JPS62267313A - Novolak type phenolic resin - Google Patents
Novolak type phenolic resinInfo
- Publication number
- JPS62267313A JPS62267313A JP11087886A JP11087886A JPS62267313A JP S62267313 A JPS62267313 A JP S62267313A JP 11087886 A JP11087886 A JP 11087886A JP 11087886 A JP11087886 A JP 11087886A JP S62267313 A JPS62267313 A JP S62267313A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- parts
- content
- novolac
- phenol
- 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 abstract description 39
- 239000005011 phenolic resin Substances 0.000 title abstract description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract description 4
- 229920001568 phenolic resin Polymers 0.000 title abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 150000002989 phenols Chemical class 0.000 claims abstract description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229930003836 cresol Natural products 0.000 claims abstract description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 3
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims 1
- 229920002866 paraformaldehyde Polymers 0.000 claims 1
- 238000006482 condensation reaction Methods 0.000 abstract description 10
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 abstract description 6
- -1 aldehyde compound Chemical class 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 7
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 7
- 229940100630 metacresol Drugs 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004312 hexamethylene tetramine Substances 0.000 description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003811 acetone extraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、遊離フェノール類を除いた樹脂成分の数平均
分子量が同程度である従来からのノボラック樹脂と比較
して、２核体成分の含有量は少ないが、遊離フェノール
類を少量含有するノボラック型フェノール樹脂に関する
ものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is characterized in that the number average molecular weight of the resin components excluding free phenols is about the same, compared to conventional novolac resins. This relates to a novolak type phenolic resin containing a small amount of free phenols, although the content is small.
元来ノボラック樹脂はフェノール類とアルデヒド類を酸
性触媒下に反応させて得られる樹脂物質であ）、遊離フ
ェノール類、２核体成分および３核体以上の成分などの
混合物から成シ立っている。近年遊離フェノール類を全
く含まないか、またはあ２シ含まないノボラック樹脂が
工業的に生産されてお９、フェノールノボラック型エゴ
キシ樹脂のベースレジン、オルソクレゾールノボラック
型エポキシ樹脂のペースレジン、エポキシ樹脂の硬化剤
用レジン、あるいは半導体高集積回路のフォトレジスト
用レジンなどに使用されている。Novolak resin is originally a resin material obtained by reacting phenols and aldehydes under an acidic catalyst), and is composed of a mixture of free phenols, dinuclear components, and trinuclear or more components. . In recent years, novolac resins containing no or no free phenols have been industrially produced. It is used as a hardener resin or a photoresist resin for semiconductor highly integrated circuits.
またその他の用途においても持性の改良、作業境の改善
、公害の防止などのために広く使用されている。そして
これらのノボラック樹脂については特開昭５８−８４８
１４、特開昭６０−５３５１６、特公昭６’ｌ −７２
１０などで公知となっている。しかし２核体成分の含有
量の少ないノボラック樹脂についてはまだ実在していな
い。この理由は実験室的製造法では限外沖過膜法や分別
沈澱法などが仮に考えられても工業的な生産が難しいた
めである。年月の経過と共に２核体成分を含有する従来
からのノボラック樹脂では、硬化後の耐熱性、耐水性、
耐湿性、耐蝕性、寸法安定性などの緒特性に満足できな
くなって来ておシ、これらの特性を左右するノボラック
樹脂の硬化性の改質が強く要求されている。It is also widely used for other purposes such as improving durability, improving work environment, and preventing pollution. Regarding these novolac resins, Japanese Patent Application Laid-Open No. 58-848
14, Japanese Patent Publication No. 60-53516, Special Publication No. 6'l-72
10 is publicly known. However, novolac resins with a low content of dinuclear components do not yet exist. The reason for this is that laboratory production methods such as ultrafiltration membrane method and fractional precipitation method are difficult to produce industrially even if such methods are considered. With the passage of time, conventional novolac resins containing dinuclear components have improved in heat resistance, water resistance, and
As the properties such as moisture resistance, corrosion resistance, and dimensional stability are becoming unsatisfactory, there is a strong demand for modification of the curability of novolak resins, which affect these properties.
