JPH0350223A - Phenol novolac resin and its production - Google Patents
Phenol novolac resin and its productionInfo
- Publication number
- JPH0350223A JPH0350223A JP18444389A JP18444389A JPH0350223A JP H0350223 A JPH0350223 A JP H0350223A JP 18444389 A JP18444389 A JP 18444389A JP 18444389 A JP18444389 A JP 18444389A JP H0350223 A JPH0350223 A JP H0350223A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- formula
- represented
- formulas
- tables
- 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
- 229920003986 novolac Polymers 0.000 title claims abstract description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 14
- 150000004780 naphthols Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- -1 o-cresol compound Chemical class 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 241000282472 Canis lupus familiaris Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、４核体フェノール類ノボラック化金物の製造
法及び該化合物を含んだフェノール類ノボラック樹脂に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a tetranuclear phenol novolak metal product and a phenol novolac resin containing the compound.
一般にフェノール樹脂は接着性、耐薬品性、電気特性、
機械特性、耐熱性に優れるため、電気絶縁材料、接着剤
等の硬化剤として広く使われている。Generally, phenolic resin has adhesive properties, chemical resistance, electrical properties,
Due to its excellent mechanical properties and heat resistance, it is widely used as a curing agent for electrical insulation materials, adhesives, etc.
とりわけ、ＩＣの封止剤にはフェノール樹脂はエポキシ
樹脂の硬化剤として用いられている。In particular, phenolic resin is used as a curing agent for epoxy resin in IC sealants.
これは、フェノール樹脂が耐熱性及び吸水性の面で、他
の硬化剤よりも有利であることに起因する。This is because phenolic resins are more advantageous than other curing agents in terms of heat resistance and water absorption.
しかしながら、このフェノール樹脂を使用し硬化させた
としても耐熱性、吸水性は未だ充分ではない。However, even if this phenolic resin is used and cured, its heat resistance and water absorption are still insufficient.
すなわち、近年の電子材料の発展にともな５表面実装に
おいて、ハンダ浴中に硬化物が浸漬されるという過酷な
温度条件に耐え得るほどの耐熱性は満足されない。しか
も、ハンダ浴中では、硬化物中に浸入した水分は爆発的
に蒸発１゜硬化物の破壊を引き起こす元となる。従って
、硬化物の吸水率を低く抑えることは耐熱性とともに極
めて重要な課題である。That is, with the recent development of electronic materials, heat resistance sufficient to withstand the harsh temperature conditions of immersing a cured product in a solder bath is not satisfied in surface mounting. Furthermore, in the solder bath, moisture that has entered the cured product evaporates explosively by 1°, causing destruction of the cured product. Therefore, keeping the water absorption of the cured product low is an extremely important issue as well as heat resistance.
本発明者らは、これらの課題を解決するため鋭意検討し
た結果、特開昭６３−７７８３２号公報に記載のオルト
クレゾール２核体のジメチロール化合物にナフトール類
を反応させることにより得られるフェノール類ノボラッ
ク樹脂を硬化剤として用いた硬化物が高い耐熱性を有し
、しかも吸水率を低く抑えることができることを見い出
し本発明を完成させるに至った。As a result of intensive studies to solve these problems, the present inventors have discovered a phenolic novolak obtained by reacting a dimethylol compound of orthocresol dinuclear substance with naphthols as described in JP-A-63-77832. The present inventors have discovered that a cured product using a resin as a curing agent has high heat resistance and can suppress water absorption to a low level, leading to the completion of the present invention.
即ち、本発明は、
（１）一般式〔■〕
で表わされる４核体フェノール類ノボラック化合物を含
むことを特徴とするフェノール類ノボラック樹脂。That is, the present invention provides: (1) A phenolic novolak resin characterized by containing a tetranuclear phenolic novolak compound represented by the general formula [■].
（２） （１）項に記載の一般式〔■〕で表わされる
４核体フェノール類ノボラック化合物を３０重量％以上
含み、一般式〔Ｓ〕
で表わされるオルトクレゾールの２核体の量が１５重量
％以下であるたとを特徴とする（１）項に記載のフェノ
ール類ノボラック樹脂。(2) Contains 30% by weight or more of a tetranuclear phenolic novolac compound represented by the general formula [■] described in (1), and contains 15% or more of the dinuclear form of orthocresol represented by the general formula [S]. The phenolic novolak resin according to item (1), characterized in that the phenolic novolac resin is at most % by weight.
