JPS6368624A - Production of phenolic resin composition - Google Patents
Production of phenolic resin compositionInfo
- Publication number
- JPS6368624A JPS6368624A JP21184686A JP21184686A JPS6368624A JP S6368624 A JPS6368624 A JP S6368624A JP 21184686 A JP21184686 A JP 21184686A JP 21184686 A JP21184686 A JP 21184686A JP S6368624 A JPS6368624 A JP S6368624A
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- acid
- resin composition
- anhydride
- resin
- 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
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 10
- 150000004820 halides Chemical class 0.000 claims abstract description 9
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 6
- 239000008158 vegetable oil Substances 0.000 claims abstract description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 11
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical group CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012346 acetyl chloride Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002383 tung oil Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- 229920003987 resole Polymers 0.000 abstract description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 abstract description 2
- OMFSJRHPFYVJSP-UHFFFAOYSA-N 2,3,4,5-tetramethylfuran Chemical compound CC=1OC(C)=C(C)C=1C OMFSJRHPFYVJSP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 238000005917 acylation reaction Methods 0.000 description 9
- 230000010933 acylation Effects 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- -1 trimethylamine Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical class BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- SHDZTIZBSYDZSH-UHFFFAOYSA-N 2-methylprop-2-enoyl bromide Chemical compound CC(=C)C(Br)=O SHDZTIZBSYDZSH-UHFFFAOYSA-N 0.000 description 1
- ICNCZFQYZKPYMS-UHFFFAOYSA-N 2-methylpropanoyl bromide Chemical compound CC(C)C(Br)=O ICNCZFQYZKPYMS-UHFFFAOYSA-N 0.000 description 1
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- VWQXLMJSFGLQIT-UHFFFAOYSA-N prop-2-enoyl bromide Chemical compound BrC(=O)C=C VWQXLMJSFGLQIT-UHFFFAOYSA-N 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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〕
本発明はフェノール樹脂組成物の製造法に関し、さらに
詳しくは、優れた可塑性を有するフェノール樹脂組成物
の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a phenolic resin composition, and more particularly, to a method for producing a phenolic resin composition having excellent plasticity.
従来、民生用の電気、電子部品の絶縁材料等に使用され
る積層板、銅張積層板等には、フェノール類とホルムア
ルデヒド類とをアルカリ性触媒の存在下で反応させて得
られるレゾール型フェノール樹脂が主に用いられている
。しかし、未変性のレゾール型フェノール樹脂は、硬化
後においては非常に硬く脆いという性質があった。そこ
で、硬く脆いという性質を改良するために、これまでは
種々の植物油や可塑剤を用いて、樹脂を可塑化する方法
が行われてきた。Conventionally, resol-type phenolic resins, which are obtained by reacting phenols and formaldehydes in the presence of an alkaline catalyst, have been used for laminates, copper-clad laminates, etc. used as insulating materials for consumer electrical and electronic components. is mainly used. However, unmodified resol type phenolic resin has the property of being extremely hard and brittle after curing. Therefore, in order to improve the hard and brittle properties, methods have been used to plasticize resins using various vegetable oils and plasticizers.
（発明が解決しようとする問題点〕
しかしながら、植物油等による変性や、可塑剤による可
塑化という方法だけでは満足のいく効果を得ることは困
難であった。この原因は、フェノール樹脂中のフェノー
ル性水酸基による水素結合のため、分子鎖の運動が抑制
され、樹脂の可塑化に対する効果が小さかったためであ
る。(Problems to be solved by the invention) However, it has been difficult to obtain a satisfactory effect only by methods such as modification with vegetable oil etc. or plasticization with a plasticizer.The reason for this is that the phenolic This is because the movement of molecular chains was suppressed due to hydrogen bonding by hydroxyl groups, and the effect on plasticization of the resin was small.
本発明は、これら従来技術のもつ問題点を解決し、硬化
後に優れた可撓性を有するフェノール樹脂組成物を製造
する方法を提供しようとするものである。The present invention aims to solve the problems of these conventional techniques and provide a method for producing a phenolic resin composition that has excellent flexibility after curing.