本発明者らはノボラック樹脂の速硬化性と硬化物特性の
向上について鋭意研究を行なった結果、遊離フェノール
類の含有量が適量であって、かつ２核体成分の含有量の
少ないノボラック型フェノール樹脂が非常に有効である
ことの知見を得、さらにこの知見に基づいて種々研究を
重ねて本発明を完成するに至ったものであシ、その目的
とするところはノボラック樹脂の本質的な特性を損うこ
となく速硬化性であって、かつ硬化物特性にすぐれた低
分子量のノボラック型フェノール樹脂を提供することに
ある。発明者は別の発明において遊離フェノール類の含
有量が殆どなく、かつ２核体成分の含有量の少ないノボ
ラック樹脂がフェノールノボラック型エゼキシ樹脂やオ
ルソクレゾールノボランク型エゴキシ樹脂のベースレジ
ン、およびエピキシ樹脂の硬化剤用レジンなどの用途に
おいて非常に有効であるとの知見を得た。しかし硬化剤
のへキサメチレンテトラミンと共に焼成硬化させる場合
には遊離フェノール類を適量含有する方が速硬化性の特
長を発揮するとの知見を得て本発明を完成した。The present inventors conducted extensive research on improving the fast curing properties and properties of cured products of novolak resins, and found that novolak-type phenols with an appropriate amount of free phenols and a low content of dinuclear components. We obtained the knowledge that the resin is very effective, and based on this knowledge, we conducted various studies and completed the present invention. It is an object of the present invention to provide a low molecular weight novolac type phenolic resin that is fast-curing without impairing the properties of the cured product and has excellent properties of the cured product. In another invention, the inventor discovered that a novolac resin with almost no content of free phenols and a low content of dinuclear components is used as a base resin for phenol novolac type ezoxy resin, orthocresol novolanc type ezoxy resin, and epixy resin. It has been found that this method is very effective in applications such as hardening agent resins. However, the present invention was completed based on the knowledge that when baking and curing together with the curing agent hexamethylenetetramine, containing an appropriate amount of free phenols exhibits the advantage of faster curing.
本発明によるノボラック型フェノール樹脂の利用分野に
は、低分子量のノボラック型樹脂からなる成形材料、結
合剤、接着剤などがちる。本発明のノボラック型フェノ
ール樹脂はへキサメチレンテトラミンを硬化剤として使
用する場合、硬化時は速硬化性でらシ、かつ硬化後は３
次元架橋が発達して耐熱性、耐水性、耐湿性、耐蝕性、
寸法安定性などの緒特性がすぐれた硬化物となる。Fields of use of the novolac type phenolic resin according to the present invention include molding materials, binders, adhesives, etc. made of low molecular weight novolac type resins. When hexamethylenetetramine is used as a curing agent, the novolac type phenolic resin of the present invention has a fast curing property and a hardening rate of 30% after curing.
Due to the development of dimensional cross-linking, it has heat resistance, water resistance, moisture resistance, corrosion resistance,
The resulting cured product has excellent properties such as dimensional stability.
本発明はフェノールまたは／およびり１／ゾールからな
るフェノール類とアルデヒド類を触媒の存在下に反応さ
せて得られるノボラック型フェノール樹脂において、遊
離フェノール類を除いた樹脂成分の数平均分子量（ｘ）
が３００〜５００．、遊離フェノール類の含有率が１．
０〜５．０ｎｆｆｉノ’−セント、および２核体成分（
ｙ）の含有率がＯ≦ｙ≦−０，０４ｘ＋２６重量ノＺ−
セントでちることを特徴とするノボラック型フェノール
樹脂である。こ＼で遊離フェノール類の含有率は１．０
〜５，０重量ツクーセントでらるが、好ましくは１．０
〜３．０重址ノ２−セントである。２核体成分の含有率
については、従来からのノボラック樹脂では遊離フェノ
ール類を除いた樹脂成分の数平均分子量が、例えば下限
の３００の場合は２３〜４５ｘ童ノＺ−セント、中間の
４００の場合は１５〜２５重量ノζ−セント、上限の５
００の場合は９〜１６重量・ぐ−でントであったのに対
して、本発明のノボラック型フェノール樹脂では遊離フ
ェノール類を除いた樹脂成分の数平均分子ｆ（ｘ）が、
例えば３００の場合は１４重ｔｆｔ ’ζ−セント以下
であυ、好ましくは７．０重量・Ｚ−セント以下である
。さらに４００の場合は１０重量パーセント以下でらシ
、好ましくは５．０重益ノぐ一セント以下である。５０
０の場合は６，０重量・ε−セント以下であり、好まし
くは３．０電波・Ｚ−セント以下である。この範囲全数
式で表わすと、遊離フェノール類を除いた樹脂成分の数
平均分子’ｔ （ｘ）が３００〜５００の場合の２核体
成分（ｙ）の含有率は、０≦ｙ≦−００４ｘ ＋ ２５
重せノぐ−セントであ）、好ましくはＯ≦ｙ≦−〇、０
２ｘ＋１３重量ノξ−セントである。The present invention relates to a novolak type phenol resin obtained by reacting phenols consisting of phenol and/or 1/sol with aldehydes in the presence of a catalyst, and the number average molecular weight (x) of the resin component excluding free phenols.
