JPH03199220A - Polyhydric phenols and curing agent for epoxy resin, comprising same phenols as main component - Google Patents
Polyhydric phenols and curing agent for epoxy resin, comprising same phenols as main componentInfo
- Publication number
- JPH03199220A JPH03199220A JP34145189A JP34145189A JPH03199220A JP H03199220 A JPH03199220 A JP H03199220A JP 34145189 A JP34145189 A JP 34145189A JP 34145189 A JP34145189 A JP 34145189A JP H03199220 A JPH03199220 A JP H03199220A
- Authority
- JP
- Japan
- Prior art keywords
- phenols
- epoxy resin
- carbonyl compound
- phenol
- curing agent
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 25
- 150000002989 phenols Chemical class 0.000 title claims description 27
- 239000003795 chemical substances by application Substances 0.000 title claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 aromatic carbonyl compound Chemical class 0.000 claims abstract description 17
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 238000009833 condensation Methods 0.000 claims abstract description 5
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 abstract description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 abstract description 4
- 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 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229930003836 cresol Natural products 0.000 abstract description 3
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 abstract description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 abstract description 2
- 235000012141 vanillin Nutrition 0.000 abstract description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 abstract description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 abstract description 2
- 235000013824 polyphenols Nutrition 0.000 description 10
- 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 9
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 238000010521 absorption reaction Methods 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-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
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- NSENZNPLAVRFMJ-UHFFFAOYSA-N 2,3-dibutylphenol Chemical compound CCCCC1=CC=CC(O)=C1CCCC NSENZNPLAVRFMJ-UHFFFAOYSA-N 0.000 description 1
- HRQPPTDGMMGDKC-UHFFFAOYSA-N 2,3-dipropylphenol Chemical compound CCCC1=CC=CC(O)=C1CCC HRQPPTDGMMGDKC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical compound CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 description 1
- AOKSOKUXKQEENT-UHFFFAOYSA-N 2-hexyl-3-methylphenol Chemical compound CCCCCCC1=C(C)C=CC=C1O AOKSOKUXKQEENT-UHFFFAOYSA-N 0.000 description 1
- SRJCJJKWVSSELL-UHFFFAOYSA-N 2-methylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C)=CC=C21 SRJCJJKWVSSELL-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- FCUBUGPGVCEURB-UHFFFAOYSA-N 3-methyl-2-propylphenol Chemical compound CCCC1=C(C)C=CC=C1O FCUBUGPGVCEURB-UHFFFAOYSA-N 0.000 description 1
- PAVVCVOUEPIKQF-UHFFFAOYSA-N 3-phenylpropane-1,1,1-triol Chemical compound OC(O)(O)CCC1=CC=CC=C1 PAVVCVOUEPIKQF-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-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
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、フェノール類と接種類のカルボニル化合物を
縮合して得られる多価フェノール類に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to polyhydric phenols obtained by condensing phenols and a carbonyl compound of the conjugate type.
さらには注型用、成型用、積層用、塗料用、接着剤等、
幅広い用途に使用されるエポキシ樹脂組成物に用いられ
る硬化剤に関する。Furthermore, for casting, molding, lamination, paint, adhesive, etc.
This invention relates to curing agents used in epoxy resin compositions used in a wide range of applications.
〈従来の技術〉
エポキシ樹脂は、接着性、加工性、耐溶剤性等に優れた
特徴を有しており、幅広い用途に使用されている。<Prior Art> Epoxy resins have excellent adhesive properties, processability, solvent resistance, etc., and are used in a wide range of applications.
しかし、近年の著しい技術進展に伴なってそれぞれの用
途分野において、より高性能特に耐熱性が要求されてい
る。However, with remarkable technological progress in recent years, higher performance, particularly heat resistance, is required in each application field.
エポキシ樹脂組成物の耐熱性を改良する方法としては、
エポキシ樹脂自身を改良する以外に、硬化剤を変更する
方法がある。As a method for improving the heat resistance of epoxy resin compositions,
In addition to improving the epoxy resin itself, there is a method of changing the curing agent.
エポキシ樹脂の硬化剤としては、アミン化合物、酸無水
物、フェノール化合物等が有る。Examples of curing agents for epoxy resins include amine compounds, acid anhydrides, and phenol compounds.
