JPS63238122A - Epoxy resin and production thereof - Google Patents
Epoxy resin and production thereofInfo
- Publication number
- JPS63238122A JPS63238122A JP7028187A JP7028187A JPS63238122A JP S63238122 A JPS63238122 A JP S63238122A JP 7028187 A JP7028187 A JP 7028187A JP 7028187 A JP7028187 A JP 7028187A JP S63238122 A JPS63238122 A JP S63238122A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- resin
- xylene
- formula
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 25
- 229920000647 polyepoxide Polymers 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 9
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 7
- 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 7
- -1 bisphenol sulfone Chemical class 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 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 5
- 239000011159 matrix material Substances 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000005489 elastic deformation Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011874 heated mixture Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 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
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
- 241000238557 Decapoda Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 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
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical group 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 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
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、新規な低分子量エポキシ樹脂およびその製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel low molecular weight epoxy resin and a method for producing the same.
このエポキシ樹脂は、耐熱性、機械的特性、作業性に優
れ、注形用、積層用、塗料用、半導体封止用等の多方面
に利用可能である。This epoxy resin has excellent heat resistance, mechanical properties, and workability, and can be used for many purposes such as casting, lamination, coating, and semiconductor sealing.
(従来の技術)
従来、エポキシ樹脂として耐熱複合材用マトリックス樹
脂や耐熱性接着剤等への利用は多種多様である。典形的
には、ビスフェノールA、ビスフェノールスルホン等の
フェノール骨格を有するものや4.4−ジアミノジフェ
ニルメタン、 3.3’−ジアミノジフェニルスルホン
等の芳香族アミン骨格を有するものがある。これらはビ
スフェノール類や芳香族ジアミン類をエビハロヒドリン
と反応させて得ることができる。このエポキシ樹脂は一
般的には適当な硬化剤と混合しそのエポキシ基と硬化剤
の官能基とを反応させることによって、先に述べたよう
な各種用途に使用される。(Prior Art) Conventionally, epoxy resins have been used in a wide variety of applications, such as matrix resins for heat-resistant composite materials and heat-resistant adhesives. Typically, there are those having a phenol skeleton such as bisphenol A and bisphenol sulfone, and those having an aromatic amine skeleton such as 4,4-diaminodiphenylmethane and 3,3'-diaminodiphenylsulfone. These can be obtained by reacting bisphenols and aromatic diamines with shrimp halohydrin. This epoxy resin is generally mixed with a suitable curing agent and used for the various applications mentioned above by reacting the epoxy groups with the functional groups of the curing agent.
また、特殊なものとしては、フェノールノボラック樹脂
のエポキシ化物やフェノール−キシレン結合樹脂のエポ
キシ化物(特公昭47−13782)等が知られており
、同様の方法で使用される。Further, as special products, epoxidized products of phenol novolac resin and epoxidized products of phenol-xylene bonded resin (Japanese Patent Publication No. 13782/1982) are known, and are used in the same manner.
前記の共形的なエポキシ樹脂の硬化物としての性能は、
電気的性質、寸法安定性、耐薬品性の点ですぐれた性能
を有しているが、まだ耐熱性の点で不十分である。The performance of the conformal epoxy resin as a cured product is as follows:
Although it has excellent performance in terms of electrical properties, dimensional stability, and chemical resistance, it is still insufficient in terms of heat resistance.
一般的に耐熱性を向上させようとすれば架橋密度を上げ
る手法がとられるが、反面、樹脂が硬くてもろくなるこ
とが避けられない。また、耐熱性を向上させるための他
の手法として、エポキシ樹脂骨格中にスルホン結合やア
ミン結合等を導入すると、硬化樹脂の吸湿性が増し、耐
水性の点で好ましくない。Generally, in order to improve heat resistance, a method is taken to increase the crosslinking density, but on the other hand, this inevitably results in the resin becoming hard and brittle. In addition, as another method for improving heat resistance, introducing sulfone bonds, amine bonds, etc. into the epoxy resin skeleton increases the hygroscopicity of the cured resin, which is not preferable in terms of water resistance.
近年、これらのエポキシ樹脂に、より高度な性能を付加
させることが要求されるようになった。In recent years, it has become necessary to add more advanced performance to these epoxy resins.
例えば、複合材用、接着剤用等は外部応力として、応力
集中等の瞬間的な衝撃に耐えることが要求されている。For example, materials for composite materials, adhesives, etc. are required to withstand instantaneous impacts such as stress concentration as external stress.
このため、理想的にはゴムのように弾性変形することが
重要な要素として注目されている。このような弾性変形
を判断する基準としては、特にマトリックス樹脂の破断
時の伸びが重要である。マトリックス樹脂の伸びが大き
い程、複合材等で要求されるガラス繊維やカーボン繊維
等の補強剤の欠点を補うことができる。すなわち、複合
材全体として強度向上になる。For this reason, ideally, elastic deformation like rubber is attracting attention as an important element. As a criterion for determining such elastic deformation, elongation of the matrix resin at break is especially important. The greater the elongation of the matrix resin, the more it can compensate for the drawbacks of reinforcing agents such as glass fiber and carbon fiber required for composite materials. In other words, the strength of the composite material as a whole is improved.