is 300~500. , the content of free phenols is 1.
0 to 5.0nffi no'-cent, and dinuclear component (
The content of y) is O≦y≦−0,04x+26 weight no Z−
It is a novolac-type phenolic resin that is characterized by its ability to drop in cents. In this case, the content of free phenols is 1.0.
~5.0 weight cents, preferably 1.0
~3.0 cents per cent. Regarding the content of the binuclear component, in conventional novolac resins, the number average molecular weight of the resin component excluding free phenols is, for example, 23 to 45 x Z-cents when the lower limit is 300, and If 15 to 25 cents by weight, the upper limit is 5
In the case of No. 00, the weight was 9 to 16 weight grams, whereas in the novolak type phenolic resin of the present invention, the number average molecule f(x) of the resin component excluding free phenols was
For example, in the case of 300, it is less than 14 tft' ζ-cents, preferably less than 7.0 wt.Z-cents. Further, in the case of 400, it is less than 10 weight percent, preferably less than 5.0 cents by weight. 50
If it is 0, it is less than 6.0 weight/ε-cents, preferably less than 3.0 radio waves/Z-cents. Expressing this range in full mathematical formula, when the number average molecule 't (x) of the resin component excluding free phenols is 300 to 500, the content of the binuclear component (y) is 0≦y≦-004x +25
overlapping cents), preferably O≦y≦−〇, 0
2x+13 weight no.xi-cents.
２核体成分の含有率が（−０，０４ｘ＋２６ ）１址パ
ーセントを上回る場合、遊離フェノール類の含有率が５
．０重量・ξ−七ントを上回ると、従来からのノボラッ
ク樹脂に比べて硬化時のへキサミンとの架橋性が目立っ
て犬きくならないため、硬化物特性に顕著な特長が現わ
れにくいし、でた遊離フェノール類の含有率が１．０重
量・ζ−七ンかを下回ると、同じ〈従来からのノボラッ
ク樹脂に比べて硬モ場合でも、遊離フェノール類の含有
率が５，０重１１．６−セントを上回ると、架橋性が充
分に大きくならないので硬化物特性に特長が発現しにく
いし、また遊離フェノール類の含有率が１．０重量・２
−セントを下回ると硬化時間が長くなシすぎるので速硬
化性を必要とする用途には適さない。When the content of dinuclear components exceeds (-0,04x+26) 1%, the content of free phenols exceeds 5%.
．． When the weight exceeds 0 weight/ξ-7, the cross-linking properties with hexamine during curing are not noticeable and poor compared to conventional novolac resins, so it is difficult for the cured product to exhibit remarkable characteristics. If the content of free phenols is less than 1.0 wt. - If it exceeds 1.0% by weight, the crosslinkability will not be sufficiently large, making it difficult to develop characteristics in the cured product, and the content of free phenols will be 1.0% by weight and 2% by weight.
- If the curing time is below cent, the curing time will be too long, making it unsuitable for applications requiring rapid curing.
こ＼で遊離フェノール類を除いた樹脂成分の数平均分子
量および２棟体成分の含有率は、東洋曹達工業■製の高
速液体クロマトグラフ型式ＨＬＣ−８０２Ａに分析カラ
ム ＴＳＫ −ＧＥＬＧ １０００Ｈ８ｘ １本、ＴＳ
Ｋ −ＧＥＬＧ ２０００Ｈｓ ｘ ２本、ＴＳＫ −
ＧＥＬＧ ３０００ Ｈａ×１本の組合せ、また遊離フ
ェノール類の含有率はガスクロマトグラフによる測定値
である。The number average molecular weight of the resin component excluding free phenols and the content of the two-block component were determined using a high-performance liquid chromatograph model HLC-802A manufactured by Toyo Soda Kogyo ■ using an analytical column TSK-GELG 1000H8 x 1, TS
K-GELG 2000Hs x 2, TSK-
The combination of GELG 3000 Ha x 1 bottle and the content of free phenols are values measured by gas chromatography.
