JPS6377915A - Phenol novolaks and its production - Google Patents
Phenol novolaks and its productionInfo
- Publication number
- JPS6377915A JPS6377915A JP22199886A JP22199886A JPS6377915A JP S6377915 A JPS6377915 A JP S6377915A JP 22199886 A JP22199886 A JP 22199886A JP 22199886 A JP22199886 A JP 22199886A JP S6377915 A JPS6377915 A JP S6377915A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- weight
- formula
- dinuclear
- phenolic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229920003986 novolac Polymers 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000002989 phenols Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 abstract 4
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 11
- 210000003323 beak Anatomy 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- -1 8eC-butyl group Chemical group 0.000 description 2
- 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
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue 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
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
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を３０重量％以
上含み２核体フェノール頑ノボラックの量が１５重量−
以下であるフェノール類ノボラック及びその製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is characterized in that it contains 30% by weight or more of tetranuclear phenolic novolac, and the amount of dinuclear phenolic novolak is 15% by weight.
The present invention relates to the following phenolic novolak and its manufacturing method.
フェノール類ノボラックはフェノールｍ脂トして、電気
、電子、建築、塗料関係等に広く使用されているが、従
来のフェノール類ノボラックは分子量分布が広く、主と
して軟化温度の違いによりそれぞれの用途に用いられて
きた。Phenolic novolaks are widely used in electrical, electronic, architectural, and paint-related applications, but conventional phenolic novolacs have a wide molecular weight distribution and are difficult to use for each purpose due to differences in softening temperature. I've been exposed to it.
しかし高性能化の要求は近年増すばかりで、従来型の分
子量分布の広いノボラックでは対応しきれなくなってき
ている。However, the demand for higher performance has only increased in recent years, and conventional novolaks with a wide molecular weight distribution are no longer able to meet the demands.
例えば、電気、ａ＋ｍ器においては高集積化。For example, electrical and A+M equipment is highly integrated.
高性能化、高信頼性化には目を見張るものがあり。The improvements in performance and reliability are remarkable.
それと共に、それに使用される絶縁材料１部品等に対し
て耐熱性、耐湿性１寸法安定性等の諸性能のより一層の
向上が望まれている。At the same time, it is desired to further improve various performances such as heat resistance, moisture resistance, and dimensional stability of the insulating material components used therein.
従来よりこれらの材料に用いられるフェノール類ノボラ
ンクは、低粘度品（低軟化温度品）では２核体等の低分
子化合物を多く（例えば２５重量％）含み、硬化物での
耐熱性に問題があり、ビスフェノール系でも常温で液体
の使いやすいものがあるが、二官能性であるため、硬化
物での耐熱性に欠点を有する。The phenolic Novolank conventionally used for these materials contains a large amount (for example, 25% by weight) of low-molecular compounds such as binuclear bodies in low viscosity products (low softening temperature products), and has problems with heat resistance in cured products. Some bisphenol-based compounds are liquid at room temperature and are easy to use, but because they are difunctional, they have a drawback in heat resistance in the cured product.
また高軟化温度のフェノール類ノボラックは。Also, the phenolic novolak has a high softening temperature.
硬化物での耐熱性は向上するものの、軟化温度が高いた
め１作業性が悪くなり、相溶性との本合いで使用が限定
される等の欠点を有する。Although the heat resistance of the cured product is improved, it has drawbacks such as poor workability due to the high softening temperature and limited use depending on compatibility.
本発明者らは、フェノール類ノボランクを種々検討の結
果、４核体フェノール類ノボラックを３０重ｉ％以上含
み、２核体フェノール類ノボランクの量が１５重量−以
下であるフェノール類ノボラックは軟化温度が低いにも
かかわらずその硬化物が耐熱性に優れたフェノール点ノ
ボラックであ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 various studies on phenolic novolaks, the present inventors found that phenolic novolaks containing 30% by weight or more of tetranuclear phenolic novolaks and 15% by weight or less of dinuclear phenolic novolaks have a softening temperature. It was discovered that the cured product is a phenol-point novolac with excellent heat resistance despite its low heat resistance, and the present invention was completed.