また、このような複合材や接着剤は湿式で含浸成形され
ることが一般的であり、エポキシ樹脂が常温で液状であ
れば、本来不要な有機溶剤の使用や加熱溶融状態での作
業が必要でなく、この結果使用量の減少や作業性の向上
になる。In addition, such composite materials and adhesives are generally wet-impregnated and molded, and if the epoxy resin is liquid at room temperature, it is necessary to use unnecessary organic solvents and work in a heated molten state. As a result, the amount used is reduced and workability is improved.
更に、これらマトリックス樹脂においては長期間の保存
安定性も重要であり、空気中の酸素による劣化が小さい
ことも要求されている。この耐酸化性は主に樹脂の構造
に由来するもので、フェノールノボラック樹脂構造では
この問題は解決し得ない。Furthermore, long-term storage stability is also important for these matrix resins, and they are also required to be less susceptible to deterioration due to oxygen in the air. This oxidation resistance is mainly derived from the structure of the resin, and this problem cannot be solved with a phenol novolac resin structure.
最近、これら求められている要素のうち、耐熱性ととも
に耐酸化性を改良したフェノール−キシレン結合樹脂の
エポキシ化物が提案されている(特公昭47−1378
2、特開昭60−112813)。Recently, among these required elements, an epoxidized product of phenol-xylene bonded resin with improved heat resistance and oxidation resistance has been proposed (Japanese Patent Publication No. 47-1378
2, Japanese Unexamined Patent Publication No. 112813/1983).
しかしながら、これらのエポキシ樹脂は、いずれもフェ
ノールとアラルキルエーテルを実質的に未反応物が残ら
ないように縮合反応させた組成物から成る。However, all of these epoxy resins are composed of a composition in which phenol and aralkyl ether are subjected to a condensation reaction so that substantially no unreacted materials remain.
このため、2官能のアラルキルエーテル1モルに対して
用いられるフェノールの量は 1.3〜3モルの範囲に
限定されているが、この範囲で得られる樹脂は分子量が
大きく、流動性や性能の点て不満足である。したがって
、作業性の面で非能率的であるばかりでなく、固有の機
械的特性、特に破断時の伸び率では複合材等で要求され
るような水準に達していない。For this reason, the amount of phenol used per mole of bifunctional aralkyl ether is limited to a range of 1.3 to 3 moles, but resins obtained within this range have a large molecular weight and have poor fluidity and performance. I am not satisfied with the results. Therefore, not only is it inefficient in terms of workability, but its inherent mechanical properties, especially its elongation at break, do not reach the level required for composite materials.
本発明は上記問題点に鑑み成されたものであり、その目
的は耐熱性、耐水性、耐酸化性において十分な性能を示
し、耐衝撃性などの機械的特性に優れ、さらには作業性
に優れた、耐熱性複合材用マトリックス樹脂、耐熱性接
着剤等に供するに有用なエポキシ樹脂およびその製造方
法を提供することにある。The present invention was made in view of the above problems, and its purpose is to exhibit sufficient performance in heat resistance, water resistance, and oxidation resistance, excellent mechanical properties such as impact resistance, and further improve workability. It is an object of the present invention to provide an epoxy resin that is excellent and useful for use as a matrix resin for heat-resistant composite materials, a heat-resistant adhesive, etc., and a method for producing the same.
(問題点を解決するための手段)
本発明者らは前記目的を達成するために鋭意検討した結
果、本発明を完成するに至ったものである。(Means for Solving the Problems) The present inventors have completed the present invention as a result of intensive studies to achieve the above object.
すなわち本発明は、
一般式(a)
(但し、式中のnは0〜5の整数を示す。)で表わされ
るフェノールアラルキル樹脂とエピハロヒドリンをハロ
ゲン化水素アクセプターの存在下に反応させて得られる
エポキシ樹脂、および一般式(b)
ROGIIべ)ocH2oR(b)
(但し、式中のRは炭素数が4以下の低級アルキル基を
示す。)
で表わされるα、α゛−ジアルコキシーp−キシレンに
4モル比以上のフェノールを反応させて得られた反応生
成物から未反応のフェノールを回収し、一般式(a)で
表わされるフェノールアラルキル樹脂を主成分とする反
応生成物とエピハロヒドリンをハロゲン化水素アクセプ
ターの存在下で反応させることを特徴とするエポキシ樹
脂の製造方法である。That is, the present invention provides an epoxy resin obtained by reacting a phenol aralkyl resin represented by the general formula (a) (wherein n is an integer of 0 to 5) and epihalohydrin in the presence of a hydrogen halide acceptor. resin, and α, α゛-dialkoxy p-xylene represented by the general formula (b) ROGII (b) (wherein R represents a lower alkyl group having 4 or less carbon atoms) Unreacted phenol is recovered from the reaction product obtained by reacting phenol in a molar ratio or higher, and the reaction product containing a phenol aralkyl resin represented by general formula (a) as a main component and epihalohydrin are combined with a hydrogen halide acceptor. This is a method for producing an epoxy resin characterized by carrying out the reaction in the presence of.