本発明のノボラック型フェノール樹脂の製造例を示すと
、前段の初期縮合反応と後段の脱水縮合反応からなる。An example of producing the novolac type phenol resin of the present invention consists of an initial condensation reaction in the first stage and a dehydration condensation reaction in the second stage.
前段では攪拌機、熱交換器、温度計の付いた反応装置で
フェノールまたは／およびクレゾールからなるフェノー
ル類とアルデヒド類を触媒の存在下に、５０〜１５０℃
の温度で１５分〜５時間程度反応させてノボラック型フ
ェノール樹脂の初期縮合反応物を得る。つづいて、後段
では第１図に示すような構造の羽根（５）を管内に有す
る配管（４）を第２図に示すように接続し、供給ピンプ
（２）を用いて配管（４）内に初期縮合反応液を定量圧
送供給する。配管内温度を１２０〜２５０℃に保持しな
がら同時に供給口（３）から配管（４）内に不活性気体
または／および水蒸気を供給混合して、混合物を反応装
置（１）へ戻すことからなる循環処理を行なって、初期
縮合反応液から遊離フェノール類や２棟体成分を除去す
る。この循環処理を所望する特性が得られるまで継続し
、その後さらに減圧下で脱水縮合反応を行なってノボラ
ック型フェノール樹脂を得る。In the first stage, phenols consisting of phenol or/and cresol and aldehydes are heated at 50 to 150°C in the presence of a catalyst in a reaction apparatus equipped with a stirrer, heat exchanger, and thermometer.
The reaction is carried out at a temperature of about 15 minutes to 5 hours to obtain an initial condensation reaction product of a novolak type phenol resin. Next, in the latter stage, a pipe (4) having a structure shown in Fig. 1 with a vane (5) inside the pipe is connected as shown in Fig. 2, and a supply pimp (2) is used to connect the pipe (4) inside the pipe (4). A fixed amount of the initial condensation reaction solution is supplied under pressure. It consists of simultaneously supplying and mixing an inert gas or/and water vapor into the pipe (4) from the supply port (3) while maintaining the temperature inside the pipe at 120 to 250°C, and returning the mixture to the reactor (1). A circulation process is performed to remove free phenols and two-body components from the initial condensation reaction liquid. This circulation treatment is continued until desired characteristics are obtained, and then a dehydration condensation reaction is further carried out under reduced pressure to obtain a novolac type phenol resin.
本発明のノボラック型フェノール樹脂を得るために使用
するフェノール類としてはフェノールまたは／およびク
レゾールであるが、クレゾールはオルソクレゾール、メ
タクレゾール、ズラクレゾールから選ばれた１種または
２種以上である。フェノールまたはクレゾール以外のフ
ェノール類を変性剤として使用しても差しつかえないが
、その変性率はフェノール類全体の３０重量／ζ−セン
ト以下であることが好ましい。The phenol used to obtain the novolac type phenolic resin of the present invention is phenol and/or cresol, and the cresol is one or more selected from orthocresol, meta-cresol, and zuracresol. Phenols other than phenol or cresol may be used as modifiers, but the modification rate is preferably 30 weight/ζ-cent or less of the total phenols.
つぎにアルデヒド類としてはホルムアルデヒド、ノぐラ
ホルムアルデヒド、ピリオキシメチレン、トリオキサン
、アセトアルデヒド、ベンズアルデヒドなどから選ばれ
た１種または２種以上であるが、好ましくはホルムアル
デヒドとノｚラホルムアルデヒドである。また、フェノ
ール″！たは、／およびクレゾールからなるフェノール
類に対するアルデヒド類の配合モル比は特に限定しない
が、０．４〜１．０で行なうのが一般的である。Next, the aldehyde is one or more selected from formaldehyde, formaldehyde, pyrioxymethylene, trioxane, acetaldehyde, benzaldehyde, etc., and formaldehyde and formaldehyde are preferred. The molar ratio of aldehydes to phenols consisting of phenol and/or cresol is not particularly limited, but is generally 0.4 to 1.0.