−１ｌｌａに、アミン化合物を用いると、耐水性が悪く
、また、毒性の問題がある。-1lla, when an amine compound is used, there is a problem of poor water resistance and toxicity.
また、酸無水物は硬化が遅く、しかも硬化物の耐水性、
接着性等が劣るという欠点がある。In addition, acid anhydride cures slowly, and the cured product has poor water resistance.
It has the disadvantage of poor adhesion.
これらに代るものとして、特に成型材料分野では、耐熱
性、耐水性のバランスのとれたフェノールノボラックが
用いられている。As a substitute for these, phenol novolaks, which have well-balanced heat resistance and water resistance, are used, particularly in the field of molding materials.
しかしながら、近年の半導体技術の進展に伴なって、フ
ェノールノボラック系の硬化剤では、耐熱性が不充分な
用途も増えてきている。However, with the recent progress in semiconductor technology, phenol novolak-based curing agents are increasingly used in applications where heat resistance is insufficient.
例えば、ＩＣ等電子部品の封止剤としては、現在、０−
タレゾールノボラックのグリシジルエーテル等をフェノ
ールノボラックで硬化する系が主流であるが、最近では
、ＩＣの高集積度化、あるいは表面実装化により半田浴
槽への浸漬等により、高耐熱性への要求が高まっている
。For example, currently 0-
The mainstream is a system in which glycidyl ether, etc. of Talesol novolac is cured with phenol novolac, but recently there has been a demand for high heat resistance due to higher integration of ICs or surface mounting, which requires immersion in solder baths. It's increasing.
高耐熱性を指向したエポキシ樹脂用硬化剤に関して、例
えば特開昭５８−１９８５２６号公報には、トリス（ヒ
ドロキシフェニル）メタンが、また特開昭６３−２２８
２４号公報には、フェノール類とサリチルアルデヒドの
縮合物が開示されている。Regarding curing agents for epoxy resins aiming at high heat resistance, for example, JP-A No. 58-198526 discloses tris(hydroxyphenyl)methane, and JP-A No. 63-228
Publication No. 24 discloses a condensate of phenols and salicylaldehyde.
〈発明が解決しようとする課題〉
一般にエポキシ樹脂硬化物の耐熱性を向上させると、耐
湿性が低下する傾向がある。<Problems to be Solved by the Invention> Generally, when the heat resistance of a cured epoxy resin product is improved, the moisture resistance tends to decrease.
前述の特開昭５８−１９８５２６号公報に開示のものは
、耐熱性の向上を意図しているが未だ充分でなく、耐湿
性が低い。Although the method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 58-198526 is intended to improve heat resistance, it is still insufficient and has low moisture resistance.
特開昭６３−２２８２４号公報のものも、耐熱性、耐湿
性のさらに向上が望まれる。The material disclosed in JP-A-63-22824 is also desired to have further improved heat resistance and moisture resistance.
本発明は、耐熱性、耐湿性共に高く、バランスが取れて
いる性質のエポキシ樹脂組成物とする、硬化剤を提供す
ることにある。An object of the present invention is to provide a curing agent that allows an epoxy resin composition to have well-balanced properties, with both high heat resistance and moisture resistance.
（課題を解決するための手段〉
本発明は、フェノール類と、フェノール性水酸基を有す
る芳香族カルボニル化合物および不飽和カルボニル化合
物の共縮合により得られる多価フェノール類である。(Means for Solving the Problems) The present invention is a polyhydric phenol obtained by co-condensation of a phenol, an aromatic carbonyl compound having a phenolic hydroxyl group, and an unsaturated carbonyl compound.
さらには、該多価フェノール類を主成分とするエポキシ
樹脂用硬化剤である。Furthermore, it is a curing agent for epoxy resin containing the polyhydric phenols as a main component.
本発明に用いるフェノール類とは、芳香環に少なくとも
１個のフェノール性水酸基を有する化合物である。The phenols used in the present invention are compounds having at least one phenolic hydroxyl group in an aromatic ring.
