C., particularly 300 ° C. or higher, and unnecessary naphthol rapidly increases. For this reason, it is essential to keep the low-viscosity condensate.
FIG. 3 shows the relationship between the melt viscosity of the α-naphthol / paraformaldehyde condensate and the amount of residual naphthol after the reduced pressure treatment.
【００２２】（ｉｖ）（ニ）について 縮合反応は一般的には酸触媒や塩基性触媒が用いられ
る。しかしながら本発明ではこれを用いずに反応を行う
ことが好しい。触媒を用いない場合は用いる場合に比較
し、反応がマイルドとなり、ナフタレン核体数３以上の
ものの生成を抑えることが可能である。触媒を用いた場
合は、反応が急激となり、ナフタレン核体数の高いもの
の生成が促進され、分布が広くなり、融点や溶融粘度が
高くなるため好しくない。(Iv) (iv) In the condensation reaction, an acid catalyst or a basic catalyst is generally used. However, in the present invention, it is preferable to carry out the reaction without using this. When a catalyst is not used, the reaction is milder than when it is used, and it is possible to suppress the production of naphthalene nuclides having a number of 3 or more. When a catalyst is used, the reaction becomes abrupt, the generation of a substance having a high number of naphthalene nuclei is promoted, the distribution is widened, and the melting point and the melt viscosity are increased, which is not preferable.
【００２３】（ｖ）（ホ）について 次に縮合反応の反応温度は８０〜１５０℃という範囲で
行われるのが好ましく、更にこの反応温度を８０℃〜１
３０℃に維持することによって、マイルドな反応が促進
され、ナフタレン核体数３以上のものの含有量を更に低
くすることができ、硬化剤としての作業性能が更によく
なる。縮合反応の反応時間は通常２〜１０時間である。Regarding (v) (e) Next, the condensation reaction is preferably carried out at a reaction temperature in the range of 80 to 150 ° C., and this reaction temperature is set to 80 ° C. to 1 ° C.
By maintaining the temperature at 30 ° C., the mild reaction is promoted, the content of the naphthalene nuclide having 3 or more can be further lowered, and the workability as a curing agent is further improved. The reaction time of the condensation reaction is usually 2 to 10 hours.
【００２４】縮合反応は、熱縮合法によることもできる
が、反応温度は前記より８０〜１５０℃の範囲で低温側
のマイルドな反応条件が特に好ましいことから、溶剤を
使用した溶剤混合熱縮合法が好ましい。使用する溶剤
は、沸点が８０℃以上、好ましくは１００℃以上で水に
不溶又は、難溶性のものであり、具体的には、トルエ
ン，キシレン，メチルイソブチルケトン等が挙げられ
る。沸点が低過ぎると反応物が液状となりにくく、又水
への溶解性が高いと縮合反応が進みにくい。これらの溶
剤の使用量は任意で良いが通常ナフトールの１０〜２０
０重量％である。この溶剤は縮合反応終了後、加熱常圧
下や、加熱減圧下で除去される。The condensation reaction may be carried out by a thermal condensation method, but the reaction temperature is in the range of 80 to 150 ° C., and mild reaction conditions on the low temperature side are particularly preferable. Is preferred. The solvent used has a boiling point of 80 ° C. or higher, preferably 100 ° C. or higher, and is insoluble or sparingly soluble in water, and specific examples thereof include toluene, xylene, and methyl isobutyl ketone. If the boiling point is too low, the reaction product is unlikely to become liquid, and if the solubility in water is high, the condensation reaction is difficult to proceed. The amount of these solvents used may be arbitrary, but usually 10 to 20 of naphthol is used.
It is 0% by weight. After completion of the condensation reaction, this solvent is removed under heating under normal pressure or under heating under reduced pressure.
【００２５】（ｖｉ）（ヘ）について 本発明に使用されるナフトールは、α−ナフトール、β
−ナフトール、ジヒドロキシナフタレン等が挙げられる
が、α−ナフトール又はα−ナフトールとβ−ナフトー
ルの組合せが好ましい。β−ナフトール単独では、安価
ではあるが低融点で低粘度の縮合物がえられない。しか
し、α−ナフトールとβ−ナフトールを組合せることに
より目的が達成されうる。配合比率は重量比で８５／１
５〜１５／８５好しくは７０／３０〜３０／７０の範囲
から選ばれる。Regarding (vi) (f) Naphthol used in the present invention includes α-naphthol and β.