本発明においてフェノール類とアルデヒド類を反応させ
るために使用する触媒は、塩酸、硫酸、スルファミン醜
などの無機酸、シゅう酸、マレイン酸、ギ酸、安息香酸
、サリチル酔、・ξラドルエンスルホン酸などの有機酸
、鉛、カルシウム、錫、亜鉛などの２ ｆｉｊ金属から
なるカルボ／・酸塩やす７テン醗などの有機酸金属塩等
から選ばれた１種または２種以上である。In the present invention, the catalysts used for reacting phenols and aldehydes include hydrochloric acid, sulfuric acid, inorganic acids such as sulfamine, oxalic acid, maleic acid, formic acid, benzoic acid, salicylic acid, and ξradluene sulfone. One or more types selected from organic acids such as acids, carboxylic acid salts made of metals such as lead, calcium, tin, and zinc, organic acid metal salts such as 7-tenthyl alcohol, and the like.
本発明のノボラック型フェノール樹脂を得るために使用
する不活性気体は窒素、炭酸ガス、ヘリウム、アルゴン
などから選ばれた１棟または２種以上であシ、また水蒸
気は公知のものである。The inert gas used to obtain the novolac type phenolic resin of the present invention may be one or more selected from nitrogen, carbon dioxide, helium, argon, etc., and water vapor is a known gas.
本発明によるノボラック型フェノール樹脂は遊離フェノ
ール類を少黛含有しているため速硬化性でｈＤ、従来か
らのノボラック樹脂に比べて２棟体成分の含有率が少な
いだめ架橋性に富み、かつ硬化性にすぐれている。また
、硬化性が良好であるので硬化後の樹脂は耐熱性、耐水
性、耐湿性、耐蝕性、寸法安定性などの緒特性が向上す
るため、本発明のノボラック型フェノール樹脂：は低分
子量のノボラック型樹脂からなる成形材料、結合剤、接
着剤などの多での分野で需要が増すものと期待される。The novolac-type phenolic resin according to the present invention has a low content of free phenols, so it has fast curing properties and hardness.Compared to conventional novolak resins, the content of the two-block component is low, so it has high crosslinking properties and cures. Excellent sex. In addition, due to its good curability, the resin after curing has improved properties such as heat resistance, water resistance, moisture resistance, corrosion resistance, and dimensional stability. Demand is expected to increase in many fields such as molding materials, binders, and adhesives made of novolac-type resins.
以下本発明を実施例によって詳細ｉて説明するが、本発
明は実施例によって限定されるものではない。な２、こ
の実施例および比較例に記載されている「部」および「
チ」は「重量部」および「重量ノ２−セント」を示す。EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited by the Examples. 2. The "parts" and "parts" described in these Examples and Comparative Examples
"CH" indicates "parts by weight" and "2 cents by weight."
実施例１
攪拌機、熱交換器、温度計の付いた反応装置にフェノー
ル１０００部、３７％ホルマリン３４５部、しゅう酸２
０部を仕込み、常圧で９０分間還流反応を行なった。引
続いて常圧で液温か１３０℃となるまで脱水して初期縮
合反応を終了した。その後固定式羽根を有する配管内に
初期縮合反応液０．１ｋｆ／分を供給し、配管内温度を
１７０℃に保持しながら同時に供給口から配管内に水蒸
気０．Ｏ５Ｎｍ３／分を供給混合して、８０Ｔｏｒｒの
減圧下で５時間循環処理を行なった。さらに温度１５０
℃、６０Ｔｏｒｒの減圧下で１時間脱水綿合反応を行な
った後、フェノール１１部を溶融混合してノボラック型
フェノール樹脂４４５部を得た。Example 1 1000 parts of phenol, 345 parts of 37% formalin, and 2 parts of oxalic acid were placed in a reaction apparatus equipped with a stirrer, heat exchanger, and thermometer.
A reflux reaction was carried out at normal pressure for 90 minutes. Subsequently, the mixture was dehydrated at normal pressure until the liquid temperature reached 130° C. to complete the initial condensation reaction. Thereafter, the initial condensation reaction liquid was supplied at 0.1 kf/min into the pipe having fixed vanes, and while the temperature inside the pipe was maintained at 170°C, at the same time, 0.1 kf/min of water vapor was introduced into the pipe from the supply port. O5Nm3/min was supplied and mixed, and circulation treatment was performed for 5 hours under a reduced pressure of 80 Torr. Further temperature 150
C. and under reduced pressure of 60 Torr for 1 hour, and then 11 parts of phenol was melt-mixed to obtain 445 parts of novolac type phenolic resin.
