JPH0314815A - Novolac epoxy resin, its preparation, epoxy resin composition, and novolac resin - Google Patents
Novolac epoxy resin, its preparation, epoxy resin composition, and novolac resinInfo
- Publication number
- JPH0314815A JPH0314815A JP19248289A JP19248289A JPH0314815A JP H0314815 A JPH0314815 A JP H0314815A JP 19248289 A JP19248289 A JP 19248289A JP 19248289 A JP19248289 A JP 19248289A JP H0314815 A JPH0314815 A JP H0314815A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- novolac
- general formula
- resin
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003986 novolac Polymers 0.000 title claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 title claims description 53
- 229920000647 polyepoxide Polymers 0.000 title claims description 53
- 239000000203 mixture Substances 0.000 title claims description 12
- 239000004843 novolac epoxy resin Substances 0.000 title abstract 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 3
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000000565 sealant Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 29
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 241000238557 Decapoda Species 0.000 description 6
- 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 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- -1 laminates Substances 0.000 description 4
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 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
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003829 resin cement Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規なエポキシ化合物、その製造方法及びエポ
キシ樹脂組成物に関し、より詳細には、硬化することに
よって耐熱性および耐水性の優れた硬化物を得ることが
できるエポキシ化合物に関するものである．
〔従来の技術〕
エポキシ樹脂は種々の硬化剤で硬化させることにより、
一般的に機械的性質、而１水性、耐薬品性、耐熱性、電
気的性質などの優れた硬化物となり、接着剤、塗料、積
層板、成形材料など幅広い分野に使用されている。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel epoxy compound, a method for producing the same, and an epoxy resin composition. It is related to epoxy compounds that can be used to obtain products. [Prior art] Epoxy resin can be cured with various curing agents.
Generally, it becomes a cured product with excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties, and is used in a wide range of fields such as adhesives, paints, laminates, and molding materials.
最も汎用的なエポキシ樹脂は、ビスフェノールＡにエビ
クロルヒドリンを反応させて得られる液状および固型の
ビスフェノールＡ型エポキシ樹脂である．
〔発明が解決しようとする課題〕
しかしながら、上記ビスフェノール型エポキシ樹脂は、
１分子当りのグリシジル基が２個よりは多くはないため
に硬化時の架４！密度が低く、耐熱性に劣る傾向にある
．
この様な欠点を改良するために、いわゆる多官能エポキ
シ樹脂であるクレゾールノボラック型エポキシ樹脂など
が使用されているが、これらの場合は確かに耐熱性は向
上ずるものの、その度合は不十分な上、耐水性が劣ると
いう欠点を有している．
本発明の目的は、優れた耐熱性、耐水性を有し、機械的
性質にも優れた樹脂硬化物を得ることのできる新規なエ
ポキシ樹脂を提｛Ｊｊすることを目的とする。The most commonly used epoxy resins are liquid and solid bisphenol A type epoxy resins, which are obtained by reacting bisphenol A with shrimp chlorohydrin. [Problem to be solved by the invention] However, the above bisphenol-type epoxy resin,
Since there are no more than 2 glycidyl groups per molecule, the number of bridges during curing is 4! It has a low density and tends to have poor heat resistance. In order to improve these drawbacks, cresol novolac type epoxy resins, which are so-called multifunctional epoxy resins, are used, but although these do improve heat resistance, the degree of improvement is insufficient. However, it has the disadvantage of poor water resistance. An object of the present invention is to provide a novel epoxy resin that has excellent heat resistance, water resistance, and can obtain a cured resin product with excellent mechanical properties.