即ち本発明は、（１）一般式（１）
（式中、Ｒは水素原子又は炭素数１０以下のアルキル基
であり、ｎは１，２又は３を示す。）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２核体
フェノール類ノボラックのｔが１５重量％以下であるフ
ェノール類ノボラック、及び
（２）式（Ｉｔ）
で表わされる０−クレゾール２核体ジメチロール化合物
に一般式（ｌｆｔ）
Ｍ
（式中、Ｒは水素原子又は炭素数１０以下のアルキル基
を示し、ｎは１，２又は３を示す。）で表わされるフェ
ノール類を反応させることを特徴とする一般式（１）
（式中、Ｒ及びｐは前記のものを示す。）で表わされる
フェノール類ノボラックの製造法、に関する。That is, the present invention provides (1) a tetranuclear phenol represented by the general formula (1) (wherein R is a hydrogen atom or an alkyl group having 10 or less carbon atoms, and n represents 1, 2, or 3); A phenolic novolak containing 30% by weight or more of a dinuclear phenolic novolak and t of 15% by weight or less, and (2) an 0-cresol dinuclear dimethylol compound represented by formula (It) is combined with the general formula ( lft) M (wherein, R represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and n represents 1, 2 or 3). ) (wherein R and p are as defined above).
前記一般式（１）及び（１）において、Ｒで表わされる
アルキル基としてはメチル基、エチル基、ｎ−プロピル
基、１−プロピル基、ｎ−ブチル基、８ｅＣ−ブチル基
、ｔ−ブチル基、ｎ−ノニル基等が例示される。特に好
ましいＲとしては、水素原子、炭素数１〜６のアルキル
基があげられる。In the general formulas (1) and (1), the alkyl group represented by R includes a methyl group, ethyl group, n-propyl group, 1-propyl group, n-butyl group, 8eC-butyl group, and t-butyl group. , n-nonyl group and the like. Particularly preferable examples of R include a hydrogen atom and an alkyl group having 1 to 6 carbon atoms.
前記一般式（１）で表わされる具体・的な化合物として
は、ロークレゾール４核体、０−クレゾール２核体ジメ
チロール化合物〔式（ＩＩ）の化合物〕（以下化合物（
ＩＩ）という）にフェノールを反応させた４核体フェノ
ール類ノボラック、化合物（１１）にｐ−クレゾールを
反応させた４核体フェノール類ノボラック、化合物（Ｉ
［）にｍ−クレゾールを反び／又は２，６−キシレノー
ルを反応させた４核体フェノール類ノボラック等を挙げ
ることができる。Specific compounds represented by the general formula (1) include lo-cresol tetranuclear and 0-cresol dinuclear dimethylol compounds [compounds of formula (II)] (hereinafter referred to as compounds (
Tetranuclear phenol novolak prepared by reacting compound (II) with phenol, tetranuclear phenol novolak prepared by reacting compound (11) with p-cresol, compound (I)
Examples include novolak, a tetranuclear phenol obtained by reacting m-cresol with 2,6-xylenol.
本発明のフェノール類ノボラクク中の一般式（１）で示
される４核体フェノール類ノボラックの含有量は３０重
量％以上であるが、この含有量はよシ好ましくは５０重
量％以上である。The content of the tetranuclear phenol novolac represented by general formula (1) in the phenolic novolac of the present invention is 30% by weight or more, and this content is preferably 50% by weight or more.
本発明のフェノール類ノボラック中に含まれる２核体フ
ェノール類ノボラックの量は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。これら２核体フェノール類ノボラ
ックと−しては１式（ＩＶ）で表わされる化合物が挙げ
られる。２核体フェノール類ノボラックの量が多すぎる
と、硬化物が十分な耐熱性を有さなくなる。The amount of dinuclear phenolic novolak contained in the phenolic novolac of the present invention is 15% by weight or less,
It is more preferably 10% by weight or less, particularly preferably 5% by weight or less. Examples of these dinuclear phenol novolaks include compounds represented by formula (IV). If the amount of the dinuclear phenolic novolac is too large, the cured product will not have sufficient heat resistance.