実施例２
実施例１と同型の反応装置にメタクレゾール６００部、
ガラクレゾール４００部、３７係ホルマリン３００部、
１５チ塩酸６部を仕込み、常圧で１２０分間還流反応を
行なった。以下配管内温度を２００℃に保持すること以
外は実施例１の場合と同様に処理した後、メタクレゾー
ル１６部を溶融混合してノボラック型フェノール樹脂３
９５部を得た。Example 2 600 parts of metacresol was added to the same type of reactor as in Example 1.
Galacresol 400 parts, Section 37 formalin 300 parts,
6 parts of 15-thihydrochloric acid was charged, and a reflux reaction was carried out at normal pressure for 120 minutes. After processing in the same manner as in Example 1 except that the temperature inside the pipe was maintained at 200°C, 16 parts of metacresol was melt-mixed and 3 parts of novolac type phenol resin were added.
Got 95 copies.
比較例１
攪拌機、熱交換器、温度計の付いた反応装置にフェノー
ル１０００部、３７条ホルマリン４７５部、しゅう酸１
０部を仕込み、常圧で９０分間還流反応を行なった。引
続いて常圧で液温か１３０℃になる着で脱水して初期縮
合反応を終了した。その後６０Ｔｏｒｒの減圧下で徐々
に昇温しながら最高温度２２０℃で３時間脱水綿合反応
を行なってノボラック樹脂７９０部を得た。Comparative Example 1 1000 parts of phenol, 475 parts of 37-article formalin, and 1 part of oxalic acid were placed in a reaction apparatus equipped with a stirrer, heat exchanger, and thermometer.
A reflux reaction was carried out at normal pressure for 90 minutes. Subsequently, the initial condensation reaction was completed by dehydration at normal pressure until the liquid temperature reached 130°C. Thereafter, a dehydrated cotton mixture reaction was carried out at a maximum temperature of 220° C. for 3 hours while gradually increasing the temperature under a reduced pressure of 60 Torr to obtain 790 parts of a novolak resin.
比較例２
比較例１で得た樹脂１００部に対してフェノール２．５
部を加熱溶融混合してノボラック樹脂１０２．５部を得
た。Comparative Example 2 2.5 parts of phenol per 100 parts of the resin obtained in Comparative Example 1
102.5 parts of a novolak resin was obtained by heating and melt-mixing 102.5 parts of a novolac resin.
比較例３
比較例１で得た樹脂１００部に対してフェノール７．０
部を加熱溶融混合してノボラック樹脂１０７部を得た。Comparative Example 3 7.0 parts of phenol per 100 parts of the resin obtained in Comparative Example 1
107 parts of novolac resin were obtained by heat-melting and mixing 107 parts of novolac resin.
を行わないこと以外は実施例１と同様の方法で処理して
ノボラック樹脂４３０部を得た。430 parts of novolac resin was obtained by the same process as in Example 1 except that .
比較例５
比較例４で得た樹脂１００部に対してフェノール７．０
部を加熱溶融混合してノボラック樹脂１０７部を得た。Comparative Example 5 7.0 parts of phenol per 100 parts of the resin obtained in Comparative Example 4
107 parts of novolac resin were obtained by heat-melting and mixing 107 parts of novolac resin.
比較例６
比較列１と同型の装置にメタクレゾール６００部、スラ
クレゾール４００ｇ１Ｓ、３７％ホルマリン３７５都、
１５チ塩酸５部を仕込み、常圧で１２０分間還流反応を
行なった。以下比較例１の場合と同様に処理してノボラ
ック樹脂５８０部を得だ。Comparative Example 6 In a device of the same type as Comparative Row 1, 600 parts of metacresol, 400 g of sulacresol, 375 parts of 37% formalin,
5 parts of 15-thihydrochloric acid was charged, and a reflux reaction was carried out at normal pressure for 120 minutes. The following treatment was carried out in the same manner as in Comparative Example 1 to obtain 580 parts of novolak resin.
比較例７
比較例６で得た樹脂１００部に対してメタクレゾール４
．０部を加熱溶融混合してノボラック樹脂１０４部を得
た。Comparative Example 7 Metacresol 4 was added to 100 parts of the resin obtained in Comparative Example 6.