本発明は、上記課題を解決するために、下記一般式（１
）で示される重合成分を有するノボラック型エポキシ樹
脂を提供するものである．（式中、Ｒは水素原子、炭素
数１ないし３のアルキル基、フェニル基、ヒドロキシフ
ェニル基、ハロゲン置換フエニル基を表わす。）
上記一般式（１）の重合戒分を有するノボラック型エポ
キシ樹脂としては次の一般式（ｎ）で示される樹脂が挙
げられ、ｎ＝０〜３が好ましい．《式中、Ｒは一般式（
１）と同じものを表わし、ｎは繰り返し単位数を表わす
。）
また、これらのノボラ゛ソク型エポキシ樹脂の製造方法
及びこのノボラック型エポキシ樹脂を用いた樹脂ｍ威物
、その中間体のノボラック樹脂を提供するものである．
次に本発明を詳細に説明する。In order to solve the above problems, the present invention provides the following general formula (1
) Novolak-type epoxy resin having the polymerization component shown in the following is provided. (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxyphenyl group, or a halogen-substituted phenyl group.) As a novolac type epoxy resin having the polymerization component of the above general formula (1) Examples include resins represented by the following general formula (n), with n=0 to 3 being preferred. 《In the formula, R is the general formula (
It represents the same as 1), and n represents the number of repeating units. ) The present invention also provides a method for producing these novolac type epoxy resins, resin products using these novolac type epoxy resins, and intermediate novolac resins thereof. Next, the present invention will be explained in detail.
本発明の上記一般式（１）のエポキシ樹脂はｎが０〜３
、すなわちノボラック型樹脂の分子中にフルオレン核を
２個以上を含むものを骨格とするものであり、好ましく
はフルオレン核を２〜５個含むもので、特に好ましくは
２．５〜４個含むものである。In the epoxy resin of the above general formula (1) of the present invention, n is 0 to 3.
That is, a novolak type resin having a skeleton containing two or more fluorene nuclei in the molecule, preferably containing 2 to 5 fluorene nuclei, particularly preferably 2.5 to 4 fluorene nuclei. .
分子中に含まれるフルオレン核の数が少ないと得られる
エポキシ樹脂の耐熱性は不十分であり、また、フルオレ
ン核の数が多くなると、エポキシ樹脂の融点が高くなり
、成形性が悪くなる．上記一般式（１）の重合成分を有
するノボラック型エポキシ樹脂の製造方法としては、９
，９−ビス（４−ヒドロキシフェニル〉フルオレンを主
たる成分とするフェノール類と下記式一般式（ ＩＩＩ
）Ｒ−ＣＩＩＯ （ＩＩＩ）（弐ψ
、Ｒは上記一般式（＋）のものと同しものを表わし、水
素原子、炭素数１ないし３のアルキル基、フェニル基、
ヒドロキシフェニル基、ハロゲン置換フエニル基を表わ
す。）
で表わされるアルデヒドとを反応させて得られる下記一
般式（Ｖ）
−（
ンを反応させるが、上記一般式（ＩＩ）のノボラック型
エポキシ樹脂の場合には分子中にフルオレン核を２個以
上含む下記一般式（ ［Ｖ）で表わされるノボラック樹
脂とエビクロルヒドリンとを反応させる．
（式中、Ｒ，ｎは一般式（ＩＩ）のものと同じものを表
わす。）
フェノール化合物としては、上記のほかにフェノール、
クレゾール、キシレノール、レゾルシノール、α−ナフ
トールなどのフェノール類の１種又は２種以上を共重合
成分として用いることができる．
また、上記一般式（Ｉｔ）のアルデヒドとしては、具体
的にはホルムアルデヒド、アセトアルデヒド、プロビル
アルデヒド、ブチルアルデヒド、ベンズアルテヒド、ｐ
−ヒドロキシベンズアルデヒド、クロルベンズアルデヒ
ドなどであり、このうちホルムアルデヒドが好ましい。If the number of fluorene nuclei contained in the molecule is small, the resulting epoxy resin will have insufficient heat resistance, and if the number of fluorene nuclei is large, the melting point of the epoxy resin will become high, resulting in poor moldability. As a method for producing a novolac type epoxy resin having the polymerization component of the above general formula (1), 9
, 9-bis(4-hydroxyphenyl) Phenols whose main component is fluorene and the following general formula (III
)R-CIIO (III) (弐ψ
, R represents the same as in the above general formula (+), and includes a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group,
Represents a hydroxyphenyl group or a halogen-substituted phenyl group. ) The following general formula (V) obtained by reacting with an aldehyde represented by A novolac resin represented by the following general formula ([V) containing the compound is reacted with shrimp chlorohydrin. (In the formula, R and n represent the same as those of the general formula (II).) As the phenol compound, In addition to the above, phenol,
One or more phenols such as cresol, xylenol, resorcinol, and α-naphthol can be used as a copolymerization component. Further, the aldehyde of the above general formula (It) is specifically formaldehyde, acetaldehyde, probilaldehyde, butyraldehyde, benzaldehyde, p
-hydroxybenzaldehyde, chlorobenzaldehyde, etc., and among these, formaldehyde is preferred.