-Naphthol, dihydroxynaphthalene and the like can be mentioned, but α-naphthol or a combination of α-naphthol and β-naphthol is preferable. Although β-naphthol alone is inexpensive, a condensate having a low melting point and a low viscosity cannot be obtained. However, the object can be achieved by combining α-naphthol and β-naphthol. 85/1 by weight
5 to 15/85, preferably 70/30 to 30/70.
【００２６】（ｖｉｉ）（ト）について アルデヒドはモノアルデヒド、すなわち分子内にアルデ
ヒド基を１個有するものが用いられ、主にホルマリン水
やパラホルムアルデヒドが用いられるが、パラホルムア
ルデヒドやパラホルムアルデヒドとホルマリン水の併用
が好ましい。また、ベンズアルデヒド，ヒドロキシベン
ズアルデヒド，サリチルアルデヒドから選ばれた芳香族
系モノアルデヒドも有用である。前記アルデヒドは単独
で用いることができるが数種を併用して用いてもよい。Regarding (vii) and (g) Aldehydes are monoaldehydes, that is, those having one aldehyde group in the molecule, and mainly formalin water and paraformaldehyde are used, but paraformaldehyde, paraformaldehyde and formalin water are used. Is preferably used in combination. An aromatic monoaldehyde selected from benzaldehyde, hydroxybenzaldehyde and salicylaldehyde is also useful. The aldehydes can be used alone, but may be used in combination of several kinds.
【００２７】このようにして製造された縮合物は、反応
終了後、必要により、不純物を水洗などにより除去した
り、溶剤洗浄したり、前記の減圧脱気などの方法で未反
応モノマーやアルデヒドなどを除去してもよく、特に未
反応モノマーの除去は欠せない。After the reaction is completed, the condensate produced in this manner is, if necessary, removed of impurities such as water washing, solvent washing, and the unreacted monomer, aldehyde, etc., by the above-mentioned degassing under reduced pressure. May be removed, and especially removal of unreacted monomer is essential.
【００２８】ナフタレン核体数及びその含有量の測定は
ゲルパーミエーションクロマトグラフィー（ＧＰＣ法）
により行い、測定条件は下記に示す通りである。また核
体数の確定は分子量既知のポリスチレンによった。The number of naphthalene nuclei and the content thereof are measured by gel permeation chromatography (GPC method).
The measurement conditions are as shown below. Further, the number of nuclei was determined by polystyrene having a known molecular weight.
【００２９】溶媒：テトラヒドロフラン、流量：０．８
ｍｌ／ｍｉｎ カラム：東ソー（株）製 Ｇ４０００Ｈ、Ｇ３０００
Ｈ、Ｇ２０００Ｈ （直列）であって、排除限界分子量がそれぞれ４００，
０００、６０，０００、１０，０００である。 担体：スチレンジビニルベンゼン共重合体Solvent: tetrahydrofuran, flow rate: 0.8
ml / min column: G4000H, G3000 manufactured by Tosoh Corporation
H and G2000H (series) with exclusion molecular weights of 400 and
000, 60,000 and 10,000. Carrier: Styrene divinylbenzene copolymer
【００３０】[0030]
【実施例】以下、実施例をあげて、本発明の実施の態様
を具体的に例示して説明する。本発明はこれらの実施例
に限定されるものではない。EXAMPLES Hereinafter, the embodiments of the present invention will be specifically illustrated and described with reference to Examples. The invention is not limited to these examples.
【００３１】実施例１ 撹拌装置，水分離除去管付還流冷却管，温度計，窒素吹
込口を備えた反応容器に、α−ナフトール１４４ｇ、パ
ラホルムアルデヒド１２ｇ（α−ナフトール：アルデヒ
ド＝１：０．４（モル比、ホルムアルデヒド換算））を
仕込み、１１０℃に加熱して連続的に反応系より水を除
去しながら、８時間撹拌して反応させた。Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser with a water separation / removal tube, a thermometer, and a nitrogen inlet, 144 g of α-naphthol and 12 g of paraformaldehyde (α-naphthol: aldehyde = 1: 0. 4 (molar ratio, converted to formaldehyde) was charged and heated to 110 ° C. to continuously remove water from the reaction system, and stirred for 8 hours for reaction.