本発明のフェノール類ノボラック中、上記４核体及び２
核体フェノール類ノボラック以外の成分は、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である
。In the phenolic novolak of the present invention, the above-mentioned tetranuclear bodies and two
Components other than the nuclear phenolic novolak include pentanuclear and hexanuclear phenols.
It is a polynuclear phenolic novolac such as nuclear and octakaryon.
本発明において、４核体フェノール類ノボラック（１）
は前記式（Ｉｆ）で表わされる０−クレゾール２核体ジ
メチロール化合物〔化合物（■）〕と一般式（Ｉｌｌ）
のフェノール類を反応させることにより得られるが８反
応は酸触媒のもとで行なうのが好ましく、脱水縮合によ
り容易に一般式ＣＩ）の化合物を得ることができる。In the present invention, the tetranuclear phenol novolac (1)
is an 0-cresol dinuclear dimethylol compound represented by the above formula (If) [compound (■)] and the general formula (Ill)
The reaction is preferably carried out under an acid catalyst, and the compound of general formula CI) can be easily obtained by dehydration condensation.
使用する触媒としては塩酸、硫酸、リン酸等のｍｔｆｉ
［、ｐ−トルエンスルホン酸、シュワ酸等）有機酸等が
挙げられるが１反応液の着色が少ないことより：ｐ−）
ルエンスルホン威、シュワ酸が好ましい。The catalyst used is mtfi such as hydrochloric acid, sulfuric acid, phosphoric acid, etc.
[, p-toluenesulfonic acid, oxalic acid, etc.) organic acids, etc., but 1. Since the reaction solution is less colored: p-)
Luenesulfonic acid and oxalic acid are preferred.
触媒の使用量は０−クレゾール２核体ジメチロール化合
物〔化合物（■）〕に対し好ましくは０．１から３０重
量％の範囲であるが、特に好ましくは０．２から１０重
量−の範囲であり、比較的少量で有効である。The amount of the catalyst used is preferably in the range of 0.1 to 30% by weight, particularly preferably in the range of 0.2 to 10% by weight, based on the 0-cresol dinuclear dimethylol compound [compound (■)]. , is effective in relatively small amounts.
フェノール類の使用量は０−クレゾール２核体ジメチロ
ール化合物〔化合物（Ｉ［） ３１モルに対して１から
５０モルの範囲が好ましく、特に２から１５モルの範囲
が好ましい。The amount of phenol used is preferably in the range of 1 to 50 moles, particularly preferably in the range of 2 to 15 moles, per 31 moles of the 0-cresol dinuclear dimethylol compound [compound (I)].
反応は、溶媒を用いず無溶媒で行うこともできるが、溶
媒中で行なってもよく、溶媒としては、ベンゼン、トル
エン、メチルイソブチルケトン等原料及び生成物と反応
しないものであれば、特に限定されずいずれも使用でき
る。The reaction can be carried out without using a solvent, but it can also be carried out in a solvent, and there are no particular restrictions on the solvent as long as it does not react with the raw materials or products, such as benzene, toluene, methyl isobutyl ketone, etc. Both can be used.
通常は常圧下で反応を行うが１反応で生成する水を反応
系外に除去しながら且つ反応に使用したフェノール類が
留出しない程度の減圧、温度下で行うこともできる。The reaction is usually carried out under normal pressure, but it can also be carried out under reduced pressure and temperature to such an extent that the water produced in one reaction is removed from the reaction system and the phenols used in the reaction are not distilled out.
反応温度は、溶媒を用いない場合は用いるフェノール類
の融点より高い温度で行うことになるが。When a solvent is not used, the reaction temperature is higher than the melting point of the phenol used.
溶媒を用いる場合にはフェノール類の融点に関係ない温
度で行うことが出来る。反応温度は通常２０℃から１５
０℃の範囲にあるが好ましくは４０℃から１００℃の範
囲にある。When a solvent is used, it can be carried out at a temperature that is not related to the melting point of the phenol. The reaction temperature is usually 20°C to 15°C.