本発明のノボラック型エポキシ樹脂の原料であるノボラ
ック型樹脂は、従来より行なわれているフェノールノボ
ラック樹脂の製造方法と同様であり、特に制限されるも
のではない。The novolac type resin which is a raw material for the novolac type epoxy resin of the present invention is the same as the conventional method for producing phenol novolak resin, and is not particularly limited.
９．９−ビス（４−ヒドロキシフエニル）フルオレンと
上記一般式（ＩＩＩ）のアルデヒドの仕込み比は目的と
するノボラック型樹脂の重合度によって調節されるが、
９，９−ビス（４−ヒドロキシフエニル）フルオレン１
モルに対して０． ５〜１．２モルの範囲が好ましい．
また、反応に使用する酸触媒は硫酸、塩酸、リン酸、塩
化アルξニウム、塩素スズ、塩化亜鉛、シュウ酸、三フ
フ化ホウ素などを用いることができる。これらのうちで
もシュウ酸を用いることが好ましい．
また、具体的反応方法としては、９，９−ビス（４一ヒ
ドロキシフェニル）フルオレン等と上記一般式（ＩＩ）
で表わされるアルデヒドとを酸性触媒の存在下、５０〜
２５０℃、好ましくは８０〜２００℃の温度で１時間〜
ＩＯ時間１３ｍ拌することにより行なわれる．
また、上記反応はプチルセロソルブ、ベンゼン、トルエ
ン、キシレン、クロロホルム、テトラヒド口フラン等の
不活性な溶媒を使用したほうが反応が円滑に進む．
次に本発明の一般式（１）のエポキシ樹脂は上記の方法
で合成されたノボラック型樹脂にエビクロルヒドリンを
反応させることによって得られる．この場合の反応条件
は、従来より行なわれているエポキシ樹脂の製造条件と
同じであり、特に制限されるものではない．
即ちノボラック型樹脂の水酸基１個に対し、エビクロル
ヒドリンを１．５〜ｌＯモル添加し、水酸化ナトリウム
のようなアルカリの存在下に４０〜１２０℃でエポキシ
化反応を行なうことができ、水酸基に対するエビクロル
ヒドリンが過剰になる過剰率を調節することにより、得
られるエポキシ化物の分子量、エポキシ当■、軟化点を
調整することができる、エピクロルヒドリンの過剰率を
下げるとエポキシ樹脂の分子螢が高くなり、靭性の高い
硬化物となり、逆に上げると分子量が低くなり、耐熱性
の高い硬化物となる傾向がある。9. The charging ratio of 9-bis(4-hydroxyphenyl)fluorene and the aldehyde of general formula (III) above is adjusted depending on the degree of polymerization of the target novolak type resin,
9,9-bis(4-hydroxyphenyl)fluorene 1
0 per mole. A range of 5 to 1.2 moles is preferred. Further, as the acid catalyst used in the reaction, sulfuric acid, hydrochloric acid, phosphoric acid, aluminum ξium chloride, tin chloride, zinc chloride, oxalic acid, boron trifluoride, etc. can be used. Among these, it is preferable to use oxalic acid. In addition, as a specific reaction method, 9,9-bis(4-hydroxyphenyl)fluorene etc. and the above general formula (II)
In the presence of an acidic catalyst, the aldehyde represented by
1 hour at a temperature of 250°C, preferably 80-200°C
This is done by stirring for an IO time of 13 m. Additionally, the above reaction will proceed more smoothly if an inert solvent such as butyl cellosolve, benzene, toluene, xylene, chloroform, or tetrahydrofuran is used. Next, the epoxy resin of the general formula (1) of the present invention can be obtained by reacting the novolac type resin synthesized by the above method with shrimp chlorohydrin. The reaction conditions in this case are the same as those for conventional production of epoxy resins, and are not particularly limited. That is, it is possible to add 1.5 to 10 moles of shrimp chlorohydrin to one hydroxyl group of a novolak type resin and carry out an epoxidation reaction at 40 to 120°C in the presence of an alkali such as sodium hydroxide. By adjusting the excess ratio of epichlorohydrin to hydroxyl groups, the molecular weight, epoxy resin, and softening point of the resulting epoxide can be adjusted.If the excess ratio of epichlorohydrin is lowered, the molecular weight of the epoxy resin increases. If the molecular weight increases, the resulting cured product tends to have high toughness; conversely, when the molecular weight increases, the molecular weight tends to decrease, resulting in a cured product with high heat resistance.