具体的に例示すると、フェノール、レゾルシノール、ヒ
ドロキノン等、無置換のフェノール類；クレゾール、エ
チルフェノール、ｎ−プロピルフェノール、ｉ−プロピ
ルフェノール、ｔブチルフェノール、オクチルフェノー
ル、ノニルフェノール、フェニルフェノール等、−置換
フエノール類；キシレノール、メチルプロピルフェノー
ル、メチルブチルフェノール、メチルへキシルフェノー
ル、ジプロピルフェノール、ジブチルフェノール等、二
置換フェノール類；トリメチルフェノールに代表される
三置換フェノール頻；ナフトール、メチルナフトール等
、ナフトール類；ビフェノール、ビスフェノール−Ａ、
ビスフェノール−Ｆ等のビスフェール類が挙げられる。Specific examples include unsubstituted phenols such as phenol, resorcinol, and hydroquinone; -substituted phenols such as cresol, ethylphenol, n-propylphenol, i-propylphenol, t-butylphenol, octylphenol, nonylphenol, and phenylphenol; Disubstituted phenols, such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol; trisubstituted phenols, often represented by trimethylphenol; naphthols, such as naphthol, methylnaphthol; biphenol, bisphenol -A,
Examples include bisphenols such as bisphenol-F.
さらには上記フェノール類に難燃性を付与する目的で、
さらにクロル基、ブロム基等、ハロゲンを導入したもの
も含まれる。Furthermore, for the purpose of imparting flame retardancy to the above phenols,
Furthermore, those into which halogens are introduced, such as chloro group and bromine group, are also included.
これら、フェノール類は、単独のみならず二種以上用い
ても良い。These phenols may be used alone or in combination of two or more.
本発明のフェノール性水酸基を有する芳香族カルボニル
化合物とは、−分子中に少なくとも１個のフェノール性
水酸基と、少なくとも１個のアルデヒドケトン等、カル
ボニル基を有する化合物であり、耐湿性、難燃性を付与
するためにヘンゼン環にアルコキシ基、アルキル基、ハ
ロゲン等が置換しているものも該当する。The aromatic carbonyl compound having a phenolic hydroxyl group of the present invention is a compound having at least one phenolic hydroxyl group and at least one carbonyl group such as an aldehyde ketone in the molecule, and has moisture resistance and flame retardancy. This also applies to those in which the Hensen ring is substituted with an alkoxy group, an alkyl group, a halogen, etc. in order to provide the following.
具体例としては、サリチルアルデヒド、０ヒドロキシベ
ンズアルデヒド、バニリン、インバニリン等のヒドロキ
シベンズアルデヒド、ヒドロキシアセトフェノン等が挙
げられる。Specific examples include salicylaldehyde, hydroxybenzaldehyde such as 0-hydroxybenzaldehyde, vanillin, and invanillin, and hydroxyacetophenone.
該フェノール性水酸基を有する芳香族カルボニル化合物
は、単独のみならず二種以上用いてもよい。The aromatic carbonyl compound having a phenolic hydroxyl group may be used alone or in combination of two or more.
本発明に用いる不飽和カルボニル化合物とは、−分子中
に少なくとも１個の不飽和二重結合と、少なくとも１個
のカルボニル基を有するものである。The unsaturated carbonyl compound used in the present invention is one having at least one unsaturated double bond and at least one carbonyl group in the molecule.
具体的に例示すると、アクロレイン、メタクロレイン、
クロトンアルデヒド、桂皮アルデヒド等、不飽和アルデ
ヒド類；ビニルメチルケトン、ビニルエチルケトン、ベ
ンザルアセトン等、不飽和ケトン類が挙げられる。Specific examples include acrolein, methacrolein,
Examples include unsaturated aldehydes such as crotonaldehyde and cinnamaldehyde; unsaturated ketones such as vinyl methyl ketone, vinyl ethyl ketone, and benzalacetone.
該不飽和カルボニル化合物も単独のみならず、二種以上
用いてもよい。The unsaturated carbonyl compound may be used alone or in combination of two or more.
フェノール性水酸基を有する芳香族カルボニル化合物と
不飽和カルボニル化合物の比率は、モル比で０．９５：
０．０５〜０．１０．９であり好ましくは０．ｌＯ，１
〜ｏ、ｓ：ｏ、５である。The molar ratio of the aromatic carbonyl compound having a phenolic hydroxyl group to the unsaturated carbonyl compound is 0.95:
0.05 to 0.10.9, preferably 0. lO,1
~o,s:o,5.