It is in the range of 0°C, preferably in the range of 40°C to 100°C.
反応時間は特に限定されないが通常１０分から２０時間
の範囲にあり、好ましくは３０分から１０時間である。The reaction time is not particularly limited, but is usually in the range of 10 minutes to 20 hours, preferably 30 minutes to 10 hours.
反応終了後、使用した触媒を水洗等で除去後使用した溶
媒及び過剰のフェノール類を減圧下で留去することによ
シ目的物の４核体フェノール類ノボラックが高収率、高
純匿で得られる。After the reaction, the used catalyst is removed by washing with water, etc., and the used solvent and excess phenol are distilled off under reduced pressure to obtain the target tetranuclear phenol novolac in high yield and high purity. can get.
このようにして得られる生成物はそのまま本発明の″４
核体フェノール頌ノボラックを５０重量−以上含み２核
体フェノール類ノボラックの量が１５重量％以下である
フェノール類ノボラック”となる。The product obtained in this way is used as it is in "4" of the present invention.
A phenolic novolak containing 50% by weight or more of a nuclear phenolic novolak and 15% by weight or less of a dinuclear phenolic novolak.
本発明の７エノール類ノボランクはイ子、電気機器用途
の耐熱性に優れたエボキ７％脂積層板やエポキシ樹脂成
型材料用の硬化剤として使用でき。The 7-enol Novolanc of the present invention can be used as a curing agent for epoxy resin molding materials and 7% epoxy resin laminates with excellent heat resistance for electrical equipment applications.
又、エポキシ樹脂の原料として使用することも出来る。It can also be used as a raw material for epoxy resin.
〔実施例〕 以下実施例を挙げて説明する。〔Example〕 This 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０−クレゾール２
核体ジメチロール化合物〔化合物（’ｎ） ）２００
ｆ （０，６９％＃）及び０−フレジーｋ ７５０２（
６・９モル）を仕込み窒素雰囲気下で室温で攪拌した。Example 1 0-Cresol 2 in a glass container equipped with a thermometer and a stirrer
Nuclear dimethylol compound [Compound ('n)) 200
f (0,69% #) and 0-Frezi k 7502 (
6.9 mol) was charged and stirred at room temperature under a nitrogen atmosphere.
ｐ−トルエンスルホン酸２Ｐ（０−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
、液温が５０℃を越えないよう徐々に添加した。p-Toluenesulfonic acid 2P (1.0% by weight based on the 0-cresol dinuclear dimethylol compound) was gradually added while being careful not to generate heat so that the liquid temperature did not exceed 50°C.
添加後前浴上で５０℃まで加温し、２時間反応させた後
、メチルインブチルケトン５００ｄ加えて２ｔの分液ロ
ートに移し水洗した。洗浄水が中性を示すまで水洗後、
有機層を減圧下濃縮し、淡黄色粘性物（Ａ） ３０６
ｒを得た。このものは室温に放置すると固化した。生成
物（Ａ）の軟化温度（ＪＩＳ Ｋ２４２５環球法）は８
１．０’Ｃで水酸基当量（２／ゴ）は１１９であった。After the addition, the mixture was heated to 50° C. on the pre-bath and reacted for 2 hours, after which 500 d of methyl in butyl ketone was added and the mixture was transferred to a 2 t separating funnel and washed with water. After washing with water until the washing water shows neutrality,
The organic layer was concentrated under reduced pressure to obtain a pale yellow viscous substance (A) 306
I got r. This solidified when left at room temperature. The softening temperature (JIS K2425 ring and ball method) of the product (A) is 8
The hydroxyl equivalent (2/g) was 119 at 1.0'C.
溶媒としてテトラヒドロ７ラン（ＴＨＦ）ｔ−用いて生
成物（Ａ）を次のＧＰＣ装置により分析した曲
ところ第１図に示される分子量分布面線を得た。The product (A) was analyzed using the following GPC apparatus using tetrahydrofuran (THF) as a solvent, and the molecular weight distribution surface line shown in FIG. 1 was obtained.