上記反応で生威した本発明のエポキシ樹脂は単独で、ま
た必用により汎用のポリエポキシ化合物、例えばビスフ
ェノールＡ型エポキシ樹脂をこれに配合し、硬化剤を添
加混合し、加熱硬化させることによって、硬化物を得る
ことができる。The epoxy resin of the present invention produced in the above reaction can be cured alone or, if necessary, by blending it with a general-purpose polyepoxy compound, such as a bisphenol A type epoxy resin, adding and mixing a curing agent, and heating and curing. can get things.
上記硬化剤としては特に限定されるものではなく、通常
エポキシ樹脂の硬化剤として常用されている化合物はす
べて使用するとかできジエチレントリアニン、トリエチ
レンテトラミンなどの脂肪族アミン類、メタフエニレン
、ジアミン、ジアミノジフエニルメタン、ジアミノジフ
エニルスルホンなどの芳香族アミン類、ボリアミド樹脂
及びこれらの変性物、無水マレイン酸、無水フタル酸、
無水へキサヒドフタル酸、無水ピロメリット酸などの酸
無水物系硬化剤ジシアンジアミド、イミダゾール、ＢＦ
ｉ−アξン金属塩、グアニジン誘導体などの潜在性硬化
剤、ノボラック樹脂などがあげられる。The above-mentioned curing agent is not particularly limited, and all compounds commonly used as curing agents for epoxy resins can be used. Aromatic amines such as enylmethane and diaminodiphenylsulfone, polyamide resins and modified products thereof, maleic anhydride, phthalic anhydride,
Acid anhydride curing agent such as hexahydrophthalic anhydride, pyromellitic anhydride, dicyandiamide, imidazole, BF
Examples include i-amine metal salts, latent curing agents such as guanidine derivatives, and novolac resins.
これらの硬化剤の使用量は、用いるエポキシ化合物の一
分子中に含まれるエポキシ基の数と硬化剤中の活性水素
の数が当量付近となる量が一般的である。The amount of these curing agents used is generally such that the number of epoxy groups contained in one molecule of the epoxy compound used and the number of active hydrogens in the curing agent are approximately equivalent.
これらの硬化剤は単独でも２種以上の併用でもよい。These curing agents may be used alone or in combination of two or more.
上記硬化剤を用いる際は、硬化促進剤を適宜使用するこ
とができる．
硬化促進剤としては公知、慣用のものがいづれも使用で
きるが、例えば第３級アミン、イξダゾール、有機酸金
属塩、ルイス酸、ア果ン金属塩等が挙げられ、これらは
単独のみならず２種以上の併用も可能である．
次に本発明を実施例により具体的に説明するが、以下に
おいて部は特に断りのない限りすべてｆｆｌｆｆｔ部で
あるものとする．
実施例１
９．９−ビス（４−ヒドロキシフエニル）フルオレン１
′？ｓ部をプチルセロソルブ ／７５部に溶解し、シュ
ウ酸１．２ｇを加え１００℃に昇温し、さらにホルマリ
ン（４１．５％）４１部を３０分間かけて滴下し、次い
で同温度で５時間加熱する。その後、昇温し脱水し、最
終的に１８０〜２００℃で減圧蒸留により脱溶剤を行な
い、フルオレンノボラック樹脂（ａ）（融点１２０℃）
１８７部を得た．ＧＰＣ（ゲルパーミネーションクロマ
トグラフィー〉分析により平均でフルオレン核を２．７
個含んでいることかわかった。When using the above curing agent, a curing accelerator can be used as appropriate. Any known or commonly used curing accelerator can be used, but examples include tertiary amines, ξdazole, organic acid metal salts, Lewis acids, and apple metal salts. It is also possible to use two or more types together. Next, the present invention will be explained in detail with reference to Examples, and in the following, unless otherwise specified, all parts are fflfft parts. Example 1 9.9-bis(4-hydroxyphenyl)fluorene 1
′? Part S was dissolved in 75 parts of butyl cellosolve, 1.2 g of oxalic acid was added, the temperature was raised to 100°C, 41 parts of formalin (41.5%) was added dropwise over 30 minutes, and then the mixture was heated at the same temperature for 5 hours. Heat. After that, the temperature is raised and dehydrated, and finally the solvent is removed by vacuum distillation at 180 to 200°C, and the fluorene novolac resin (a) (melting point 120°C)
Obtained 187 copies. GPC (gel permeation chromatography) analysis shows that fluorene nuclei are on average 2.7
I found out that it contains .