．． 0 parts were heat-melted and mixed to obtain 104 parts of novolak resin.
比較例８
比較例６で得た樹脂１００部に対してメタクレゾール７
．０部を加熱溶融混合してノボラック樹脂１０７部を得
た。Comparative Example 8 Metacresol 7 was added to 100 parts of the resin obtained in Comparative Example 6.
．． 0 parts were heated and melted and mixed to obtain 107 parts of novolac resin.
実施例２（て １６部の溶融混合を行わ
ないこと以外は実施例２と同様の方法で処理してノボラ
ック樹脂３７５部を得た。Example 2 (375 parts of novolac resin) was obtained in the same manner as in Example 2 except that 16 parts of the resin was not melt-mixed.
比較例１０
比較例９で得た樹脂１００部に対してメタクレゾール７
．０部を加熱溶融混合してノボラック樹脂１０７部を得
た。Comparative Example 10 Metacresol 7 was added to 100 parts of the resin obtained in Comparative Example 9.
．． 0 parts were heated and melted and mixed to obtain 107 parts of novolak resin.
実施例１、実施例２で得たノボラック型フェノール樹脂
、および比較例１、比較例６で得たノボラック樹脂の高
速液体クロマトグラフによる分子率を第１表または第２
表に示す。さらに実施例１〜２、比較例１〜１０で得た
樹脂の遊離フェノール類の含有率についても第１表また
は第２表に掲げる。The molecular rates of the novolac type phenolic resins obtained in Example 1 and Example 2, and the novolac resins obtained in Comparative Example 1 and Comparative Example 6, as measured by high performance liquid chromatography, are shown in Table 1 or 2.
Shown in the table. Further, the contents of free phenols in the resins obtained in Examples 1 to 2 and Comparative Examples 1 to 10 are also listed in Table 1 or Table 2.
第 １ 表
第２表
（）内は実施例２τ、たは比較例６からのスライド値実
施例１、実施例２で得たノボラック型フェノール樹脂は
、数平均分子量が３６１と４４８であってどちらも３０
０〜５００の範囲内にちシ、また遊離フェノール類の含
有率も２．５チと３．９％であって、どちらも１．０〜
５．０俤の範囲内にある。さらに２核体成分の含有率に
ついても０７％と３、Ｏチであって、数平均分子量がそ
れぞれ３６１と４４８の場合における本発明の２核体成
分の含有率０〜１１．６％とＯ〜７．３チの範囲内に入
っている。Table 1 The values in Table 2 () are slide values from Example 2τ or Comparative Example 6. Also 30
The content of free phenols is 2.5% and 3.9%, both of which are 1.0% to 500%.
It is within the range of 5.0 yen. Furthermore, the content of the dinuclear component of the present invention is 0 to 11.6% when the number average molecular weight is 361 and 448, respectively. It is within the range of ~7.3ch.
つぎに実施例１〜２で得たノボラック型フェノ〜ル樹脂
、および比較例１〜１０で得たノボラック樹脂について
、熱板ゲル化時間とアセトン抽出率を測定した結果を第
３表と第４表にこ示す。Next, Tables 3 and 4 show the results of measuring the hot plate gelation time and acetone extraction rate for the novolac type phenol resins obtained in Examples 1 to 2 and the novolac resins obtained in Comparative Examples 1 to 10. This is shown in the table.
第 ３ 表
第 ４ 表
〈熱板ゲル化時間の測定方法〉
１） ＪＩＳ Ｋ ６９０９
２）へキサミン量： １５ ｐｈｒ
３）熱板表面温度：１５０℃
〈アセトン抽出率の測定方法〉
１）装置：ソソクスレー抽出器
２）試料の作製：
ヘキサミン１１５ｐｈｒと共に微粉砕して混合する。タ
ブレット状に成形して硬化条件１５０℃／ＩＨｒで硬化
させる。硬化樹脂を６０メツシユ篩の通過分を試料とす
る。Table 3 Table 4 <Method of measuring hot plate gelation time> 1) JIS K 6909 2) Amount of hexamine: 15 phr 3) Hot plate surface temperature: 150°C <Method of measuring acetone extraction rate> 1) Apparatus: Soxhlet extractor 2) Preparation of sample: Pulverize and mix with 115 phr of hexamine. It is molded into a tablet shape and cured under curing conditions of 150°C/IHr. The amount of cured resin that passes through a 60-mesh sieve is used as a sample.