ＧＰＣ装！＝島津裏作所
（力５ム： ＴＳＫ−Ｇ−ｓ ｏｏｏＸＬ（１本）＋Ｔ
ＳＫ−Ｇ−２０００ＸＬ（２本））
溶媒：テトラヒドロフラン １ ｄ ／ 分検出 σｖ
（２５４ｎｍ ）
この分析条件でのビスフェノールＦの現われるリテンシ
ョンタイムは２４．７分であるので、メインビークのリ
テンションタイムはベンゼン核を４個有する４核体のり
テン７ヨンタイムに相当し、第１図よりメインビークの
組成量は８４重量％であった。GPC outfit! = Shimadzu Urasakusho (Strength 5m: TSK-G-s oooXL (1 piece) + T
SK-G-2000XL (2 bottles) Solvent: Tetrahydrofuran 1 d/min detection σv
(254nm) The retention time at which bisphenol F appears under these analysis conditions is 24.7 minutes, so the retention time of the main beak corresponds to the time of the four-nuclear substance having four benzene nuclei. The composition of the main beak was 84% by weight.
生成物（Ａ）のマススペクトル（ＦＡＢ−ＭＳ）でＭ”
４６８が得られたことより次の化学補遺を有する成分が
主成分であることがわかった。Mass spectrum (FAB-MS) of product (A) shows M”
From the fact that 468 was obtained, it was found that the main component was a component having the following chemical addendum.
また、第１図より生成物（Ａ）は２核体フェノール類／
ｙＷラックを０・７重量％含んでいることがわかった。Also, from Figure 1, the product (A) is a dinuclear phenol/
It was found that it contained 0.7% by weight of yW Lac.
実施例２
実施例１において、０−クレゾールの代りにフェノール
６５０ ｆ （６，９１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（ｆｌ） ２８８ ｉ／を得
た。生成物（ｆｌ）の軟化温度は８４・２℃でろりた。Example 2 Example 1 except that phenol 650 f (6.91 mol) was used instead of 0-cresol in Example 1.
The reaction was carried out in the same manner as above to obtain a yellow solid (fl) 288 i/. The softening temperature of the product (fl) was 84.2°C.
生成物（ｆｌ）のＧＰＣ装置による分析結果を第２図に
示す（なお１分析条件は実施例１と同じ。）。The results of analysis of the product (fl) using a GPC device are shown in FIG. 2 (1 analysis conditions are the same as in Example 1).
メインビークのリテンションタイムは第１図と同じく４
核体のリテンションタイムに相当し、第２図よりメイン
ビークの組成量は８００重量％であることがわかった。The retention time of the main beak is 4 as in Figure 1.
It corresponds to the retention time of the core, and from FIG. 2 it was found that the composition amount of the main beak was 800% by weight.
又、生成物ＣＢ）のマススペクトル（ＴＡＢ−ＭＳ）で
Ｍ＋４４０が得られ、つぎの構造を有する成分が主成分
であることがわかった。Moreover, M+440 was obtained in the mass spectrum (TAB-MS) of the product CB), and it was found that the main component was a component having the following structure.
また、第２図より生成物ＣＢ）は２核体フェノール類ノ
ボラックを０．８重量％含んでいることがわかった。Further, from FIG. 2, it was found that the product CB) contained 0.8% by weight of a dinuclear phenolic novolac.
実施例５
実施例１において、０−クレゾールの代、りＫｐ−し−
ブチルフェノール１ｏｓｓｒ（６−９モル）を用い、又
、溶媒としてメチルイソブチルケトン１５００ｄを加え
１反応温度８０℃とした以外は実施例１と同様に反応さ
せ黄色固体（Ｃ） ３６１ ｐを得た。生成物（Ｃ）の
軟化温度は１０５℃であった。Example 5 In Example 1, instead of 0-cresol, RIKp-
The reaction was carried out in the same manner as in Example 1, except that 1 ossr (6-9 mol) of butylphenol was used, 1500 d of methyl isobutyl ketone was added as a solvent, and the reaction temperature was 80° C. to obtain a yellow solid (C) 361 p. The softening temperature of product (C) was 105°C.