【００３２】反応終了物は２核体量が３５．３重量％、
３核体量が２０．７重量％、４以上の核体量が１３重量
％、未反応ナフトールが３１重量％であり、２量体リッ
チな縮合物が得られた。これをエバポレーターに移し、
２００℃に加熱して５ｍｍＨｇに減圧した処、未反応ナ
フトールは０．３重量％に減少（除去率９９％）した。The reaction product has a binuclear amount of 35.3% by weight,
The trinuclear amount was 20.7% by weight, the nuclear amount of 4 or more was 13% by weight, the unreacted naphthol was 31% by weight, and a dimer-rich condensate was obtained. Transfer this to an evaporator,
When heated to 200 ° C. and depressurized to 5 mmHg, unreacted naphthol was reduced to 0.3% by weight (removal rate 99%).
【００３３】このものは、２核体量が５１重量％、３核
体量が２９．７重量％、４以上の核体量が１９重量％で
あり、２核体量が多く、かつ未反応ナフトールが少ない
融点６１℃、１５０℃における溶融粘度３０ｃｐの作業
性能の優れたナフトール・アルデヒド縮合物であった。This product has a dinuclear content of 51% by weight, a trinuclear content of 29.7% by weight, and a nuclear content of 4 or more is 19% by weight. It was a naphthol-aldehyde condensate having a low melting point of 61 ° C. and a melt viscosity of 30 cp at 150 ° C. and excellent workability.
【００３４】実施例２ 実施例１においてメチルイソブチルケトン（沸点１１８
℃）２００ｇを追加して同様に反応した。反応終了物は
２核体量が４３．５重量％、３核体量が２１．７重量
％、４以上の核体量が９．８重量％、未反応ナフトール
が２５重量％であり、２量体リッチな縮合物が得られ
た。これをエバポレーターに移し、２００℃に加熱して
５ｍｍＨｇに減圧した処、未反応ナフトールは０．１重
量％に減少（除去率９９．６％）した。Example 2 In Example 1, methyl isobutyl ketone (boiling point 118
(° C) 200 g was added, and the same reaction was performed. The reaction-terminated product has a dinuclear amount of 43.5% by weight, a trinuclear amount of 21.7% by weight, a nuclear amount of 4 or more is 9.8% by weight, and unreacted naphthol is 25% by weight. A condensate rich in monomers was obtained. This was transferred to an evaporator, heated to 200 ° C. and depressurized to 5 mmHg, and unreacted naphthol was reduced to 0.1% by weight (removal rate 99.6%).
【００３５】このものは、２核体量が５８重量％、３核
体量が２８．９重量％、４以上の核体量が１３重量％と
２核体量が多く、かつ未反応ナフトールが少ない融点５
８℃、１５０℃における溶融粘度２０ｃｐの作業性能の
優れたナフトール・アルデヒド縮合物であった。本縮合
物のＧＰＣチャートを図４に示す。This product has a high dinuclear amount of 58% by weight, a trinuclear amount of 28.9% by weight, a 4 or more nuclear amount of 13% by weight, and a large amount of unreacted naphthol. Low melting point 5
It was a naphthol-aldehyde condensate having a melt viscosity of 20 cp at 8 ° C. and 150 ° C. and excellent workability. The GPC chart of this condensate is shown in FIG.
【００３６】実施例３ 実施例１においてパラホルムアルデヒドの代わりに、ベ
ンズアルデヒドを３７ｇ（α−ナフトール：アルデヒド
＝１：０．３５（モル比）を用い、反応温度を１３０℃
にして、同様に反応した。Example 3 Instead of paraformaldehyde in Example 1, 37 g of benzaldehyde (α-naphthol: aldehyde = 1: 0.35 (molar ratio) was used, and the reaction temperature was 130 ° C.
And reacted in the same manner.
【００３７】反応終了物は２核体量が４２．７重量％、
３核体量が１３．７重量％、４以上の核体量が３．６重
量％、未反応ナフトールが４０重量％であり、２量体リ
ッチな縮合物が得られた。これをエバポレーターに移
し、２００℃に加熱して２０分間５ｍｍＨｇに減圧した
処、未反応ナフトールは０．２重量％に減少（除去率９
９．５％）した。The reaction product has a binuclear amount of 42.7% by weight,
The trinuclear amount was 13.7% by weight, the amount of 4 or more nuclei was 3.6% by weight, and the unreacted naphthol was 40% by weight, and a dimer-rich condensate was obtained. This was transferred to an evaporator, heated to 200 ° C. and depressurized to 5 mmHg for 20 minutes, and unreacted naphthol was reduced to 0.2% by weight (removal rate 9
9.5%).