本発明の方法で得られるフェノールアラルキル樹脂のエ
ポキシ化物は、種々の硬化剤と組み合せることによって
良好な硬化物を与える。例えば、酸無水物(商品名エピ
キュアY II −306、シェル化学製)を硬化剤と
して組み合せた場合、ビスフェノールAを骨格とするエ
ポキシ樹脂に対し、引張強度、伸び率とも2倍以上の数
値を示す。また特公昭47−13782に例示された範
囲のモル比により得たフェノール−キシレン結合樹脂を
骨格とするもの(フェノール対α、α°−ジアルコキシ
−p−キシレンのモル比が1.9対1;軟化点73.5
℃)と比較しても、引張強度、伸び率とも約1.5倍優
れていることが認められる。The epoxidized phenol aralkyl resin obtained by the method of the present invention provides a good cured product when combined with various curing agents. For example, when an acid anhydride (trade name Epicure Y II-306, manufactured by Shell Chemical Co., Ltd.) is combined as a curing agent, the tensile strength and elongation rate are more than double that of epoxy resin with a bisphenol A skeleton. . Also, those having a skeleton of a phenol-xylene bonded resin obtained with a molar ratio within the range exemplified in Japanese Patent Publication No. 47-13782 (the molar ratio of phenol to α,α°-dialkoxy-p-xylene is 1.9:1) ; Softening point 73.5
℃), both tensile strength and elongation rate are found to be about 1.5 times better.
更に、本発明のエポキシ樹脂は常温で油状であるため、
配合、塗布、含浸等の操作は極めて良好であり、均質な
硬化生成物が得られることも特徴として挙げられる。Furthermore, since the epoxy resin of the present invention is oily at room temperature,
Operations such as blending, coating, and impregnation are extremely easy, and a homogeneous cured product can be obtained.
上述のような効果を得るために、一般式(a)で表わさ
れるフェノールアラルキル樹脂の繰り返し単位nが5以
下のものを、本発明に用いる。ただし、より顕著な効果
を得るためには、n=5のものが15重量%未満である
ことが望ましく、あるいはn=oとn=1のものの合計
が50モル%以上であることが望ましく、さらにはn=
oとn=1のものの合計が60モル%以上であることが
より望ましい。In order to obtain the above effects, a phenol aralkyl resin represented by the general formula (a) having a repeating unit n of 5 or less is used in the present invention. However, in order to obtain a more remarkable effect, it is desirable that the amount of n=5 is less than 15% by weight, or the total of n=o and n=1 is preferably 50% by mole or more, Furthermore, n=
It is more desirable that the total of o and n=1 is 60 mol% or more.
上記のような繰り返し単位nの範囲を有する一般式(a
)で表わされるフェノールアラルキル樹脂を得るための
方法の具体例を以下で述べる。General formula (a
A specific example of a method for obtaining a phenol aralkyl resin represented by () will be described below.
まず、一般式(b)で表わされるα、α°−ジアルコキ
シーp−キシレン1モルに対して、フェノールを4モル
以上、望ましくは5〜20モル、さらに好ましくは6〜
15モルの範囲で加え、酸触媒の存在下でそのまま昇温
して後述の温度で反応させる。First, 4 or more moles of phenol, preferably 5 to 20 moles, more preferably 6 to 20 moles, is added to 1 mole of α,α°-dialkoxy p-xylene represented by the general formula (b).
It is added in an amount of 15 mol, and the temperature is raised as it is in the presence of an acid catalyst to cause the reaction to occur at the temperature described below.
反応が進行するにつれて生成するアルコールを系外にト
ラップする。必要によっては系内に残存する微量のアル
コールを窒素により糸外に除去する。反応終了後、当然
のことながら未反応のフェノールが残存するが、これを
真空下で留去させるか、または水蒸気蒸留によって留去
させて得られた残査の樹脂が上記のようなフェノールア
ラルキル樹脂である。The alcohol produced as the reaction progresses is trapped outside the system. If necessary, trace amounts of alcohol remaining in the system are removed from the thread using nitrogen. After the reaction is completed, unreacted phenol naturally remains, but this is distilled off under vacuum or by steam distillation, and the residual resin obtained is the phenol aralkyl resin as described above. It is.
このα、α°−ジアルコキシーp−キシレンにおいてア
ルキル基Rの炭素原子数が4以下であると反応が早く、
また炭素原子数が4、すなわちブチル基においでter
t−ブチル基は反応が遅い傾向にある。したがって、本
発明で用いるものとしては、好ましくは、α、α°−ジ
メトキシーp−キシレン、α、α°−ジェトキシーp−
キシレン、α、α゛−ジーn−プロポキシーp−キシレ
ン、α、α°−イソプロポキシーp−キシレン、α、α
“−ジ−n−ブトキシ−p−キシレン、α、α°−ジー
5ec−ブトキシーp−キシレン、α、α°−ジイソブ
チルーp−キシレン等が挙げられるが、これらに限定さ
れるものではない。When the number of carbon atoms in the alkyl group R in this α, α°-dialkoxy p-xylene is 4 or less, the reaction is rapid;
In addition, the number of carbon atoms is 4, that is, in the butyl group, ter
T-butyl groups tend to react slowly. Therefore, those used in the present invention are preferably α, α°-dimethoxy p-xylene, α, α°-dimethoxy p-xylene, α, α°-dimethoxy p-xylene,
xylene, α, α゛-di-n-propoxy p-xylene, α, α°-isopropoxy p-xylene, α, α
Examples include, but are not limited to, -di-n-butoxy-p-xylene, α,α°-di-5ec-butoxy-p-xylene, α,α°-diisobutyl-p-xylene, and the like.