生成物（Ｃ）のＧＰＣ装置による分析結果を第５図に示
す（なお１分析条件は実施例１と同じ）。The results of analysis of product (C) using a GPC device are shown in FIG. 5 (note that one analysis condition is the same as in Example 1).
メインビークのリテンションタイムは第１図と同じく、
４核体のりテンションタイムに相当し、第３図よりメイ
ンビークの組成量は７０重量％であり、生成物（Ｃ）の
マススペクトル（ＴＡＢ−ＭＳ）でＭ＋５５２が得られ
、つぎの構造を有する取分が主成分であることがわかっ
た。The retention time of the main beak is the same as in Figure 1.
This corresponds to the tension time of the tetranuclear glue, and from Figure 3, the composition of the main beak is 70% by weight, and the mass spectrum (TAB-MS) of the product (C) shows M+552, and has the following structure. It was found that the share was the main component.
又、第３図より生成物（Ｃ）は２核体フェノール類ノボ
ラックの含有ｔは０．１重量−以下であった。Further, from FIG. 3, the content of the dinuclear phenol novolak in the product (C) was 0.1 weight or less.
実施例４
実施例１においてＯ−クレゾールの代りに２，６−キシ
レノールＢ４２ｆ（６，９モル）を用い、又。Example 4 In Example 1, 2,6-xylenol B42f (6.9 mol) was used instead of O-cresol.
溶媒としてメチルイソブチルケトン１５００ａｒ７１加
え反応温度８０℃とした以外は実施例１と同様に反応し
て黄色固体（Ｄ） ３３５ ｆを得た。The reaction was carried out in the same manner as in Example 1 except that 1,500 ar71 of methyl isobutyl ketone was added as a solvent and the reaction temperature was 80° C. to obtain a yellow solid (D) 335 f.
生成物ＣＤ）の軟化温度は８２．７℃で水酸基当量（ｙ
／ｍｏｌ）は１２７であった。ＧＰＣ分析（分析条件は
実施例１に同じ）による分子量分布曲線を第４図に示し
たが、メインビークのリテンションタイムはベンゼン核
４個有する４核体のリテンションタイムに相当し、メイ
ンビークの組成量は８５重量％であった。生成物（Ｄ）
のマススペクトル（ＦＡＢ−ＭＳ）でＭ ４９６が得ら
れたことより、次の構造を有する化合物が主成分である
ことがわかった。The softening temperature of the product CD) is 82.7°C and the hydroxyl equivalent (y
/mol) was 127. Figure 4 shows the molecular weight distribution curve obtained by GPC analysis (analysis conditions are the same as in Example 1). The amount was 85% by weight. Product (D)
From the fact that M496 was obtained in the mass spectrum (FAB-MS), it was found that the main component was a compound having the following structure.
（分子量４９６）
又、第４図より生成物ＣＤ）は２核体フェノール類ノボ
ラックを２．５重量％含んでいることがわかった。(Molecular weight: 496) Furthermore, from FIG. 4, it was found that the product CD) contained 2.5% by weight of the dinuclear phenolic novolac.
実施例５
０−クレゾールを２９８９（２，７６モル）用い、又、
溶媒としてメチルイソブチルケトン６００ゴを加えた以
外は実施例１と同様に反応させ黄色固体（Ｅ） ｓ １
Ｓ ｆを得た。Example 5 Using 2989 (2.76 mol) of 0-cresol,
The reaction was carried out in the same manner as in Example 1 except that 600 g of methyl isobutyl ketone was added as a solvent to obtain a yellow solid (E) s 1
S f was obtained.
生成物＜ＩＡ）の軟化温度は８８・３℃で水酸基当量（
ｆ／’ｍ召は１２０であった。The softening temperature of the product <IA) is 88.3°C and the hydroxyl equivalent (
The f/'m call was 120.