（３）一般式〔■〕
で表わされるオルトクレゾール２核体ジメチロール化合
物と一般式〔匪
で表わされるナフトール類を酸触媒下反応させて一般式
（”Ｉ）
で表わされる４核体フェノール類ノボラク
を得ることを特徴とする（１）項記載の４核体フェノー
ル類ノボラッ
ク化合物の製造法。(3) An orthocresol dinuclear dimethylol compound represented by the general formula [■] is reacted with a naphthol compound represented by the general formula [匪] under an acid catalyst to form a tetranuclear phenol novolac compound represented by the general formula (''I). The method for producing a tetranuclear phenolic novolak compound according to item (1), characterized in that it obtains the following:
（４）
一般式〔■〕
で表わされるオルトクレゾール２核体ジメチロール化合
物と一般式〔■〕
で表わされるナフ
トール類を酸触媒下反応さ
せて一般式〔■〕
で表わされる４核体フェノール類ノボラク
を３０重量％以上含み、
一般式〔Ｓ〕
で表わされるオルトクレゾールの２核体の量が１５重量
％以下であるフェノール類ノボラックを得ることを特徴
とする（２）項記載のフェノール類ノボラック樹脂の製
造法。(4) An orthocresol dinuclear dimethylol compound represented by the general formula [■] and a naphthol compound represented by the general formula [■] are reacted together under an acid catalyst to form a tetranuclear phenol novolak compound represented by the general formula [■]. The phenolic novolak resin according to item (2), characterized in that the resin contains 30% by weight or more of orthocresol dinuclear substance represented by the general formula [S] and has a content of 15% by weight or less of orthocresol binuclear. manufacturing method.
本発明のフェノール樹脂は、従来のフェノール樹脂を使
用して得られる硬化物に較べて高い耐熱性を有し、しか
も吸水率が低い硬化物を与える。The phenolic resin of the present invention provides a cured product that has higher heat resistance and lower water absorption than cured products obtained using conventional phenolic resins.
本発明のフェノール類ノボラック樹脂は、−数式〔■〕
の４核体フェノール類ノボラック化合物を含むが好まし
くは３０重量％以上含み、さらに好ましい含有量は３５
重量％以上である。The phenolic novolak resin of the present invention has the formula [■]
It contains a tetranuclear phenolic novolak compound, preferably 30% by weight or more, and more preferably 35% by weight or more.
% by weight or more.
本発明のフェノール類ノボラック樹脂中に含まれるオル
トクレゾール２核体の量は好ましくは１５重量％以下で
あるが、より好ましくは１０重量％以下であり、特に好
ましくは５重量％以下である。The amount of orthocresol binuclear substance contained in the phenolic novolac resin of the present invention is preferably 15% by weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less.
オルトクレゾール２核体の量が多すぎると、硬化物が十
分な耐熱性を有さなくなる恐れがある。If the amount of orthocresol binuclear is too large, the cured product may not have sufficient heat resistance.
本発明のフェノール類ノボラック樹脂中、上記、工核体
及びオルトクレゾール２核体化合物以外の成分は５核体
、６核体、８核体等の多核体フェノール類ノボラック化
合物である。In the phenolic novolac resin of the present invention, the components other than the above-mentioned engineered nuclei and orthocresol dinuclear compounds are polynuclear phenolic novolak compounds such as pentanuclear, hexanuclear, and octoknuclear compounds.
−数式ＣＩ、ｌで表わされる４核体フェノール類ノボラ
ック化合物及び該化合物を含む本発明のフェノール類ノ
ボラック樹脂は、次のようにして製造することが出来る
。即ち、−数式〔■〕で表わされるオルトクレゾール２
核体ジメチロール化合物〔以下化合物〔■〕という〕と
−数式で表わされるナフトール類を酸触媒の存在下に脱
水縮合させることにより製造できる。ナフトール類とし
ては、α−ナフトール１、β−ナフトールが挙げられる
。酸触媒としては、塩酸、硫酸、リン酸、ｐ−トルエン
スルホン酸、シュウ酸等が使用でき、酸触媒は化合物Ｃ
ＩＤの０．１〜３０重量％用いるのが好ましい。又、ナ
フトール類は化合物ＣＩＤに対して２〜１５モル倍用い
るのが好ましい。反応は、無溶媒でも、ベンゼン、トル
エン、メチルイソブチルケトン等の溶媒中で行うことも
できる。反応温度は２０〜１５０℃の範囲が好ましい。- The tetranuclear phenolic novolak compound represented by formula CI, 1 and the phenolic novolak resin of the present invention containing the compound can be produced as follows. That is, - orthocresol 2 represented by the formula [■]
It can be produced by dehydrating and condensing a nuclear dimethylol compound [hereinafter referred to as compound [■]] and a naphthol represented by the formula - in the presence of an acid catalyst. Examples of naphthols include α-naphthol 1 and β-naphthol. As the acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, oxalic acid, etc. can be used.