反応温度は110℃以上の温度であることが必要であり
、 110℃より低いと反応は極端に遅くなる。また反
応時間を出来るだけ短縮するためには約130〜240
℃の温度範囲が望ましい。反応時間は 1〜20時間で
ある。The reaction temperature needs to be 110°C or higher; if it is lower than 110°C, the reaction will be extremely slow. In addition, in order to shorten the reaction time as much as possible, approximately 130 to 240
A temperature range of °C is preferred. Reaction time is 1 to 20 hours.
酸触媒としては無機または有機の酸、殊に鉱酸、例えば
塩酸、リン酸、硫酸またはギ酸を、あるいは塩化亜鉛、
塩化第二錫、塩化第二鉄の様なフリーゾルタラフッ形触
媒を、メタンスルホン酸またはp−トルエンスルホン酸
などの有機スルホン酸を単独で使用するかまたは併用し
てもよい。Acid catalysts include inorganic or organic acids, in particular mineral acids, such as hydrochloric acid, phosphoric acid, sulfuric acid or formic acid, or zinc chloride,
A free sol fluorine catalyst such as stannic chloride or ferric chloride may be used alone or in combination with an organic sulfonic acid such as methanesulfonic acid or p-toluenesulfonic acid.
触媒の使用量は、フェノール、α、α°−ジアルコキシ
ーp−キシレンの全重量の約0.01〜5重量%である
。The amount of catalyst used is about 0.01 to 5% by weight of the total weight of phenol, α, α°-dialkoxy p-xylene.
このようにして得られたフェノールアラルキル樹脂を主
成分とする反応生成物をエポキシ化する方法は、公知の
方法が適用できる。A known method can be applied to epoxidize the reaction product containing the phenol aralkyl resin as a main component.
すなわち、残査樹脂とエピハロヒドリン、好適にはエピ
クロルヒドリンにより通常40〜120℃の温度範囲内
でハロゲン化水素アクセプターの存在下に行なわれる。That is, the reaction is carried out using residual resin and epihalohydrin, preferably epichlorohydrin, usually within a temperature range of 40 to 120 DEG C., in the presence of a hydrogen halide acceptor.
本発明のハロゲン化水素アクセプターとして特に適当な
ものは、アルカリ金属水酸化物、例えば水酸化カリウム
、水酸化ナトリウムである。ハロゲン化水素アクセプタ
ーは前記フェノールアラルキル樹脂とエピハロヒドリン
との加熱された混合物に徐々に添加され反応混合物のp
Hを約6.5〜10に維持するようにするのが好適であ
る。Particularly suitable as hydrogen halide acceptors according to the invention are alkali metal hydroxides such as potassium hydroxide, sodium hydroxide. A hydrogen halide acceptor is gradually added to the heated mixture of the phenolic aralkyl resin and epihalohydrin and the hydrogen halide acceptor is added slowly to the heated mixture of the phenolic aralkyl resin and epihalohydrin.
It is preferred to maintain H between about 6.5 and 10.
反応に使用されるエピハロヒドリンの割合は残査樹脂の
水酸基含有量によるが、通常、 2.0〜30当量、好
ましくは経済性を考慮すれば10当量以下の過剰量のエ
ピハロヒドリンが使用される。反応生成物から過剰のア
クセプター物質および副生する塩の除去は真空蒸留や水
洗等の手段によって行なわれる。The proportion of epihalohydrin used in the reaction depends on the hydroxyl group content of the residual resin, but usually an excess of 2.0 to 30 equivalents, preferably 10 equivalents or less in consideration of economic efficiency, is used. Excess acceptor substances and by-product salts are removed from the reaction product by means such as vacuum distillation or washing with water.
また本発明の方法によって製造されたエポキシ樹脂は慣
用の硬化剤で硬化させることができる。The epoxy resin produced by the method of the invention can also be cured with conventional curing agents.
硬化剤の典型的な例は、エポキシ樹脂のための慣用硬化
剤でビス(4−アミノフェニル)メタン、アニリン/ホ
ルムアルデヒド樹脂、ビス(4−アミノフェニル)スル
ホン、プロパン−1,3−ジアミン、ヘキサメチレンジ
アミン、ジエチレントリアミン、トリエチレンテトラミ
ン、2,2.4−トリメチルへキサミノ−1,6−ジア
ミン、m−キシリレンジアミン、ビス(4−アミノシク
ロヘキシル)メタン、2.2−ビス(4−アミノシクロ
ヘキシル)プロパンおよび3−アミノメチル−3,5,
5−トリメチルシクロヘキシルアミン(イソホロンジア
ミン)のような脂肪族、脂環式、芳香族および複素環式
アミン;脂肪族ポリアミンと三量化又は三量化脂肪酸か
ら得られるようなポリアミノアミド;レゾルシノール、
ヒドロキノン、2.2−ビス(4−ヒドロキシフェニル
)プロパンおよびフェノール/アルデヒド樹脂のような
ポリフェノール; “チオコールズとして市販されてい
るようなポリチオール;例えば無水フタル酸、無水テト
ラヒドロフタル酸、ヘキサヒドロフタル酸無水物、ヘキ
サクロロエンドメチレンテトラヒドロフタル酸無水物、
ピロメリト酸無水物、3,3°、4,4−ベンゾフェノ
ンテトラカルボン酸2無水物、前記無水物の酸並びにイ
ソフタル酸およびテレフタル酸のようなポリカルボン酸
およびその無水物を含む。硬化剤がポリカルボン酸また
はそれらの無水物であるなら、通常0.4ないし1.1
当量のカルボキシル基または無水物基が1当量のエポキ
シ基に対して用いられる。硬化剤がポリフェノールであ
るなら、1当量のエポキシ基につき0.75ないし1.