本発明者らは、上記問題点を解決すべく鋭意検討した結
果、フェノール樹脂中のフェノール性水酸基による水素
結合を取り除くことにより、硬化樹脂の弾性率が低下し
、伸びが大きくなることを見い出し、本発明を完成する
に至った。As a result of intensive studies to solve the above problems, the present inventors discovered that by removing the hydrogen bonds due to the phenolic hydroxyl groups in the phenolic resin, the elastic modulus of the cured resin decreases and the elongation increases. The present invention has now been completed.
すなわち、本発明のフェノール樹脂組成物の製造法は、
レゾール型フェノール樹脂のフェノール性水酸基の５％
〜９５％を一般式
％式％
（式中、Ｒはアルキル基またはアリール基を表す）
で表される酸無水物または一般式
（式中、Ｒはアルキル基またはアリール基を表し、Ｘは
ＣＩまたはＢｒを表す）
で表される酸ハロゲン化物でアシル化することを特徴と
する。That is, the method for producing the phenolic resin composition of the present invention is as follows:
5% of phenolic hydroxyl groups in resol type phenolic resin
~95% of the acid anhydride or the general formula (wherein R represents an alkyl group or an aryl group, and X represents CI or Br) is characterized by being acylated with an acid halide represented by:
本発明で用いられるレゾール型フェノール樹脂は、フェ
ノールやクレゾール、ブチルフェノール、ノニルフェノ
ール等のアルキルフェノール等のフェノール類の中から
選ばれた少なくとも一種と、ホルムアルデヒド、ホルマ
リン、アセトアルデヒド等のアルデヒド類およびバラホ
ルムアルデヒド、ヘキサメチレンテトラミン等のアルデ
ヒド源の中から選ばれた少なくとも一種とを、水酸化カ
リウム、水酸化すトリウム、アンモニア、トリメチルア
ミン等の有機アミン等のアルカリ性触媒の存在下、６０
℃〜１００℃で３０分〜１８０分間反応させることによ
り得ることができる。The resol type phenolic resin used in the present invention contains at least one phenol selected from phenols such as phenol and alkylphenols such as cresol, butylphenol, and nonylphenol, and aldehydes such as formaldehyde, formalin, acetaldehyde, paraformaldehyde, and hexamethylene. At least one selected from aldehyde sources such as tetramine, in the presence of an alkaline catalyst such as potassium hydroxide, thorium hydroxide, ammonia, and an organic amine such as trimethylamine, for 60 min.
It can be obtained by reacting at a temperature of 100°C to 100°C for 30 minutes to 180 minutes.
またこの時に、乾性植物油で任意に変性する方がさらに
望ましい。変性に用いる乾性植物油としては桐油、アマ
ニ油、オイシチカ油、ヒマシ油、脱水ヒマシ油等が挙げ
られるが、フェノール類との反応性との観点から、桐油
を用いることが好ましい。At this time, it is even more desirable to optionally modify it with a drying vegetable oil. Examples of the drying vegetable oil used for modification include tung oil, linseed oil, oishitica oil, castor oil, and dehydrated castor oil, but from the viewpoint of reactivity with phenols, it is preferable to use tung oil.
このようにして製造したレゾール型フェノール樹脂を、
次に塩基性触媒または酸受容剤の存在化にアシル化試薬
と反応させてアシル化する。The resol type phenolic resin produced in this way,
Next, acylation is carried out by reacting with an acylating reagent in the presence of a basic catalyst or acid acceptor.
本発明方法においては、アシル化試薬として一般式
％式％
（式中、Ｒは上記と同じ意味を有する）で表される酸無
水物または一般式
（式中、ＲおよびＸは上記と同じ意味を有する）で表さ
れる酸ハロゲン化物を用いる。In the method of the present invention, an acid anhydride represented by the general formula % (wherein R has the same meaning as above) or a general formula (wherein R and X have the same meaning as above) is used as an acylating reagent. An acid halide having the following formula is used.