【００３８】このものは、２核体量が７１重量％、３核
体量が２２．８重量％、４以上の核体量が６重量％と２
核体量が多く、かつ未反応ナフトールが少ない融点７８
℃、１５０℃における溶融粘度１５ｃｐの作業性能の優
れたナフトール・アルデヒド縮合物であった。This product had a dinuclear content of 71% by weight, a trinuclear content of 22.8% by weight, and a nuclear content of 4 or more was 6% by weight.
Melting point 78 with high nuclear content and low unreacted naphthol
It was a naphthol-aldehyde condensate having a melt viscosity of 15 cp at 150C and excellent workability.
【００３９】実施例４ 実施例１においてキシレン（沸点１４０℃）２００ｇを
追加し、パラホルムアルデヒドのかわりにヒドロキシベ
ンズアルデヒド４８．８ｇ（α−ナフトール：アルデヒ
ド＝１：０．４（モル比））を用い、反応温度を１３０
℃にして、同様に反応した。Example 4 200 g of xylene (boiling point: 140 ° C.) was added in Example 1, and 48.8 g of hydroxybenzaldehyde (α-naphthol: aldehyde = 1: 0.4 (molar ratio)) was used instead of paraformaldehyde. , Reaction temperature 130
The reaction was carried out in the same manner at a temperature of ℃.
【００４０】反応終了物は２核体量が６９．３重量％、
３核体量が３．９重量％、４以上の核体量が２．８重量
％、未反応ナフトールが２４重量％であり、２量体リッ
チな縮合物が得られた。これをエバポレーターに移し、
２００℃に加熱して５ｍｍＨｇに減圧した処、未反応ナ
フトールは０．４重量％に減少（除去率９８．３％）し
た。The reaction product has a binuclear amount of 69.3% by weight,
The trinuclear amount was 3.9% by weight, the amount of 4 or more nuclei was 2.8% by weight, and the unreacted naphthol was 24% by weight, and a dimer-rich condensate was obtained. Transfer this to an evaporator,
When heated to 200 ° C. and reduced in pressure to 5 mmHg, unreacted naphthol was reduced to 0.4% by weight (removal rate 98.3%).
【００４１】このものは、２核体量が９１重量％、３核
体量が５重量％、４以上の核体量が３．６重量％と２核
体量が多く、かつ未反応ナフトールが少ない融点１０５
℃、１５０℃における溶融粘度２０ｃｐの作業性能の優
れたナフトールアルデヒド縮合物であった。This product has a high dinuclear amount of 91% by weight, a trinuclear amount of 5% by weight, a nuclear amount of 4 or more of 3.6% by weight, and a large amount of unreacted naphthol. Low melting point 105
It was a naphtholaldehyde condensate having a melt viscosity at 20 ° C and 150 ° C of 20 cp and excellent workability.
【００４２】実施例５ 実施例２において、α−ナフトールのかわりに、α−ナ
フトール７２ｇとβ−ナフトール７２ｇを用いて同様に
反応した。反応終了物は２核体量が６７重量％、３核体
量が６．９重量％、４以上の核体量が３．１重量％、未
反応ナフトールが２３重量％であり、２量体リッチな縮
合物が得られた。これをエバポレーターに移し、２００
℃に加熱して５ｍｍＨｇに減圧した処、未反応ナフトー
ルは０．１重量％に減少（除去率９９．５％）した。Example 5 In Example 2, the same reaction was carried out using 72 g of α-naphthol and 72 g of β-naphthol instead of α-naphthol. The reaction-terminated product has a dinuclear amount of 67% by weight, a trinuclear amount of 6.9% by weight, a nuclear amount of 4 or more is 3.1% by weight, and unreacted naphthol is 23% by weight. A rich condensate was obtained. This is transferred to the evaporator, 200
When heated to 0 ° C. and depressurized to 5 mmHg, unreacted naphthol was reduced to 0.1% by weight (removal rate 99.5%).