25のフェノール性水酸基を使用することが都合よい。Typical examples of hardeners are conventional hardeners for epoxy resins such as bis(4-aminophenyl)methane, aniline/formaldehyde resins, bis(4-aminophenyl)sulfone, propane-1,3-diamine, hexa Methylenediamine, diethylenetriamine, triethylenetetramine, 2,2,4-trimethylhexamino-1,6-diamine, m-xylylenediamine, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl) ) propane and 3-aminomethyl-3,5,
Aliphatic, cycloaliphatic, aromatic and heterocyclic amines such as 5-trimethylcyclohexylamine (isophorone diamine); polyaminoamides such as those obtained from aliphatic polyamines and trimerization or trimerized fatty acids; resorcinol,
Polyphenols such as hydroquinone, 2,2-bis(4-hydroxyphenyl)propane and phenol/aldehyde resins; polythiols such as those commercially available as Thiochols; e.g. phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride Hexachloroendomethylenetetrahydrophthalic anhydride,
Includes pyromellitic anhydride, 3,3°,4,4-benzophenonetetracarboxylic dianhydride, the acids of said anhydrides and polycarboxylic acids and their anhydrides such as isophthalic acid and terephthalic acid. If the curing agent is a polycarboxylic acid or anhydride thereof, usually 0.4 to 1.1
An equivalent amount of carboxyl or anhydride group is used per equivalent of epoxy group. If the curing agent is a polyphenol, 0.75 to 1.0% per equivalent of epoxy group.
It is convenient to use 25 phenolic hydroxyl groups.
触媒的硬化剤は重量でエポキシ100部につき1ないし
40部が一般に用いられる。Catalytic hardeners are generally used in amounts of 1 to 40 parts by weight per 100 parts of epoxy.
以下、本発明を実施例により更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例1
攪拌器、温度計、およびディーンスターク共沸蒸留トラ
ップを装着した反応容器にα、α°−ジメトキシーp−
キシレン250g(1,5モル)、フェノール847g
(9,0モル)、およびパラトルエンスルホン酸1.1
gを装入し、その混合溶液を130℃〜150℃に保ち
ながら攪拌を続けた。反応中、生成するメタノールは順
次トラップより糸外へ除去した。Example 1 α, α°-Dimethoxy p-
250 g (1.5 moles) of xylene, 847 g of phenol
(9.0 mol), and para-toluenesulfonic acid 1.1
g was charged, and stirring was continued while maintaining the mixed solution at 130°C to 150°C. During the reaction, generated methanol was sequentially removed from the thread through the trap.
3時間でメタノールの発生が無くなり縮合が完了した。After 3 hours, no methanol was generated and the condensation was completed.
次に、未反応のフェノールを2圧蒸留し、一般式(a)
の構造を持つ393gのフェノールアラルキル樹脂組成
物を得た。Next, unreacted phenol is distilled under two pressures, and the general formula (a) is expressed as
393 g of a phenol aralkyl resin composition having the structure was obtained.
得られた樹脂の組成を、高速液体クロマトグラフィーで
測定した結果、n=oが60J、n=1が24.3、n
=2が9.2、n=3が3.8、n≧4のものが2.4
(モル%)であった。The composition of the obtained resin was measured by high performance liquid chromatography and found that n=o was 60J, n=1 was 24.3, and n
=2 is 9.2, n=3 is 3.8, n≧4 is 2.4
(mol%).
この樹脂393gとエピクロルヒドリン1100g(1
1,9モル)を混合し攪拌器、ディーンスターク共沸蒸
留トラップおよび滴下ロートを装着した反応容器に装入
した。393g of this resin and 1100g of epichlorohydrin (1
1.9 mol) was mixed and charged into a reaction vessel equipped with a stirrer, a Dean-Stark azeotropic distillation trap, and a dropping funnel.
この混合物を攪拌しながら 115〜119℃に昇温し
たのち同温度で40%水酸化ナトリウム水溶液275g
を4時間で滴下し、留出した水は連続的に分離回収し、
エピクロルヒドリンの相は反応器に戻した。滴下終了後
留出水の除去により反応は終了する。While stirring this mixture, the temperature was raised to 115-119°C, and then at the same temperature, 275 g of a 40% aqueous sodium hydroxide solution was added.
was added dropwise over 4 hours, and the distilled water was continuously separated and collected.