ＧＰＣ分析（分析条件は実施例１に同じ）による分子量
分布曲線を第５図に示した。メインビークのリテンショ
ンタイムは実施例１と同じであったがメインビークより
高分子の化合物が実施例１に比べやや多く、メインビー
クの組成量は５４重量％であった。The molecular weight distribution curve obtained by GPC analysis (analysis conditions are the same as in Example 1) is shown in FIG. The retention time of the main beak was the same as in Example 1, but the amount of polymeric compounds in the main beak was slightly higher than in Example 1, and the composition amount of the main beak was 54% by weight.
又、第５図より生成物ＣＩ！’）は２核体フェノール類
ノボラククを１．１重量％含んでいることがわかった。Also, from FIG. 5, the product CI! ') was found to contain 1.1% by weight of dinuclear phenolic novolac.
参考例１
第１表に示す割合で０−クレゾールノボラック型エポキ
シ樹脂（ＥＯＣＮ １０２０：日本化薬（株）製、軟
化温度６７．９℃）に実施例１．２．３．４及び５で得
られた４核体フェノール類ノボラックを主成分とするフ
ェノール類ノボラック （Ａ）。Reference Example 1 0-Cresol novolak type epoxy resin (EOCN 1020: manufactured by Nippon Kayaku Co., Ltd., softening temperature 67.9°C) was added to the 0-cresol novolac type epoxy resin obtained in Example 1.2.3.4 and 5 in the proportions shown in Table 1. A phenolic novolac (A) whose main component is a tetranuclear phenolic novolac.
ＣＢ） ｌ （Ｃ） ｌ ＣＤ） ｌ ＣＢ） を配
合し、２−メチルイミダゾールを触媒に用いて加熱硬化
させた。CB) l (C) l CD) l CB) was blended and cured by heating using 2-methylimidazole as a catalyst.
比較例として、実施例１．２．３．４及び５で得られた
４核体フェノール類ノボラックを主成分とするフェノー
ル類ノボラックの代りに第１表に示す割合で市販のフェ
ノールノボラック（ＰＮＨ−１：日本化薬（株）［、軟
化温度８５．０℃、２核体及び４核体をそれぞれ２１．
１３重量％含む。）、ビスフェノールＦ（宇部興産（株
）製、２核体含有量９１重量％）及び０−クレゾールノ
ボラック〔日本化薬（株）製、軟化温度８１・５℃、２
核体及び４核体をそれぞれ１７．１５重量％含む、ＧＰ
Ｃ分析（分析条件は実施例１に同じ）による分子量分布
曲線を第６図に示す。〕を用いて加熱硬化した。As a comparative example, a commercially available phenol novolak (PNH- 1: Nippon Kayaku Co., Ltd., softening temperature 85.0°C, dinuclear and tetranuclear bodies, respectively, 21.
Contains 13% by weight. ), bisphenol F (manufactured by Ube Industries, Ltd., dinuclear content 91% by weight) and 0-cresol novolac (manufactured by Nippon Kayaku Co., Ltd., softening temperature 81.5°C, 2
GP containing 17.15% by weight each of nuclear bodies and tetranuclear bodies
The molecular weight distribution curve obtained by C analysis (analysis conditions are the same as in Example 1) is shown in FIG. ] was used for heat curing.
以上の硬化物について、ガラス転移温度（Ｔｇ）及び熱
変形温度（ＨＤＴ）を測定しその結果を第１表に示した
。第１表から明らかなように本発明のフェノール類ノボ
ラックを用いた場合、得られる硬化物は耐熱性に優れて
いることがわかる。The glass transition temperature (Tg) and heat distortion temperature (HDT) of the above cured product were measured and the results are shown in Table 1. As is clear from Table 1, when the phenolic novolac of the present invention is used, the resulting cured product has excellent heat resistance.
来１）エポキシ当量（＠／ｍｏｌ ） ２０２米２）熱
機械測定装置（ＴＭＡ）真空理工（株）製ＴＭ〜７００
０米３）Ｊ工Ｓ Ｋ７２０７
〔発明の効果〕
本発明のフェノール類ノボラックは従来のものに比し分
子量分布が狭く、軟化温度が低いため取り扱い易く１作
業性が優れ、又、これを用いて得られる硬化物は耐熱性
に優れている。1) Epoxy equivalent (@/mol) 202 US 2) Thermomechanical measuring device (TMA) manufactured by Shinku Riko Co., Ltd. TM~700
0 US 3) J Engineering S K7207 [Effects of the Invention] The phenolic novolac of the present invention has a narrower molecular weight distribution and lower softening temperature than conventional ones, so it is easy to handle and has excellent workability. The resulting cured product has excellent heat resistance.