It is preferable to use 0.1 to 30% by weight of ID. Moreover, it is preferable to use naphthols in an amount of 2 to 15 times the mole of compound CID. The reaction can be carried out without a solvent or in a solvent such as benzene, toluene, methyl isobutyl ketone, or the like. The reaction temperature is preferably in the range of 20 to 150°C.
反応終了後、使用した触媒を水洗等により除去し、溶媒
及び過剰のナフトール類を減圧下に留去することにより
目的の一般式（Ｉ）で表わされる４核体フェノール類ノ
ボラック化合物及び該化合物を含むフェノール類ノボラ
ック樹脂が得られる。After the reaction, the used catalyst is removed by washing with water, etc., and the solvent and excess naphthol are distilled off under reduced pressure to obtain the desired tetranuclear phenol novolac compound represented by general formula (I) and the compound. A phenolic novolak resin containing phenols is obtained.
本発明のフェノール類ノボラック樹脂は、耐熱性、低吸
水率の要求される広範な分野で主に硬化剤として用いる
ことができる。具体的には絶縁材料、積層板、封止材料
等を例示することができる。The phenolic novolak resin of the present invention can be used mainly as a curing agent in a wide range of fields where heat resistance and low water absorption are required. Specifically, insulating materials, laminates, sealing materials, etc. can be exemplified.
以下、本発明を実施例で説明する。 The present invention will be explained below with reference to Examples.
実施例１゜
温度計、撹拌機を付けたガラス容器にＯ−クレゾール２
核体ジメチロール化合物〔化合物（２）〕２２００ｇ０
．６９モル）及びα−ナフトール９９５ｇ（６，９モル
）を仕込み、溶媒としてメチルイソブチルケトン１５０
０ｍｌを加えて窒素雰囲気下で室温で撹拌した。Example 1 O-cresol 2 was placed in a glass container equipped with a thermometer and a stirrer.
Nuclear dimethylol compound [compound (2)] 2200g0
．． 69 mol) and 995 g (6.9 mol) of α-naphthol, and 150 g (6.9 mol) of methyl isobutyl ketone as a solvent.
0 ml was added and stirred at room temperature under nitrogen atmosphere.
ｐ−）ルエンスルホン酸２ｇ（ｏ−クレゾール２核体ジ
メチロール化合物に対し１．０重量％）を発熱に注意し
、液晶が５０℃を越えないよう徐々に添加した。2 g of p-)luenesulfonic acid (1.0% by weight based on the o-cresol dinuclear dimethylol compound) was gradually added while being careful not to generate heat so that the temperature of the liquid crystal did not exceed 50°C.
添加後油浴上で５０°Ｃまで加温し２時間反応させた後
、メチルイソブチルケトン５００ ｍｌ加えて物（Ａ）
３３５ ｇを得た。このものは室温に放置すると固化し
た。生成物囚の軟化温度ＪＩＳ Ｋ２４２５環球法）は
１０５°Ｃで水酸基当量（ｇ／ｍｏｌ）は１３５であっ
た。After the addition, heat to 50°C on an oil bath and react for 2 hours, then add 500 ml of methyl isobutyl ketone to form product (A).
335 g was obtained. This solidified when left at room temperature. The softening temperature of the product (JIS K2425 ring and ball method) was 105°C, and the hydroxyl equivalent (g/mol) was 135.
実施例２゜
実施例１において、α−ナフトール４００ｇ（２，７６
モル）を用いた以外は実施例１と同様に反応させ黄色固
体ＣＢ ３３４ ｇを得た。生成物（Ｂ）の軟化温度は
１１８℃で水酸基当量（ｇ／ｍｏｌ）は１３４であった
。Example 2 In Example 1, 400 g of α-naphthol (2,76
The reaction was carried out in the same manner as in Example 1 except that 334 g of yellow solid CB was obtained. The product (B) had a softening temperature of 118° C. and a hydroxyl equivalent (g/mol) of 134.
実施例３゜
実施例１において、α−ナフトールの代りに、β−ナフ
トール９９５ｇ（５，９モル）を用い、反応温度を８０
℃とした以外は実施例１と同様に反応させ黄色固体（Ｑ
ａ３２ｇを得た。生成物（Ｑの軟化温度は１０７℃で水
酸基当量（ｇ／ｍｏｌ）は１３５であった。Example 3 In Example 1, 995 g (5.9 mol) of β-naphthol was used instead of α-naphthol, and the reaction temperature was changed to 80°C.