不飽和カルボニル化合物の比率を高くする程硬化エポキ
シ樹脂の耐湿性は向上するものの、耐熱性が低下する傾
向があるので使途によって適宜調整する。Although the moisture resistance of the cured epoxy resin improves as the proportion of the unsaturated carbonyl compound increases, the heat resistance tends to decrease, so it should be adjusted appropriately depending on the intended use.
またフェノール類と上記カルボニル化合物の共縮合反応
はノボラック合成用のする周知の方法で行い得る。Further, the co-condensation reaction of phenols and the above carbonyl compound can be carried out by a well-known method for novolak synthesis.
つまり周知の酸性触媒、例えば塩酸、硫酸等の無機酸、
トルエンスルホン酸等の有機酸、酢酸亜鉛等の存在下、
加熱混合することにより行なわれる。In other words, known acidic catalysts, such as inorganic acids such as hydrochloric acid and sulfuric acid,
In the presence of organic acids such as toluenesulfonic acid, zinc acetate, etc.
This is done by heating and mixing.
なおフェノール類とカルボニル化合物類の比率は、フェ
ノール類が過剰に用いる。Regarding the ratio of phenols and carbonyl compounds, phenols are used in excess.
その範囲内でもカルボニル化合物類の比率を大きくして
行くと、平均分子量が大きくなりエポキシ樹脂硬化物の
耐熱性を上げることができるが、硬化前のエポキシ樹脂
Ｍｉ戒物の粘度も高くなるので使途により適宜選択する
。If the ratio of carbonyl compounds is increased even within this range, the average molecular weight will increase and the heat resistance of the cured epoxy resin can be improved, but the viscosity of the epoxy resin before curing will also increase, so it is not suitable for use. Select as appropriate.
本発明の多価フェノール類を硬化剤として用いるエポキ
シ樹脂としては、公知のエポキシ樹脂が工亥当する。As the epoxy resin using the polyhydric phenols of the present invention as a curing agent, known epoxy resins are suitable.
例えば、ビスフェノールＡ１ビスフエノールＦ、ビスフ
ェノールＡＤ、臭素化ビスフエノルＡ、レゾルシン、ハ
イドロキノン等のジフェノール類のグリシジルエーテル
：フェノールノボラック、クレゾールノボラック、レヅ
ルシンノポラソク、トリヒドロキシフェニルメタン、ト
リヒドロキシフェニルプロパン、テトラヒドロキシフェ
ニルエタン、ポリビニルフェノール、ポリイソプロペニ
ルフェノール等のグリシジルエーテル；フェノール類と
芳香族カルボニル化合物との縮合反応により得られる多
価フェノル類のグリシジルエーテル；ジアミノジフェニ
ルメタン、アミノフェノール等のグリシジルアミン類；
ビニルシクロヘキセンジオキサイド、アリシリンクジエ
ポキシアセクール、アリシリソクジエボキシカルボキシ
レート等の脂環式エポキシ樹脂；ヒダントイン型エポキ
シ樹脂、トリグリシジルイソシアヌレート等の複素環式
エポキシ樹脂等である。For example, glycidyl ethers of diphenols such as bisphenol A1 bisphenol F, bisphenol AD, brominated bisphenol A, resorcinol, and hydroquinone: phenol novolac, cresol novolac, redulucin nopolasoc, trihydroxyphenylmethane, trihydroxyphenylpropane, Glycidyl ethers such as tetrahydroxyphenylethane, polyvinylphenol, and polyisopropenylphenol; Glycidyl ethers of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds; Glycidylamines such as diaminodiphenylmethane and aminophenol;
These include alicyclic epoxy resins such as vinyl cyclohexene dioxide, allysylink diepoxy acecool, and allysilisoxydiepoxycarboxylate; heterocyclic epoxy resins such as hydantoin type epoxy resins and triglycidyl isocyanurate;
本発明の多価フェノール類の硬化剤の使用量は、グリシ
ジル基に対し、フェノール性水酸基が０，２〜１．５当
量となる量である。The amount of the polyhydric phenol curing agent used in the present invention is such that the amount of phenolic hydroxyl group is 0.2 to 1.5 equivalents to glycidyl group.