本発明方法に用いられる酸無水物としては、例えば、無
水酢酸、無水プロピオン酸、無水酪酸、無水イソ酪酸、
無水カプロン酸、無水アクリル酸、無水メタクリル酸等
の脂肪族カルボン酸無水物、および無水安息香酸、核置
換無水安息香酸等の芳香族カルボン酸無水物を挙げるこ
とができる。Examples of the acid anhydride used in the method of the present invention include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride,
Examples include aliphatic carboxylic anhydrides such as caproic anhydride, acrylic anhydride, and methacrylic anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride and nuclear-substituted benzoic anhydride.
本発明方法に用いられる酸ハロゲン化物としては、例え
ば、塩化アセチル、塩化プロピオニル、塩化ｎ−ブチリ
ル、塩化イソブチリル、塩化カブリリル、塩化アクリリ
ル、塩化メタクリロイル等の脂肪族酸塩化物、臭化アセ
チル、臭化プロピオニル、臭化ｎ−ブチリル、臭化イソ
ブチリル、臭化カブリリル、臭化アクリリル、臭化メタ
クリロイル等の脂肪族酸臭化物、塩化ベンゾイル、核置
換塩化ベンゾイル等の芳香族酸塩化物、臭化ベンゾイル
、核置換臭化ベンゾイル等の芳香族酸臭化物等を挙げる
ことができる。Examples of acid halides used in the method of the present invention include aliphatic acid chlorides such as acetyl chloride, propionyl chloride, n-butyryl chloride, isobutyryl chloride, cabrylyl chloride, acrylyl chloride, and methacryloyl chloride; acetyl bromide; Aliphatic acid bromides such as propionyl, n-butyryl bromide, isobutyryl bromide, cabrylyl bromide, acrylyl bromide, and methacryloyl bromide; aromatic acid chlorides such as benzoyl chloride and nuclear-substituted benzoyl chloride; benzoyl bromide; Examples include aromatic acid bromides such as substituted benzoyl bromide.
しかしながら、レゾール型フェノール樹脂のフェノール
性水酸基だけを選択的にアシル化するには、酸ハロゲン
化物よりも酸無水物の方が望ましい。酸ハロゲン化物、
特に酸塩化物は、フェノール性水酸基だけでな（、アル
コール性水酸基にも反応しやすく、フェノール性水酸基
だけを選択的に反応させることは困難である。However, in order to selectively acylate only the phenolic hydroxyl groups of the resol type phenolic resin, acid anhydrides are more desirable than acid halides. acid halide,
In particular, acid chlorides tend to react not only with phenolic hydroxyl groups (but also with alcoholic hydroxyl groups), and it is difficult to react selectively with only phenolic hydroxyl groups.
アシル化に用いられる塩基性触媒または酸受容剤として
はピリジンやトリエチルアミン等が挙げられる。Examples of the basic catalyst or acid acceptor used for acylation include pyridine and triethylamine.
このアシル化反応は、例えば、アシル化試薬として酸無
水物を用いる場合には、フェノール樹脂に用いたフェノ
ール類１モルに対し酸無水ＷＯ，Ｏ５〜１モルを、塩基
性触媒または酸受容剤の存在下、常温で、１２〜２４時
間反応させることにより行うことができる。アシル化試
薬として酸ハロゲン化物を用いる場合には、テトラメチ
ルフラン等の溶媒の存在下、反応液を−２０〜−１０℃
に冷却して１時間程度反応させることが好ましい。In this acylation reaction, for example, when an acid anhydride is used as the acylation reagent, 5 to 1 mole of acid anhydride WO, O is added to 1 mole of the phenol used in the phenol resin as a basic catalyst or an acid acceptor. This can be carried out by reacting for 12 to 24 hours at room temperature. When using an acid halide as an acylation reagent, the reaction solution is heated at -20 to -10°C in the presence of a solvent such as tetramethylfuran.
It is preferable to cool the mixture to a temperature of 100 mL and allow the reaction to occur for about 1 hour.
フェノール性水酸基のアシル化の程度は５％〜９５％と
する。アシル化が５％未満の場合には、レゾール型フェ
ノール樹脂の可塑化効果が小さく、また９５％を越える
と、樹脂の硬化時間が長くなりすぎ、樹脂硬化物を得る
ことが難しくなる。The degree of acylation of the phenolic hydroxyl group is 5% to 95%. When the acylation is less than 5%, the plasticizing effect of the resol type phenol resin is small, and when it exceeds 95%, the curing time of the resin becomes too long, making it difficult to obtain a cured resin product.