３）抽出時間： ６ Ｈｒ
同原料の樹脂同士を比較すると実施例１の樹脂しｎ−ｔ
ｋ／１１１１４ ｅ ｂｒ ＬＬ ＋＃ イー＋ｋ
上ｃＬｒ −ｋｋ ｆｆａｌり小太１↓１薔９１オ比
較例６〜１０１て比べて熱板ゲル化時間が速く、かつア
セトン抽出率が小さいという両特長を兼ね備えている。3) Extraction time: 6 Hr When comparing resins made from the same raw materials, the resin of Example 1 was n-t.
k/11114 e br LL +# e+k
Upper cLr -kk ffal 1 ↓ 1 薤91 O Compared to Comparative Examples 6 to 101, it has both the advantages of a faster hot plate gelation time and a lower acetone extraction rate.
このことは実施９」１〜２のノボラック型フェノール樹
脂は速硬化性であり、かつ架橋性に富んでいて硬化性に
すぐｎていることを表わしている。This indicates that the novolac type phenolic resins of Examples 1 and 2 of Example 9 are fast-curing, have high crosslinking properties, and are readily curable.
第１図はス・Ｓイラル式固定式羽根を有する配管の部分
断面正面図である。
第２図は固定式羽根を有する配管を用いた場合の設備概
要図である。
第３図、第４図はそれぞれ実施例１と比咬例１、実施例
２と比較例６で得られたノボラック型フェノール樹脂の
高速液体クロマトグラフによる分子量分布のチャートで
ある。FIG. 1 is a partially sectional front view of a pipe having spiral fixed vanes. FIG. 2 is a schematic diagram of the equipment when piping with fixed vanes is used. 3 and 4 are charts of the molecular weight distributions of the novolac type phenolic resins obtained in Example 1, Ratio Example 1, Example 2, and Comparative Example 6, respectively, as measured by high performance liquid chromatography.
Claims (1)
ノール類とアルデヒド類を触媒の存在下に反応させて得
られるノボラック型フェノール樹脂において、遊離フェ
ノール類を除いた樹脂成分の数平均分子量（ｘ）が３０
０〜５００、遊離フェノール類の含有率が１．０〜５．
０重量パーセント、および２核体成分（ｙ）の含有率が
０≦ｙ≦−０．０４ｘ＋２６重量パーセントであること
を特徴とするノボラック型フェノール樹脂。 ２）アルデヒド類がホルムアルデヒドまたは／およびパ
ラホルムアルデヒドであることを特徴とする特許請求の
範囲第１項記載のノボラック型フェノール樹脂。[Claims] 1) In a novolac type phenolic resin obtained by reacting phenols consisting of phenol or/and cresol with aldehydes in the presence of a catalyst, the number average molecular weight of the resin component excluding free phenols ( x) is 30
0 to 500, and the content of free phenols is 1.0 to 5.
0 weight percent, and the content of the binuclear component (y) is 0≦y≦−0.04x+26 weight percent. 2) The novolac type phenolic resin according to claim 1, wherein the aldehyde is formaldehyde and/or paraformaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11087886A JPS62267313A (en) | 1986-05-16 | 1986-05-16 | Novolak type phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11087886A JPS62267313A (en) | 1986-05-16 | 1986-05-16 | Novolak type phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62267313A true JPS62267313A (en) | 1987-11-20 |
Family
ID=14546985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11087886A Pending JPS62267313A (en) | 1986-05-16 | 1986-05-16 | Novolak type phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62267313A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0270721A (en) * | 1988-09-07 | 1990-03-09 | Sumitomo Durez Co Ltd | Epoxy resin compositon for sealing material |
| JP2019094397A (en) * | 2017-11-21 | 2019-06-20 | 住友ベークライト株式会社 | Phenol resin composition and refractory |
-
1986
- 1986-05-16 JP JP11087886A patent/JPS62267313A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0270721A (en) * | 1988-09-07 | 1990-03-09 | Sumitomo Durez Co Ltd | Epoxy resin compositon for sealing material |
| JP2019094397A (en) * | 2017-11-21 | 2019-06-20 | 住友ベークライト株式会社 | Phenol resin composition and refractory |
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