得られたフルオレンノボラック樹脂（ａｌの赤外吸収ス
ペクトルを図−１に示す。顕著な吸収は下記の如くであ
る。The infrared absorption spectrum of the obtained fluorene novolac resin (al) is shown in Figure 1. The remarkable absorptions are as follows.
なおＡｒは芳香環を示す。以下同様である．３３００Ｃ
ｌ１−’ 八ｒ−０１１３０５０ａｉ
−’ −Ｃ−ＩＩ （Ａｒ−ＩＩ）２９５０
〜２８５０ ａｎ − ’ −Ｃｌｌ ｚま
た、ＮＭＲスペクトルを図３に示す。Note that Ar represents an aromatic ring. The same applies below. 3300C
l1-' 8r-0113050ai
-' -C-II (Ar-II) 2950
~2850 an − ' -Cll z The NMR spectrum is also shown in FIG.
実施例２
ホルマリンの量を４１部から、４６．０部に変更した以
外は実施例１と同様にしてフルオレンノボラック樹脂（
ｂ）（融点１３０℃）１８９部を得た．ＧＰＣ分析によ
り平均でフルオレン核を３．５個含んでいることが分か
った。Example 2 Fluorene novolac resin (
b) (melting point: 130°C) 189 parts were obtained. GPC analysis revealed that it contained 3.5 fluorene nuclei on average.
実施例３
実施例１で得られたフルオレンノボラック樹脂（ａｌｌ
７’７ｇをエピクロルヒドリン４６３ｇ（５モル）に溶
解させた後、撹拌下８０℃で、２０％Ｎ ａ Ｏ１ｌ水
溶液２２０ｇ（１．１モル）を５時間かけて滴下し、更
に１時間反応させ、次いで水層を棄却した後、過剰のエ
ビクロルヒドリンを蒸留回収して、得られた反応生成物
にメヂルイソブチルケトン４！；Ｑｇを加え、均一に溶
解させ、水１４０ｇを加えて水洗した後、油水分離し、
油層から共沸蒸留により水を除いた後、濾過し、さらに
メチルイソブチルケトンを留去させて、エポキシ当撥２
７３、融点８０℃なるエポキシ樹脂（ｃｌ ２−ＬＯ
ｇを得た。その赤外吸収スペクトルを図−２に示す。Example 3 Fluorene novolak resin obtained in Example 1 (all
After dissolving 7'7g in 463g (5 mol) of epichlorohydrin, 220g (1.1 mol) of 20% NaO1 aqueous solution was added dropwise at 80°C with stirring over 5 hours, the reaction was continued for another 1 hour, and then After discarding the aqueous layer, excess shrimp chlorohydrin was distilled and recovered, and the resulting reaction product contained methyl isobutyl ketone 4! ; Add Qg and dissolve it uniformly, add 140 g of water and wash with water, then separate the oil and water.
After water is removed from the oil layer by azeotropic distillation, it is filtered, and methyl isobutyl ketone is distilled off to remove the epoxy resin.
73, epoxy resin with a melting point of 80°C (cl 2-LO
I got g. Its infrared absorption spectrum is shown in Figure 2.
顕著な吸収は下記の如くである。The notable absorptions are as follows.