【００４３】このものは、２核体量が８７重量％、３核
体量が９重量％、４以上の核体量が３．９重量％と２核
体量が多く、かつ未反応ナフトールが少ない融点６７
℃、１５０℃における溶融粘度１５ｃｐの作業性能の優
れたナフトールアルデヒド縮合物であった。This product has a high dinuclear amount of 87% by weight, a trinuclear amount of 9% by weight, a nucleoside amount of 4 or more is 3.9% by weight, and a high amount of unreacted naphthol. Low melting point 67
It was a naphtholaldehyde condensate having a melt viscosity of 15 cp at 150C and excellent workability.
【００４４】比較例１ パラホルムアルデヒド１２ｇを２１．９ｇ（α−ナフト
ール：アルデヒド＝１：０．７３（モル比））にする以
外は、実施例１と同様にして縮合物を得、同様にエバポ
レーター処理した。このものは２核体量が１８重量％
（３核体量が４４重量％、４以上の核体量が３５．５重
量％）と低く、ナフトールが２．５重量％残存してお
り、１５０℃における溶融粘度は１８２０ｃｐとかなり
高かった。Comparative Example 1 A condensate was obtained in the same manner as in Example 1 except that 12 g of paraformaldehyde was changed to 21.9 g (α-naphthol: aldehyde = 1: 0.73 (molar ratio)). Processed. This product has a dinuclear content of 18% by weight
(Trinuclear amount is 44% by weight, 4 or more nuclei amount is 35.5% by weight), naphthol remains at 2.5% by weight, and the melt viscosity at 150 ° C. is as high as 1820 cp.
【００４５】比較例２ 触媒としてパラトルエンスルホン酸を０．５ｇ及びパラ
ホルムアルデヒドの代わりにホルマリン水（３５％）を
６０ｇ用いる以外は実施例１と同様に縮合物を得（α−
ナフトール：アルデヒド＝１：０．７（モル比））、同
様にエバポレーター処理した。このものは、２核体量が
９％（３核体量が３０重量％、４以上の核体量が５２．
５重量％））と少なく、ナフトールは８．５重量％残存
し、１５０℃における溶融粘度は７０００ｃｐときわめ
て高かった。Comparative Example 2 A condensate was obtained in the same manner as in Example 1 except that 0.5 g of paratoluenesulfonic acid was used as a catalyst and 60 g of formalin water (35%) was used instead of paraformaldehyde (α-
Naphthol: aldehyde = 1: 0.7 (molar ratio)), and similarly treated with an evaporator. This product had a dinuclear content of 9% (a trinuclear content of 30% by weight and a nuclear content of 4 or more of 52.
5% by weight)), 8.5% by weight of naphthol remained, and the melt viscosity at 150 ° C. was 7,000 cp, which was extremely high.
【００４６】[0046]
【発明の効果】本発明の製造方法により、低い融点及び
溶融粘度を持った作業性能に優れた、かつ未反応ナフト
ールが極めて少ない（０．３重量％以下）ナフトール・
アルデヒド縮合物が得られる。EFFECTS OF THE INVENTION According to the production method of the present invention, naphthol having a low melting point and melt viscosity, excellent workability, and a very small amount of unreacted naphthol (0.3% by weight or less)
An aldehyde condensate is obtained.
【図１】α−ナフトールとパラホルムアルデヒドの反応
におけるアルデヒドの仕込みモル比と縮合物中の２核体
量の関係図である。FIG. 1 is a diagram showing the relationship between the molar ratio of aldehyde charged in the reaction of α-naphthol and paraformaldehyde and the amount of binuclear bodies in the condensate.
【図２】α−ナフトールとパラホルムアルデヒドの反応
における未反応α−ナフトールと縮合物中の２核体量の
関係図である。FIG. 2 is a diagram showing the relationship between unreacted α-naphthol and the amount of binuclear bodies in the condensate in the reaction between α-naphthol and paraformaldehyde.
【図３】α−ナフトールとパラホルムアルデヒドの縮合
物の溶融粘度と減圧処理後に存在するα−ナフトール量
の関係図である。FIG. 3 is a diagram showing the relationship between the melt viscosity of a condensate of α-naphthol and paraformaldehyde and the amount of α-naphthol existing after the reduced pressure treatment.
【図４】実施例２のα−ナフトール・アルデヒド縮合物
のＧＰＣチャートである。FIG. 4 is a GPC chart of an α-naphthol / aldehyde condensate of Example 2.
Claims (4)
満のモノアルデヒドを反応させ、次いで未反応ナフトー
ルを除去することからなるナフトールアルデヒド縮合物
の製造方法。1. A process for producing a naphthol aldehyde condensate, which comprises reacting less than 0.5 mol of monoaldehyde with respect to 1 mol of naphthol and then removing unreacted naphthol.