The epichlorohydrin phase was returned to the reactor. After the dropwise addition is completed, the reaction is completed by removing the distilled water.
この後過剰のエピクロルヒドリンを減圧蒸留し、反応生
成物をメチルイソブチルケトン(MIBに)1500g
に溶解し、塩化ナトリウムおよび少過剰の水酸化ナトリ
ウムを濾過した後、溶剤を減圧蒸留により留去し、黄色
油状のエポキシ樹脂を465g得た。After that, excess epichlorohydrin was distilled under reduced pressure, and 1500 g of the reaction product was converted into methyl isobutyl ketone (MIB).
After filtering out sodium chloride and a slight excess of sodium hydroxide, the solvent was distilled off under reduced pressure to obtain 465 g of a yellow oily epoxy resin.
エポキシ当量は227g/eq 、粘度(東京計器製E
型粘度計による)は、468g/cm−sec (35
℃)であった。Epoxy equivalent is 227g/eq, viscosity (Tokyo Keiki E)
(by type viscometer) is 468 g/cm-sec (35 g/cm-sec)
℃).
このIR分析結果(液膜法)を第1図に示す。The results of this IR analysis (liquid film method) are shown in FIG.
実施例2
攪拌器、温度計、およびディーンスターク共沸蒸留トラ
ップを装着した反応容器にα、α゛−ジメトキシーp−
キシレン250g(1,5モル)、フェノール1411
g(15モル)、およびパラトルエンスルホン酸8.3
gを装入し、その混合溶液を130〜150℃に保ちな
がら攪拌を行った。Example 2 α,α゛-dimethoxyp-
250 g (1.5 moles) of xylene, 1411 phenol
g (15 mol), and para-toluenesulfonic acid 8.3
g was charged, and the mixed solution was stirred while being maintained at 130 to 150°C.
生成するメタノールを蒸留除去した。The methanol produced was removed by distillation.
2時間でメタノールの発生が無くなり、縮合が完了した
ところで未反応のフェノールを減圧蒸留除去し、一般式
(a)の構造を持つ385gのフェノールアラルキル樹
脂組成物を得た。After 2 hours, no methanol was generated and the condensation was completed. Unreacted phenol was removed by distillation under reduced pressure to obtain 385 g of a phenol aralkyl resin composition having the structure of general formula (a).
得られた樹脂の組成を、高速液体クロマトグラフィーで
測定した結果、n=oが76.5.n=1が18.6、
n=2が4.4、n≧3のものが0.5(モル%)であ
った。The composition of the obtained resin was measured by high performance liquid chromatography and found that n=o was 76.5. n=1 is 18.6,
n=2 was 4.4, and n≧3 was 0.5 (mol%).
この樹脂385gとエピクロルヒドリンt ioo g
(11,9モル)を混合し攪拌器、ディーンスターク共
沸蒸留トラップおよび滴下ロートを装着した反応容器に
装入した。385g of this resin and epichlorohydrin
(11.9 mol) were mixed and charged to a reaction vessel equipped with a stirrer, a Dean-Stark azeotropic distillation trap, and a dropping funnel.
この混合物を攪拌しながら115〜119℃に昇温した
のち同温度で40%水酸化ナトリウム水溶液275gを
4時間で滴下し、留出した水は連続的に分離回収し、エ
ピクロルヒドリンの相は反応器に戻した。滴下終了後留
出水の除去により反応は終了する。The temperature of this mixture was raised to 115-119°C while stirring, and at the same temperature, 275 g of a 40% aqueous sodium hydroxide solution was added dropwise over 4 hours. The distilled water was continuously separated and collected, and the epichlorohydrin phase was transferred to the reactor. I returned it to . After the dropwise addition is completed, the reaction is completed by removing the distilled water.
この後過剰のエピクロルヒドリンを減圧蒸留し、反応生
成物をメチルイソブチルケトン(MIBK)1500g
に溶解し、塩化ナトリウムおよび少過剰の水酸化ナトリ
ウムを濾過した後、溶剤を減圧蒸留により留去し、黄色
油状のエポキシ樹脂を451g得た。After that, excess epichlorohydrin was distilled under reduced pressure, and 1500 g of methyl isobutyl ketone (MIBK) was obtained as a reaction product.
After filtering out sodium chloride and a slight excess of sodium hydroxide, the solvent was distilled off under reduced pressure to obtain 451 g of a yellow oily epoxy resin.
エポキシ当量は219g/eq、粘度(東京計器製E型
粘度計による)は、 123g/cm−sec (15
℃)であった。The epoxy equivalent is 219 g/eq, and the viscosity (according to Tokyo Keiki E-type viscometer) is 123 g/cm-sec (15
℃).
比較例1
攪拌器、温度計、およびディーンスターク共沸蒸留トラ
ップを装着した反応容器にα、α°−ジメトキシーp−
キシレン166g(1,0モル)、フェノール179g
(1,9モル)、パラトルエンスルホン酸1.5gを装
入し、その混合溶液を130℃〜150℃に保ちながら
攪拌を行った。Comparative Example 1 α, α°-Dimethoxy p-
Xylene 166g (1.0 mol), phenol 179g
(1.9 mol) and 1.5 g of para-toluenesulfonic acid were charged, and the mixed solution was stirred while being maintained at 130°C to 150°C.