３０５０ａｌ−’ −Ｃ−ＩＩ （Ａｒ−Ｉ
Ｉ）（ ０）１
２９５０〜２８５０ｃｍ−’ −Ｃｌｌ，１２
５０ｃ１ｍ−’ −０ 一８６０ｃ
ｍ−’
また、ＮＭＲスペクトルを図４に示す．実施例４
エビクロルヒドリン４６３ｇの代りに２７０ｇ（３モル
）を使用した以外は実施例３と同様にして、エポキシ当
量が２８５融点９０℃なるエポキシ樹脂＋ｄ） Ｚ Ｉ
Ｓ ｇを得た．実施例５
フルオレンノボラック樹脂（ａ）の代りに（ｂ） ヲ使
用した以外は実施例３と同様にして、エポキシ当量が２
，８０，融点８６℃なるエポキシ樹脂（ｅｌを得た．実
施例６〜Ｂおよび比較例１〜２（エポキシ樹脂組成物）
エポキシ樹脂として実施例３〜５で得られたエポキシ樹
脂（Ｃ）〜（ｅ》（実施例６〜８）、フェノールノボラ
ック型エポキシ樹脂エビクロント７３Ｂ （大Ｂ本イ
ンキ化学工業ａ着製、エポキシ当ｉｌｌ ８ ０）（比
較例１）、オルソクレゾールノボランク型エポキシ樹脂
エピクロンＮ−６７０ （同社製、エポキシ当ｆｆｌ２
１ ０） （比較例２）、硬化剤としてエピクロンＢ
−５７０ （同社製、メチルテトラヒドロフタル酸無
水物）、硬化促進剤としてペンジルジメチルアξンを用
い、エポキシ樹脂のエポキシ基１個に対して硬化剤のＭ
無水物基が１個になる様に下記表−１に示す組威で配合
して、本発明および比較対照用のエポキシ樹脂組戒物を
得た。3050al-' -C-II (Ar-I
I) (0) 1 2950-2850cm-' -Cll, 12
50c1m-' -0 -860c
m-' Also, the NMR spectrum is shown in Figure 4. Example 4 An epoxy resin with an epoxy equivalent of 285 and a melting point of 90°C was prepared in the same manner as in Example 3, except that 270 g (3 mol) was used instead of 463 g of shrimp chlorohydrin + d) Z I
I got S g. Example 5 The same procedure as in Example 3 was carried out except that fluorene novolak resin (b) was used instead of (a), but the epoxy equivalent was 2.
, 80, an epoxy resin (el) having a melting point of 86° C. was obtained. Examples 6 to B and Comparative Examples 1 to 2 (epoxy resin compositions) Epoxy resins (C) obtained in Examples 3 to 5 as epoxy resins (e) (Examples 6 to 8), Phenol novolak type epoxy resin Ebicuront 73B (manufactured by Dai-Bon Ink Kagaku Kogyo A, epoxy per illumination 80) (Comparative example 1), Orthocresol novolac type epoxy resin Epiclon N -670 (manufactured by the same company, epoxy ffl2
10) (Comparative Example 2), Epiclon B as a curing agent
-570 (manufactured by the same company, methyltetrahydrophthalic anhydride), using penzyldimethylamine as a curing accelerator,
Epoxy resin compositions for the present invention and for comparison were obtained by blending the compositions as shown in Table 1 below so that the number of anhydride group was one.
これらのエポキシ権脂組成物をｌＯＯ℃で２時間、次い
で１６０℃で２時間、更に１８０℃で２時間の条件で硬
化せしめて試験片とし、ＪＩＳκ６９１１に準拠して熱
変形温度、曲げ強度、聞げ郵性率、引張り強度、引張り
伸び率および煮沸吸水率を測定した．結果を下記表に示
す。These epoxy resin compositions were cured at 100°C for 2 hours, then at 160°C for 2 hours, and then at 180°C for 2 hours. The tensile strength, tensile elongation, and boiling water absorption were measured. The results are shown in the table below.