本発明の製造法によれば、４核体フェノール類ノボラッ
クを高収率、高純度で容易に得ることが出来る。According to the production method of the present invention, a tetranuclear phenol novolac can be easily obtained in high yield and high purity.
第１図〜第６図はそれぞれ実施例１〜５で得られた生成
物ｃＡ） ＊ （ｆｌ） ＋ （Ｃ） ＋ ＣＤ） ｐ
（Ｆり及び比較例に用いた市販のロークレゾールノボ
ラックの分子量分布曲線である。Figures 1 to 6 show the products cA) * (fl) + (C) + CD) p obtained in Examples 1 to 5, respectively.
(This is a molecular weight distribution curve of commercially available low cresol novolak used in F and comparative examples.
Claims (2)
であり、ｎは１、２又は３を示す。）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２核体
フェノール類ノボラックの量が１５重量％以下であるフ
ェノール類ノボラック。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a hydrogen atom or an alkyl group having 10 or less carbon atoms, and n represents 1, 2, or 3.) A phenolic novolac containing 30% by weight or more of a dinuclear phenolic novolac and 15% by weight or less of a dinuclear phenolic novolak.
に一般式 ▲数式、化学式、表等があります▼ （式中、Ｒは水素原子又は炭素数１０以下のアルキル基
を示し、ｎは１、２又は３を示す。）で表わされるフェ
ノール類を反応させることを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ及びｎは前記のものを示す。）で表わされる
フェノール類ノボラックの製造法。(2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available for the 0-cresol dinuclear dimethylol compound represented by the formula ▼ (In the formula, R is a hydrogen atom or has a carbon number of 10 There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ that are characterized by reacting phenols represented by the following alkyl groups, n is 1, 2, or 3. indicates the above.) A method for producing a phenolic novolak represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22199886A JPH0730151B2 (en) | 1986-09-22 | 1986-09-22 | Method for producing phenolic novolac composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22199886A JPH0730151B2 (en) | 1986-09-22 | 1986-09-22 | Method for producing phenolic novolac composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6377915A true JPS6377915A (en) | 1988-04-08 |
| JPH0730151B2 JPH0730151B2 (en) | 1995-04-05 |
Family
ID=16775488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22199886A Expired - Fee Related JPH0730151B2 (en) | 1986-09-22 | 1986-09-22 | Method for producing phenolic novolac composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730151B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01135814A (en) * | 1987-11-20 | 1989-05-29 | Sumitomo Deyurezu Kk | Novolak-type phenolic resin for use in shell mold |
| JP2003286387A (en) * | 2002-03-28 | 2003-10-10 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and paper base phenolic resin laminate |
| JP2003286330A (en) * | 2002-03-28 | 2003-10-10 | Mitsui Chemicals Inc | Epoxy resin composition having excellent curability, its cured product and its use |
| JP2004018720A (en) * | 2002-06-18 | 2004-01-22 | Mitsui Chemicals Inc | Adhesive for semiconductor device |
-
1986
- 1986-09-22 JP JP22199886A patent/JPH0730151B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01135814A (en) * | 1987-11-20 | 1989-05-29 | Sumitomo Deyurezu Kk | Novolak-type phenolic resin for use in shell mold |
| JP2003286387A (en) * | 2002-03-28 | 2003-10-10 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and paper base phenolic resin laminate |
| JP2003286330A (en) * | 2002-03-28 | 2003-10-10 | Mitsui Chemicals Inc | Epoxy resin composition having excellent curability, its cured product and its use |
| JP2004018720A (en) * | 2002-06-18 | 2004-01-22 | Mitsui Chemicals Inc | Adhesive for semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0730151B2 (en) | 1995-04-05 |
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