反応中生成するメタノールを蒸留除去した。Methanol produced during the reaction was distilled off.
3時間でメタノールの発生が無くなり、縮合が完了する
と一般式(a)の構造を持つフェノールアラルキル樹脂
組成物を280g得た。After 3 hours, no methanol was generated, and when the condensation was completed, 280 g of a phenol aralkyl resin composition having the structure of general formula (a) was obtained.
得られた樹脂の平均分子量は2054であり、この平均
分子量から推定すると平均繰返し単位πはIOである。The average molecular weight of the obtained resin was 2054, and estimated from this average molecular weight, the average repeating unit π was IO.
また、軟化点(JIS−に−2548の環球法軟化点測
定装置による)は、73.5℃であった。Further, the softening point (according to a JIS-2548 ring and ball softening point measuring device) was 73.5°C.
この樹脂240gとエピクロルヒドリン694g(7,
5モル)を混合し攪拌器、ディーンスターク共沸蒸留ト
ラップおよび滴下ロートを装着した反応容器に装入した
。240g of this resin and 694g of epichlorohydrin (7,
5 mol) were mixed and charged into a reaction vessel equipped with a stirrer, a Dean-Stark azeotropic distillation trap, and a dropping funnel.
この混合物を攪拌しながら115〜119℃に昇温した
のち同温度で40%水酸化ナトリウム水溶液165gを
3時間で滴下し、留出した水は連続的に分離回収し、エ
ピクロルヒドリンの相は反応器に戻した。滴下終了後、
留出水の除去により反応は終了する。The temperature of this mixture was raised to 115-119°C with stirring, and then 165 g of a 40% aqueous sodium hydroxide solution was added dropwise over 3 hours at the same temperature, the distilled water was continuously separated and collected, and the epichlorohydrin phase was transferred to the reactor. I returned it to . After the dripping is finished,
The reaction is terminated by removing the distillate water.
この後、過剰のエピクロルヒドリンを減圧蒸留し、反応
生成物をメチルイソブチルケトン(MIBに〉1500
gに溶解し、塩化ナトリウムおよび少過剰の水酸化ナト
リウムを濾過した後、溶剤を減圧蒸留により留去し、黄
色固体状のエポキシ樹脂を275g得た。After this, excess epichlorohydrin was distilled under reduced pressure, and the reaction product was converted to methyl isobutyl ketone (MIB)
After filtering out sodium chloride and a slight excess of sodium hydroxide, the solvent was distilled off under reduced pressure to obtain 275 g of a yellow solid epoxy resin.
エポキシ当量は274g/eq 、軟化点(JIS−に
−2548による環球法軟化点測定装置による)は、5
4℃であフた。The epoxy equivalent is 274 g/eq, and the softening point (according to JIS-2548 ring and ball softening point measurement device) is 5.
Cool at 4°C.
使用例1
実施例1.2、および比較例1によって得られたエポキ
シ樹脂、並びにビスフェノールAから導入されるエビコ
ー)828(シェル化学製)の各々に、硬化剤として液
状MDA (エビキュア2;シェル化学製)を表−1に
示す条件で配合し、その混合物をそれぞれ注型加工し、
加工後の硬化樹脂の機械的性質を測定した。その結果を
表−1に示す。Usage Example 1 Each of the epoxy resins obtained in Example 1.2 and Comparative Example 1, and Ebicure 828 (manufactured by Shell Chemical Co., Ltd.) introduced from bisphenol A was added with liquid MDA (Ebicure 2; Shell Chemical Co., Ltd.) as a curing agent. ) were mixed under the conditions shown in Table 1, and each mixture was cast into a mold.
The mechanical properties of the cured resin after processing were measured. The results are shown in Table-1.
使用例2
実施例1.2、および比較例1によって得られたエポキ
シ樹脂、並びにビスフェノールAから導入されるエピコ
ート828(シェル化学製)の各々に、硬化剤として酸
無水物(エビキュアYH−306:シエル化学製)、促
進剤として2,4.6−トリス(ジメチルアミノメチル
)フェノール(TAP)を、表−2に示す条件で配合し
、その混合物をそれぞれ注型加工し、加工後の硬化樹脂
の機械的性質を測定した。その結果を表−2に示す。Use Example 2 An acid anhydride (Ebicure YH-306: (manufactured by Ciel Chemical) and 2,4.6-tris(dimethylaminomethyl)phenol (TAP) as an accelerator were blended under the conditions shown in Table 2, the mixtures were cast, and the cured resin after processing. Mechanical properties were measured. The results are shown in Table-2.
(表−1,2の注) ・配 合・・・・・・・・・・・・重量比。(Notes on Tables 1 and 2) ・Distribution・・・・・・・・・Weight ratio.
・ゲル化時間・・・・・・JIS、に−6910による
。・Gelation time: Based on JIS-6910.
・熱変形温度・・・・・−JIS 、に−7207によ
る。・Heat deformation temperature: According to JIS, 7207.
・煮沸時吸水率・・・煮沸100℃/2時間。・Water absorption rate when boiling: Boiling at 100℃/2 hours.
・曲げ強度・・−−−−−−−JIS、に−7203に
よ兆。・Bending strength: According to JIS-7203.