実施例９〜ｌ１および比較応用例３〜４硬化剤としてエ
ピクロンＢ−５７０の代りにノボラック型フェノール樹
脂バーカムＴＯ−２１３１ （大日本インキ化学工業■
製、軟化点８０℃〕を用い、エポキシ樹脂のエポキシ基
１個に対して硬化剤のフェノール性水酸基が１個になる
様に下記表−１に示す組威で配合した以外は実施例ｌと
同様にして、本発明および比較対照用のヱポキシ樹脂組
或物を得た．
これらのエポキシ樹脂組成物を１００℃で２時間、次い
で１２０℃で２時間、更に１５０℃で２時間の条件で硬
化せしめて試験片とし、実施例１と同様の測定を行った
。結果を下記表−１に示す．〔発明の効果〕
本発明によれば、上記一般式（１）で示される新規なエ
ポキシ樹脂及びその製造方法を提供できるので、このエ
ポキシ１Ｍ脂を種々の硬化剤により、硬化させることに
よって優性耐熱性、耐水性を有し、機械的性質にも優れ
た硬化物にすることができ、電気、電子部品等の封子剤
、ブリプレグ等の成形材料、注型材料、積層板等の複合
材料、ハニカムパネル等の構造材料、各種接着剤、各種
塗料、ブライマー、シール剤、樹脂モルタル、樹脂セメ
ント、舗装材等の用途に有用なエポキシ樹脂を提供でき
る．Examples 9 to 11 and Comparative Application Examples 3 to 4 Novolac type phenolic resin Barkum TO-2131 (Dainippon Ink & Chemicals) was used instead of Epiclon B-570 as a curing agent.
Example 1 was used, except that the composition was blended with the composition shown in Table 1 below so that the number of phenolic hydroxyl groups in the curing agent was one for each epoxy group in the epoxy resin. Epoxy resin compositions for the present invention and for comparative purposes were obtained in the same manner. These epoxy resin compositions were cured at 100° C. for 2 hours, then at 120° C. for 2 hours, and then at 150° C. for 2 hours to prepare test pieces, and the same measurements as in Example 1 were performed. The results are shown in Table 1 below. [Effects of the Invention] According to the present invention, it is possible to provide a novel epoxy resin represented by the above general formula (1) and a method for producing the same. By curing this 1M epoxy resin with various curing agents, it is possible to obtain superior heat resistance. It can be made into a cured product that has excellent hardness, water resistance, and mechanical properties, and can be used as a sealant for electrical and electronic parts, molding materials such as Bripreg, casting materials, and composite materials such as laminates. We can provide epoxy resins useful for structural materials such as honeycomb panels, various adhesives, various paints, brimers, sealants, resin mortars, resin cements, paving materials, etc.
第１図は本発明の一実施例のエポキシ樹脂の赤外線スペ
クトル図、第２図は他の実施例のエポキシ樹脂の赤外線
スペクトル図、第３図は第１図に示すエポキシ樹脂のＮ
ＭＲスペクトル図、第４図は第２図に示すエポキシ樹脂
のＮＭＲスペクトル図である。FIG. 1 is an infrared spectrum diagram of an epoxy resin according to one embodiment of the present invention, FIG. 2 is an infrared spectrum diagram of an epoxy resin according to another embodiment, and FIG. 3 is an N of the epoxy resin shown in FIG.
MR spectrum diagram, FIG. 4 is an NMR spectrum diagram of the epoxy resin shown in FIG. 2.
Claims (7)
るノボラック型エポキシ樹脂。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは水素原子、炭素数１ないし３のアルキル基
、フェニル基、ヒドロキシフェニル基、ハロゲン置換フ
ェニル基を表わす。）(1) A novolac-type epoxy resin having a polymerization component represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxyphenyl group, or a halogen-substituted phenyl group.)
ボラック型エポキシ樹脂。 ▲数式、化学式、表等があります▼ （式中、Ｒは一般式（ I ）のものと同じものを表わし
、ｎは繰り返し単位数を表わす。）(2) The novolac type epoxy resin according to claim 1, which is represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents the same thing as in general formula (I), and n represents the number of repeating units.)
ポキシ樹脂。(3) The novolac type epoxy resin according to claim 2, wherein n is 0 to 3.
型エポキシ樹脂と硬化剤を含有することを特徴とするエ
ポキシ樹脂組成物。(4) An epoxy resin composition comprising the novolak epoxy resin according to any one of claims 1 to 3 and a curing agent.
レンを主成分とするフェノール化合物と下記一般式（I
II） Ｒ−ＣＨＯ（III） （式中、Ｒは請求項１記載の一般式（ I ）とおなじも
のを表わす。） で表わされるアルデヒドとを反応させて得られるノボラ
ック型樹脂とエピクロルヒドリンとから得られるノボラ
ック型エポキシ樹脂の製造方法。(5) A phenolic compound containing 9,9-bis(4-hydroxyphenyl)fluorene as a main component and the following general formula (I
II) R-CHO(III) (wherein R represents the same thing as the general formula (I) according to claim 1): obtained from a novolac type resin obtained by reacting with an aldehyde represented by R-CHO(III) and epichlorohydrin. A method for producing novolak-type epoxy resin.