媒を用いず、更にナフトール１モルに対してモノアルデ
ヒドを０．２５〜０．４５モルで反応させる請求項１記
載の製造方法。2. The production method according to claim 1, wherein in the condensation reaction, a monoaldehyde is reacted in an amount of 0.25 to 0.45 mol with respect to 1 mol of naphthol without using a catalyst in the reaction.
上の水に不溶又は難溶性の溶剤を用い、かつ反応温度が
８０〜１５０℃である請求項１又は２記載の製造方法。3. The production method according to claim 1, wherein in the condensation reaction, a solvent insoluble or hardly soluble in water having a boiling point of 80 ° C. or higher is used, and a reaction temperature is 80 to 150 ° C.
ナフトールとβ−ナフトールである請求項１，２又は３
記載の製造方法。4. Naphthol is α-naphthol or α-naphthol.
4. Naphthol and β-naphthol.
The manufacturing method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2880394A JPH07215902A (en) | 1994-01-31 | 1994-01-31 | Production of naphthol aldehyde condensate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2880394A JPH07215902A (en) | 1994-01-31 | 1994-01-31 | Production of naphthol aldehyde condensate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07215902A true JPH07215902A (en) | 1995-08-15 |
Family
ID=12258589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2880394A Pending JPH07215902A (en) | 1994-01-31 | 1994-01-31 | Production of naphthol aldehyde condensate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07215902A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011096273A1 (en) | 2010-02-03 | 2011-08-11 | Dic株式会社 | Phenol resin composition, process for production thereof, curable resin composition, cured products tehreof, and printed wiring board |
| KR20190070282A (en) | 2017-12-12 | 2019-06-20 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Epoxy resin composition and cured product thereof |
-
1994
- 1994-01-31 JP JP2880394A patent/JPH07215902A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011096273A1 (en) | 2010-02-03 | 2011-08-11 | Dic株式会社 | Phenol resin composition, process for production thereof, curable resin composition, cured products tehreof, and printed wiring board |
| US8394911B2 (en) | 2010-02-03 | 2013-03-12 | Dic Corporation | Phenol resin composition, production method therefor, curable resin composition, cured product thereof, and printed circuit board |
| KR20190070282A (en) | 2017-12-12 | 2019-06-20 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Epoxy resin composition and cured product thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001385B (en) | Narrowly-dispersed phenol-phenolic varnish resin preparation method and narrowly-dispersed phenol-phenolic varnish resin obtained by means of the preparation method | |
| JPH07215902A (en) | Production of naphthol aldehyde condensate | |
| JPS6252764B2 (en) | ||
| JP3395161B2 (en) | Method for producing phenolic novolak epoxy resin | |
| JPH07224142A (en) | Epoxy resin and epoxy resin composition | |
| JPS61228013A (en) | Production of highly reactive aromatic hydrocarbon-formaldehyde resin | |
| JPS63275620A (en) | Production of polyhydroxy compound | |
| JPH07216041A (en) | Naphtholaldehyde condensate and epoxy resin composition containing the same | |
| JPH04142324A (en) | Production of modified phenol/aralkyl resin | |
| JPH0680599A (en) | Production of polyhydroxynaphthalene | |
| JPS6198717A (en) | Production of high molecular weight novolak type substituted phenolic resin | |
| JPS62119220A (en) | Production of polyhydroxyl compound | |
| JPH0672934A (en) | Production of polyhydroxynaphthalene compound | |
| JPS6322824A (en) | Epoxy resin molding material for sealing electronic part | |
| JPH07216052A (en) | Epoxy resin and epoxy resin composition | |
| JPH11302350A (en) | Production of phenolic resin | |
| JP4855641B2 (en) | Method for producing novolac type phenolic resin | |
| JPS62267313A (en) | Novolak type phenolic resin | |
| JPH07119268B2 (en) | Method for producing novolac type phenolic resin | |
| JPH09124756A (en) | Novolak phenol resin and production thereof | |
| JPH0570552A (en) | Epoxy resin composition | |
| JPH05320291A (en) | Production of naphthol resin | |
| JPH0593038A (en) | Epoxy resin composition | |
| JPH10158352A (en) | Production of phenol resin | |
| JPH04332714A (en) | Production of naphthol resin |