A yellow solid (Q
32g of a was obtained. The product (Q) had a softening temperature of 107°C and a hydroxyl equivalent (g/mol) of 135.
実施例１〜３で得られた生成物（Ａ） 、 （Ｂ） 、
（ＱをＧＰＣ分析した結果、−数式〔Ｉ〕で表わされ
る４核体及びオルトクレゾールの２核体の含有量は次の
とおりであった。Products (A), (B), obtained in Examples 1 to 3
(As a result of GPC analysis of Q, the contents of the tetranuclear body represented by formula [I] and the dinuclear body of orthocresol were as follows.
（Ａ） ８２ ０．５
ＣＢ） ４８ １．５（
Ｃ） ８１ ０．７な
お分析条件は次のとおり。(A) 82 0.5
CB) 48 1.5(
C) 81 0.7 The analysis conditions are as follows.
ＧＰＣ装置：島津製作所
（カラム： ＴＳＫ−Ｇ−３０００ＸＬ（１本）＋ＴＳ
Ｋ−Ｇ−２０００ＸＬ（２本））
溶 媒：テトラヒドロフラン１ｍ１１分検 出：
ＵＶ（２５４ｎｍ）
又、生成物（５）、（Ｅのマススペクトル（ＦＡＢ−Ｍ
Ｓ）でｋｉ” ５４０が得られたことにより次の構造を
有する成分が主成分であることを確認した。GPC device: Shimadzu (Column: TSK-G-3000XL (1 piece) + TS
K-G-2000XL (2 bottles) Solvent: Tetrahydrofuran 1 ml 11 minutes Detection:
UV (254 nm) Also, mass spectrum of product (5), (E (FAB-M
By obtaining ki'' 540 in S), it was confirmed that the main component was a component having the following structure.
（分子量５４０）
応用例１〜３゜
第１表に示す割合でエポキシ樹脂として市販のオルトク
レゾールノボラック型エポキシ樹脂（日本化薬■製、Ｅ
ＯＣＮ １０２０、エポキシ当量（ｇ／ｍｏｌ ） ２
００ｓ軟軟化度６７℃）を、硬化剤として実施例１．２
．３で得られた生成物（Ａ） 、 （Ｂ） 、 （Ｑを
、硬化促進剤として２−メチルイミダゾールを配合して
加熱硬化させた。(Molecular weight: 540) Application examples 1 to 3゜ Ortho-cresol novolac type epoxy resin (manufactured by Nippon Kayaku ■, E
OCN 1020, epoxy equivalent (g/mol) 2
Example 1.2: 00s Softening degree: 67°C)
．． The products (A), (B), and (Q) obtained in Step 3 were heat-cured with 2-methylimidazole added as a curing accelerator.
応用比較例として実施例１．２．３で得られた生成物（
Ａ） 、 （Ｂ） 、 （Ｑの代りに、第１表に示す割
合で市販のフェノールノボラック樹脂（日本化薬■製、
軟化温度８５℃、水酸基当量（ｇ／ｍｏｌ）、０−クレ
ゾールノボラック樹脂（日・本化薬■製、軟化温度１１
０℃、水酸基当量（ｇ／ｍｏｌ ） １２０ ）を用い
て加熱硬化した。As an applied comparative example, the product obtained in Example 1.2.3 (
A), (B), (Instead of Q, commercially available phenol novolac resin (manufactured by Nippon Kayaku ■,
Softening temperature: 85°C, hydroxyl equivalent (g/mol), 0-cresol novolak resin (manufactured by Nippon Kayaku ■, softening temperature: 11
Heat curing was carried out at 0° C. using a hydroxyl equivalent (g/mol) of 120).
以上の硬化物についてガラス転移温度（Ｔｇ）、熱変形
温度（ＨＤＴ）及び吸水率を測定し、その結果を第１表
に示した。The glass transition temperature (Tg), heat distortion temperature (HDT), and water absorption rate of the above cured product were measured, and the results are shown in Table 1.
尚、ガラス転移温度、熱変形温度、吸水率の測定条件は
下記のとおり。The measurement conditions for glass transition temperature, heat distortion temperature, and water absorption are as follows.