また、本発明の硬化剤とエポキシ樹脂との組成物には、
必要により他の硬化剤、充填剤、硬化促進剤、離型剤、
難燃剤、表面処理剤等、公知の添加剤を添加することが
できる。Furthermore, the composition of the curing agent and epoxy resin of the present invention includes:
Other curing agents, fillers, curing accelerators, mold release agents, if necessary.
Known additives such as flame retardants and surface treatment agents can be added.
本発明の硬化剤とエポキシ樹脂とによる＆Ｉ或物を用い
て半導体等、電子部品を樹脂封止するには、トランスフ
ァーモールド、コンプレッションモールド、インジェク
ションモールド等が、また特に該樹脂組成物が液状の場
合には注型法、ディッピング法、ドロッピング法等、従
来から公知の成型法が適用される。Transfer molding, compression molding, injection molding, etc. can be used to resin-seal electronic components such as semiconductors using the curing agent and epoxy resin of the present invention, and especially when the resin composition is liquid. Conventionally known molding methods such as a casting method, a dipping method, and a dropping method are applied.
また、該樹脂組成物を積Ｎ板用に用いるには、樹脂Ｍｉ
戒物をメチルエチルケトンやトルエン、エチレングリコ
ールモノメチルエーテル等の溶剤を用いて均一に溶解し
、これをガラス繊維や有機繊維に含浸させ、加熱乾燥し
、プリプレグとし、これをプレス成型すれば良い。In addition, in order to use the resin composition for N-laminated plates, the resin Mi
The samurai may be uniformly dissolved using a solvent such as methyl ethyl ketone, toluene, or ethylene glycol monomethyl ether, impregnated into glass fibers or organic fibers, heated and dried to form a prepreg, and this may be press-molded.
〈発明の効果〉
本発明の多価フェノール類は、エポキシ樹脂の硬化剤と
して有用である。<Effects of the Invention> The polyhydric phenols of the present invention are useful as curing agents for epoxy resins.
本発明の多価フェノール類を硬化剤として用いることに
より、従来エポキシ樹脂用硬化剤として広く用いられて
きたフェノールノボラックより高い耐熱性で、耐湿性、
成型性等にバランスのとれた硬化成型物を得ることがで
きる。By using the polyhydric phenols of the present invention as a curing agent, it has higher heat resistance, moisture resistance,
A cured molded product with well-balanced moldability etc. can be obtained.
なお、本発明の多価フェノール類を周知の技術でグリシ
ジルエーテル化すれば、耐熱性、耐湿性の高いエポキシ
樹脂とすることもできる。Incidentally, by converting the polyhydric phenol of the present invention into a glycidyl ether using a well-known technique, an epoxy resin having high heat resistance and moisture resistance can be obtained.
〈実施例〉 以下、実施例でもって、本発明を説明する。<Example> The present invention will be explained below with reference to Examples.
ここで、用いる硬化成型物の評価項目及びその方法は以
下の通りである。Here, the evaluation items and methods for the cured molded product used are as follows.
・ガラス転移温度（Ｔｇ）：熱機械的分析装置（セイコ
ー電子工業部製ＴＭＡＩＯ型）を用いて測定した。- Glass transition temperature (Tg): Measured using a thermomechanical analyzer (TMAIO type, manufactured by Seiko Electronics Industries).
・吸水率（プレッシャークツカーテスト）ニブレス硬化
成形体から２ ＱｍＸ２５ｍＸ２ｆｉの大きさの試験片
を２個取り出し、これを高圧真気環境試験器（−平山製
作所製ＰＣ−３０５３）に入れ１２１℃、２気圧、２０
時間かけて試験片の重量増加を測定し、百分率で表した
。・Water absorption rate (Pressure Kutsuker test) Two test pieces with a size of 2Qm x 25m x 2fi were taken out from the cured Nibles molded product, and placed in a high-pressure vacuum environment tester (-PC-3053 manufactured by Hirayama Seisakusho) at 121℃, 2 atmospheric pressure, 20
The weight increase of the specimen over time was measured and expressed as a percentage.
なお、この吸水率は、耐湿性の指標である。Note that this water absorption rate is an index of moisture resistance.