ク型エポキシ樹脂の製造方法。 ▲数式、化学式、表等があります▼（IV） （式中、Ｒは一般式（ I ）と同じものを表わし、ｎは
繰り返し単位数を表わす。）(6) The method for producing a novolak-type epoxy resin according to claim 5, wherein the novolak-type resin is a resin represented by the following general formula (IV). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R represents the same thing as the general formula (I), and n represents the number of repeating units.)
ノボラック樹脂。 ▲数式、化学式、表等があります▼（Ｖ） （式中、Ｒは一般式（ I ）と同じものを表わす。）（
８）請求項６記載の一般式（IV）で表わされるノボラッ
ク樹脂。(7) A novolac resin having a polymerization component represented by the following general formula (V). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R represents the same thing as the general formula (I).)
8) A novolak resin represented by the general formula (IV) according to claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4660989 | 1989-03-01 | ||
| JP1-46609 | 1989-04-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0314815A true JPH0314815A (en) | 1991-01-23 |
Family
ID=12752046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19248289A Pending JPH0314815A (en) | 1989-03-01 | 1989-07-27 | Novolac epoxy resin, its preparation, epoxy resin composition, and novolac resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0314815A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11199656A (en) * | 1998-01-12 | 1999-07-27 | Nippon Kayaku Co Ltd | Novolak resin, epoxy resin, epoxy resin composition and cured product thereof |
| US7303855B2 (en) * | 2003-10-03 | 2007-12-04 | Shin-Etsu Chemical Co., Ltd. | Photoresist undercoat-forming material and patterning process |
| JP2008274000A (en) * | 2007-04-06 | 2008-11-13 | Osaka Gas Co Ltd | Thermosetting resin composition and its cured material |
| CN105273149A (en) * | 2014-07-15 | 2016-01-27 | 罗门哈斯电子材料有限责任公司 | Resin for underlayer |
| WO2020213992A1 (en) * | 2019-04-19 | 2020-10-22 | 국도화학 주식회사 | Epoxy resin, preparation method thereof, and epoxy resin composition comprising same |
-
1989
- 1989-07-27 JP JP19248289A patent/JPH0314815A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11199656A (en) * | 1998-01-12 | 1999-07-27 | Nippon Kayaku Co Ltd | Novolak resin, epoxy resin, epoxy resin composition and cured product thereof |
| US7303855B2 (en) * | 2003-10-03 | 2007-12-04 | Shin-Etsu Chemical Co., Ltd. | Photoresist undercoat-forming material and patterning process |
| JP2008274000A (en) * | 2007-04-06 | 2008-11-13 | Osaka Gas Co Ltd | Thermosetting resin composition and its cured material |
| CN105273149A (en) * | 2014-07-15 | 2016-01-27 | 罗门哈斯电子材料有限责任公司 | Resin for underlayer |
| JP2016029160A (en) * | 2014-07-15 | 2016-03-03 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Resin for underlayer |
| US9880469B2 (en) | 2014-07-15 | 2018-01-30 | Rohm And Haas Electronic Materials Llc | Resins for underlayers |
| WO2020213992A1 (en) * | 2019-04-19 | 2020-10-22 | 국도화학 주식회사 | Epoxy resin, preparation method thereof, and epoxy resin composition comprising same |
| KR20200123028A (en) * | 2019-04-19 | 2020-10-28 | 국도화학 주식회사 | Epoxy resin, preparation method thereof, and epoxy resin composition comprising the same |
| CN113710720A (en) * | 2019-04-19 | 2021-11-26 | 国都化学株式会社 | Epoxy resin, method for preparing the same, and epoxy resin composition comprising the same |
| JP2022529361A (en) * | 2019-04-19 | 2022-06-21 | クク・ト・ケミカル・カンパニー・リミテッド | Epoxy resin, a method for producing the same, and an epoxy resin composition containing the same. |
| CN113710720B (en) * | 2019-04-19 | 2023-06-13 | 国都化学株式会社 | Epoxy resin, method for preparing the same, and epoxy resin composition comprising the same |
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