・引張強度・・・・−−−−−J I S 、に−71
13による。・Tensile strength...---JIS, ni-71
According to 13.
以上説明したきたように、本発明のエポキシ樹脂は、常
温において液体であるため作業性に優れ、またその硬化
物は、耐熱性、耐水性、耐酸化性において十分な性能を
示し、さらには耐8T撃性などの機械的特性が優れるの
で、各種用途への展開が期待でき、特に従来から上記の
ような性能が要望されていた電子材料分野への展開が有
望視される。As explained above, the epoxy resin of the present invention is liquid at room temperature, so it has excellent workability, and its cured product shows sufficient performance in heat resistance, water resistance, oxidation resistance, and furthermore, Since it has excellent mechanical properties such as 8T impact resistance, it can be expected to be used in a variety of applications, especially in the field of electronic materials, where the above-mentioned performance has long been desired.
第1図は、実施例1のエポキシ樹脂のIR分析結果(液
膜法)を示す図である。FIG. 1 is a diagram showing the IR analysis results (liquid film method) of the epoxy resin of Example 1.
Claims (1)
るフェノールアラルキル樹脂とエピハロヒドリンをハロ
ゲン化水素アクセプターの存在下に反応させて得られる
エポキシ樹脂。 2)一般式(b) ▲数式、化学式、表等があります▼(b) (但し、式中のRは炭素数が4以下の低級アルキル基を
示す。) で表わされるα,α′−ジアルコキシ−p−キシレンに
4モル比以上のフェノールを反応させて得られた反応生
成物から未反応のフェノールを回収し、 一般式(a) ▲数式、化学式、表等があります▼(a) (但し、式中のnは0〜5の整数を示す。)で表わされ
るフェノールアラルキル樹脂を主成分とする反応生成物
とエピハロヒドリンをハロゲン化水素アクセプターの存
在下で反応させることを特徴とするエポキシ樹脂の製造
方法。[Claims] 1) General formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) (However, n in the formula represents an integer from 0 to 5.) Phenol aralkyl resin and An epoxy resin obtained by reacting epihalohydrin in the presence of a hydrogen halide acceptor. 2) General formula (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(b) (However, R in the formula represents a lower alkyl group having 4 or less carbon atoms.) Unreacted phenol is recovered from the reaction product obtained by reacting alkoxy-p-xylene with phenol in a molar ratio of 4 or more. (where n in the formula is an integer of 0 to 5.) An epoxy resin characterized by reacting a reaction product containing a phenol aralkyl resin represented by the formula as a main component with epihalohydrin in the presence of a hydrogen halide acceptor. manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62070281A JPH0753790B2 (en) | 1987-03-26 | 1987-03-26 | Epoxy resin composition and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62070281A JPH0753790B2 (en) | 1987-03-26 | 1987-03-26 | Epoxy resin composition and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63238122A true JPS63238122A (en) | 1988-10-04 |
JPH0753790B2 JPH0753790B2 (en) | 1995-06-07 |
Family
ID=13426949
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62070281A Expired - Lifetime JPH0753790B2 (en) | 1987-03-26 | 1987-03-26 | Epoxy resin composition and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0753790B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0390075A (en) * | 1989-09-01 | 1991-04-16 | Nippon Steel Chem Co Ltd | Epoxy resin, its intermediate and production thereof |
JPH04244803A (en) * | 1991-01-29 | 1992-09-01 | Noritake Co Ltd | Molding equipment using gypsum mold |
US5223602A (en) * | 1992-01-24 | 1993-06-29 | Nippon Steel Chemical Co., Ltd. | Naphthol aralkyl resins and cured products thereof |
CN103694450A (en) * | 2013-11-15 | 2014-04-02 | 山东圣泉化工股份有限公司 | Fire retardation epoxy resin and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60112813A (en) * | 1983-11-24 | 1985-06-19 | Dainippon Ink & Chem Inc | Epoxy resin composition for molding material |
-
1987
- 1987-03-26 JP JP62070281A patent/JPH0753790B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60112813A (en) * | 1983-11-24 | 1985-06-19 | Dainippon Ink & Chem Inc | Epoxy resin composition for molding material |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0390075A (en) * | 1989-09-01 | 1991-04-16 | Nippon Steel Chem Co Ltd | Epoxy resin, its intermediate and production thereof |
US5068293A (en) * | 1989-09-01 | 1991-11-26 | Nippon Steel Chemical Co., Ltd. | Naphthol-based epoxy resins, intermediates for the same, process for preparing the same, and epoxy resin compositions containing the same |
JPH05393B2 (en) * | 1989-09-01 | 1993-01-05 | Shinnittetsu Kagaku | |
JPH04244803A (en) * | 1991-01-29 | 1992-09-01 | Noritake Co Ltd | Molding equipment using gypsum mold |
US5223602A (en) * | 1992-01-24 | 1993-06-29 | Nippon Steel Chemical Co., Ltd. | Naphthol aralkyl resins and cured products thereof |
CN103694450A (en) * | 2013-11-15 | 2014-04-02 | 山东圣泉化工股份有限公司 | Fire retardation epoxy resin and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH0753790B2 (en) | 1995-06-07 |
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