参考例１〜７、比較参考例１〜２
温度計、撹拌器、コンデンサーを付けた反応器中に表１
に記載の量のフェノール類とフェノール性水酸基を有す
る芳香族カルボニル化合物及び不飽和カルボニル化合物
を入れ、さらに触媒としてｐ−トルエンスルホン酸（−
水塩）１ｇを加え５０℃２時間予備縮合した１ｊ！ｔＧ
ＰＣ（ケルバーミニ−シコンクロマトグラフィー ）
でフェノ −ル性水酸基含有カルボニル化合物及び不飽
和カルボニル化合物の両方が消失したのを確認した後、
１０％苛性ソーダ水溶液で中和した。Reference Examples 1 to 7, Comparative Reference Examples 1 to 2 Table 1 was placed in a reactor equipped with a thermometer, stirrer, and condenser.
phenols, an aromatic carbonyl compound having a phenolic hydroxyl group, and an unsaturated carbonyl compound in the amounts described in , and p-toluenesulfonic acid (-
Water salt) 1g was added and precondensed at 50°C for 2 hours 1j! tG
PC (Kerber Mini-Sikon Chromatography)
After confirming that both the phenolic hydroxyl group-containing carbonyl compound and the unsaturated carbonyl compound had disappeared,
It was neutralized with a 10% aqueous solution of caustic soda.
続いて水洗を５回行った後、蒸留により未反応モノマー
を留去し、目的とする多価フェノ−実施例１〜７、比較
例１〜３
エポキシ樹脂として、フェノール類とヒドロキシベンズ
アルデヒトの縮合により得られたポリフェノールのグリ
シジルエーテル（住友化学工業陣製、商品名スξ■エポ
キシＥＳＸ−２２１、エポキシ当量２１０）２１０ｇ、
硬化剤として表２に示す各種多価フェノール類、硬化促
進剤としてトリフェニルホスフィン３．２ｇ配合し、ロ
ールで加熱混練した後、１７５℃で５分間プレス底形を
行った。Subsequently, after washing with water five times, unreacted monomers were removed by distillation, and the desired polyhydric phenol-Examples 1 to 7, Comparative Examples 1 to 3 was produced by condensation of phenols and hydroxybenzaldehyde as epoxy resins. 210 g of glycidyl ether of polyphenol obtained (manufactured by Sumitomo Chemical Industries, trade name: Epoxy ESX-221, epoxy equivalent: 210),
Various polyhydric phenols shown in Table 2 as a curing agent and 3.2 g of triphenylphosphine as a curing accelerator were blended, heated and kneaded with rolls, and then bottom-pressed at 175° C. for 5 minutes.
さらに１８０℃オーブン中で、５時間ポストキュアーを
行い硬化成型物を得た。Further, post-curing was performed for 5 hours in an oven at 180° C. to obtain a cured molded product.
この硬化成型物のガラス転移温度及び吸水率を測定した
。The glass transition temperature and water absorption rate of this cured molded product were measured.
結果を表２に表す。The results are shown in Table 2.
ル類を得た。I got the class.
Claims (2)
カルボニル化合物および不飽和カルボニル化合物の共縮
合により得られる多価フェノール類。(1) Polyhydric phenols obtained by co-condensation of phenols, phenolic hydroxyl group-containing aromatic carbonyl compounds, and unsaturated carbonyl compounds.
エポキシ樹脂用硬化剤。(2) A curing agent for epoxy resin containing the polyhydric phenol according to claim (1) as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34145189A JPH03199220A (en) | 1989-12-27 | 1989-12-27 | Polyhydric phenols and curing agent for epoxy resin, comprising same phenols as main component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34145189A JPH03199220A (en) | 1989-12-27 | 1989-12-27 | Polyhydric phenols and curing agent for epoxy resin, comprising same phenols as main component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03199220A true JPH03199220A (en) | 1991-08-30 |
Family
ID=18346179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34145189A Pending JPH03199220A (en) | 1989-12-27 | 1989-12-27 | Polyhydric phenols and curing agent for epoxy resin, comprising same phenols as main component |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03199220A (en) |
-
1989
- 1989-12-27 JP JP34145189A patent/JPH03199220A/en active Pending
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