ガラス転移温度
熱機械測定装置（ＴＭＡ）； 真空理工■ＴＭ−７００
０昇温速度；２℃／ｍｉｎ
熱変形温度 ＪＩＳ Ｋ７２０７
吸 水 率 試験片 直径 ５ Ｑ ｍｍ厚さ ３ｍｍ
円板
条 件 １００℃の水中で５０時間煮沸した後の１景増
加量による吸水率（重量％）
〔発明の効果〕
第１表から明らかなように、本発明のフェノール類ノボ
ラック樹脂は高い耐熱性を有し、しかも吸水率が低い硬
化物を与えることから、主に硬化剤として有用であり、
耐熱性、低吸水性が要求される分野での工業的価値が犬
である。Glass transition temperature thermomechanical measuring device (TMA); Vacuum Riko TM-700
0 Heating rate: 2℃/min Heat deformation temperature JIS K7207 Water absorption rate Test piece Diameter 5 Q mm Thickness 3 mm
Disc conditions: Water absorption rate (weight %) based on the increase in volume after boiling in water at 100°C for 50 hours [Effects of the invention] As is clear from Table 1, the phenolic novolak resin of the present invention has high heat resistance. It is mainly useful as a curing agent because it provides a cured product with high properties and low water absorption.
Dogs have industrial value in fields where heat resistance and low water absorption are required.
Claims (4)
むことを特徴とするフェノール類ノボラック樹脂。(1) A phenolic novolak resin characterized by containing a tetranuclear phenolic novolak compound represented by the general formula [I] ▲Mathematical formula, chemical formula, table, etc.▼[I].
核体フェノール類ノボラック化合物を３０重量％以上含
み、一般式〔Ｓ〕 ▲数式、化学式、表等があります▼〔Ｓ〕 で表わされるオルトクレゾールの２核体の量が１５重量
％以下であることを特徴とする請求項１に記載のフェノ
ール類ノボラック樹脂。(2) 4 represented by the general formula [I] according to claim 1
Contains 30% by weight or more of a nuclear phenolic novolac compound, and the amount of ortho-cresol binuclear represented by the general formula [S] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [S] 15% by weight or less The phenolic novolak resin according to claim 1, characterized by:
物と一般式〔III〕 ▲数式、化学式、表等があります▼〔III〕 で表わされるナフトール類を酸触媒下反応させて一般式
〔 I 〕 ▲数式、化学式、表等があります▼〔 I 〕 で表わされる４核体フェノール類ノボラックを得ること
を特徴とする請求項１記載の４核体フェノール類ノボラ
ック化合物の製造法。(3) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] Orthocresol dinuclear dimethylol compound represented by and general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] Claim 1, characterized in that a tetranuclear phenolic novolak represented by the general formula [I] ▼Numerical formula, chemical formula, table, etc.▼[I] is obtained by reacting naphthols represented by the following under an acid catalyst. A method for producing a tetranuclear phenolic novolac compound.
と一般式〔III〕 ▲数式、化学式、表等があります▼〔III〕 で表わされるナフトール類を酸触媒下反応させて一般式
〔 I 〕 ▲数式、化学式、表等があります▼〔 I 〕 で表わされる４核体フェノール類ノボラックを３０重量
％以上含み、一般式〔Ｓ〕 ▲数式、化学式、表等があります▼〔Ｓ〕 で表わされるオルトクレゾールの２核体の量が１５重量
％以下であるフェノール類ノボラックを得ることを特徴
とする請求項２記載のフェノール類ノボラック樹脂の製
造法。(4) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] O-cresol dinuclear dimethylol compound represented by and general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III ] The naphthols represented by the formula [I] are reacted under an acid catalyst to form the general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. S] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [S] The phenol according to claim 2, characterized in that the phenol novolac in which the amount of orthocresol dinuclear substance represented by is 15% by weight or less is obtained. Method for producing novolak resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18444389A JPH0350223A (en) | 1989-07-19 | 1989-07-19 | Phenol novolac resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18444389A JPH0350223A (en) | 1989-07-19 | 1989-07-19 | Phenol novolac resin and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0350223A true JPH0350223A (en) | 1991-03-04 |
Family
ID=16153238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18444389A Pending JPH0350223A (en) | 1989-07-19 | 1989-07-19 | Phenol novolac resin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0350223A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014065829A (en) * | 2012-09-26 | 2014-04-17 | Dic Corp | Cresol-naphthol resin, curable resin composition, cured material of the composition, and printed circuit board |
-
1989
- 1989-07-19 JP JP18444389A patent/JPH0350223A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014065829A (en) * | 2012-09-26 | 2014-04-17 | Dic Corp | Cresol-naphthol resin, curable resin composition, cured material of the composition, and printed circuit board |
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