このようにしてアシル化したレゾール型フェノール樹脂
を、スペーサー等を使用して、加熱、加圧することによ
り硬化樹脂とすることができる。The thus acylated resol type phenolic resin can be made into a cured resin by heating and pressurizing it using a spacer or the like.
このようにして製造した硬化樹脂は、低弾性率かつ高伸
び率の性質を有しており、電気、電子部品用の積層板、
銅張積層板等への使用に極めて好適である。The cured resin produced in this way has a low modulus of elasticity and a high elongation rate, and can be used as a laminate for electrical and electronic parts.
It is extremely suitable for use in copper-clad laminates, etc.
以下、本発明を実施例にもとづいてさらに詳細に説明す
るが、本発明の範囲はこれら例によってなんら限定され
るものではない。Hereinafter, the present invention will be explained in more detail based on Examples, but the scope of the present invention is not limited in any way by these Examples.
二二玉聞濾二企底
メタクレゾール３０００ ｇ、桐油２０００ｇ、パラト
ルエンスルホン酸２ｇを混合し、９０℃で１時間反応さ
せた。次いでこの反応液にフェノール７２０ｇを添加し
、８０％バラホルムアルデヒド１４５０ｇ、３０％トリ
メチルアミン水溶液１１５ｇを加えた後、８０℃で３時
間反応させた。3000 g of 22 Yumonfila Nikidou metacresol, 2000 g of tung oil, and 2 g of paratoluenesulfonic acid were mixed and reacted at 90° C. for 1 hour. Next, 720 g of phenol was added to this reaction solution, followed by 1450 g of 80% paraformaldehyde and 115 g of a 30% aqueous trimethylamine solution, followed by reaction at 80° C. for 3 hours.
縮合水を留去し、反応液のゲルタイムが１６０℃の熱板
上で３分３０秒となった点を終点とし、ベース樹脂とし
た。The condensation water was distilled off, and the end point was when the gel time of the reaction solution reached 3 minutes and 30 seconds on a hot plate at 160° C., and a base resin was obtained.
実施例１
ベース樹脂１０００ｇに、ピリジン５０ｇ１無水酢酸３
００ｇを加え、室温で２４時間反応させた。樹脂を大量
の水で２〜３回洗浄した後、減圧下で濃縮し、１６０℃
の熱板上でのゲルタイムが２分３０秒となった点を終点
とした。得られたワニス中の樹脂のフェノール性水酸基
のアシル化率は６０％（計算値）であった。Example 1 To 1,000 g of base resin, 50 g of pyridine, 1 acetic anhydride, 3
00g was added and reacted at room temperature for 24 hours. After washing the resin 2-3 times with large amounts of water, it was concentrated under reduced pressure and heated to 160 °C.
The end point was the gel time on the hot plate of 2 minutes and 30 seconds. The acylation rate of the phenolic hydroxyl groups of the resin in the obtained varnish was 60% (calculated value).
実施例２
ベース樹脂３００ｇにテトラヒドロフラン１０００ｇを
加え、系の温度を一１０℃に冷却した。Example 2 1000 g of tetrahydrofuran was added to 300 g of the base resin, and the temperature of the system was cooled to -10°C.
次いで、塩化ベンゾイル１００ｇを徐々に添加した。添
加終了後、３０分間攪拌したのち、トリエチルアミン７
５ｇを加えた。３０分間攪拌したのち、トリエチルアミ
ン塩酸塩をろ別し、減圧下で加熱濃縮して、樹脂のゲル
タイムが１６０℃の熱板上で２分４０秒となった点を終
点とした。得られなワニス中の樹脂のフェノール水酸基
のアシル化率は４８％（計算値）であった。Then 100 g of benzoyl chloride was added gradually. After stirring for 30 minutes after the addition, triethylamine 7
Added 5g. After stirring for 30 minutes, triethylamine hydrochloride was filtered off and concentrated by heating under reduced pressure, and the end point was when the gel time of the resin reached 2 minutes and 40 seconds on a hot plate at 160°C. The acylation rate of the phenolic hydroxyl groups of the resin in the obtained varnish was 48% (calculated value).
比較例
ベース樹脂１０００ｇをさらに加熱濃縮し、樹脂のゲル
タイムが１６０℃の熱板上で２分３０秒となった点を終
点とした。Comparative Example 1000 g of the base resin was further heated and concentrated, and the end point was when the gel time of the resin reached 2 minutes and 30 seconds on a hot plate at 160°C.
上記実施例、比較例で調整したワニスをあらかじめ加熱
反応させ、樹脂をＢステージ化させた後粉砕し、スペー
サーを間にはさんだ鏡板の中に入れ、製品圧力１４０ｋ
ｇ／ｃＪで１７０℃、９０分加熱成形し、樹脂板を得た
。The varnishes prepared in the above Examples and Comparative Examples were heated and reacted in advance to make the resin B-stage, then crushed, placed in a mirror plate with a spacer in between, and the product pressure was 140K.
A resin plate was obtained by heat molding at 170° C. for 90 minutes at g/cJ.
樹脂板の特性をＪＩＳ−に−６９１１に従った引張試験
により評価し、その結果を表１に示す。The properties of the resin plate were evaluated by a tensile test according to JIS-6911, and the results are shown in Table 1.
（以下余白）
表１ 樹脂板の特性樫温時）
表１から明らかなように、レゾール型フェノール樹脂の
フェノール性水酸基をアシル化することによるフェノー
ル樹脂の可塑化に対する効果は著しく大きい。(The following is a blank space) Table 1 Characteristics of resin plate At oak temperature) As is clear from Table 1, the effect of acylating the phenolic hydroxyl group of the resol type phenolic resin on the plasticization of the phenolic resin is extremely large.
本発明の方法によって得られたフェノール樹脂組成物は
、硬化後の可撓性に掻めて優れており、その工業的価値
は大である。The phenol resin composition obtained by the method of the present invention has excellent flexibility after curing, and has great industrial value.
Claims (1)
５％〜９５％を一般式 ▲数式、化学式、表等があります▼ （式中、Ｒはアルキル基またはアリール基を表す） で表される酸無水物または一般式 ▲数式、化学式、表等があります▼ （式中、Ｒはアルキル基またはアリール基を表し、Ｘは
ＣｌまたはＢｒを表す） で表される酸ハロゲン化物でアシル化することを特徴と
するフェノール樹脂組成物の製造法。 ２、レゾール型フェノール樹脂が、乾性植物油変性レゾ
ール型フェノール樹脂である特許請求の範囲第１項記載
のフェノール樹脂組成物の製造法。 ３、酸無水物が無水酢酸または無水安息香酸である特許
請求の範囲第１項または第２項記載のフェノール樹脂組
成物の製造法。 ４、酸ハロゲン化物が塩化アセチルまたは塩化ベンゾイ
ルである特許請求の範囲第１項または第２項記載のフェ
ノール樹脂組成物の製造法。[Claims] 1. 5% to 95% of the phenolic hydroxyl groups of the resol type phenolic resin are expressed by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents an alkyl group or an aryl group) Acid anhydrides or general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents an alkyl group or an aryl group, and X represents Cl or Br) A method for producing a phenolic resin composition characterized by: 2. The method for producing a phenolic resin composition according to claim 1, wherein the resol type phenolic resin is a resol type phenolic resin modified with dry vegetable oil. 3. The method for producing a phenol resin composition according to claim 1 or 2, wherein the acid anhydride is acetic anhydride or benzoic anhydride. 4. The method for producing a phenolic resin composition according to claim 1 or 2, wherein the acid halide is acetyl chloride or benzoyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21184686A JPS6368624A (en) | 1986-09-09 | 1986-09-09 | Production of phenolic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21184686A JPS6368624A (en) | 1986-09-09 | 1986-09-09 | Production of phenolic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6368624A true JPS6368624A (en) | 1988-03-28 |
Family
ID=16612556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21184686A Pending JPS6368624A (en) | 1986-09-09 | 1986-09-09 | Production of phenolic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6368624A (en) |
-
1986
- 1986-09-09 JP JP21184686A patent/JPS6368624A/en active Pending
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