JP6925853B2 - New benzoxazine resin composition and cured product thereof - Google Patents
New benzoxazine resin composition and cured product thereof Download PDFInfo
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- JP6925853B2 JP6925853B2 JP2017087138A JP2017087138A JP6925853B2 JP 6925853 B2 JP6925853 B2 JP 6925853B2 JP 2017087138 A JP2017087138 A JP 2017087138A JP 2017087138 A JP2017087138 A JP 2017087138A JP 6925853 B2 JP6925853 B2 JP 6925853B2
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- 239000011342 resin composition Substances 0.000 title claims description 28
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title description 14
- -1 benzoxazine compound Chemical class 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 150000005130 benzoxazines Chemical class 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 claims 1
- 229940116224 behenate Drugs 0.000 claims 1
- 239000000047 product Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000009849 vacuum degassing Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 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 3
- 238000005266 casting Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-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
- 239000002966 varnish Substances 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
本発明は、新規なベンゾオキサジン樹脂組成物及びその硬化物に関する。詳しくは、ジフェニルエーテル基の両末端に、ベンゾオキサジン環を有するベンゾオキサジン化合物を含有する樹脂組成物及びその硬化物に関する。 The present invention relates to a novel benzoxazine resin composition and a cured product thereof. More specifically, the present invention relates to a resin composition containing a benzoxazine compound having a benzoxazine ring at both ends of a diphenyl ether group and a cured product thereof.
ベンゾオキサジン化合物は、フェノール類、アミン類及びホルムアルデヒドを反応させることにより合成される化合物であり、加熱することにより揮発性の副生物を生ずることなく、ベンゾオキサジン環が開環重合して硬化する熱硬化性樹脂原料として知られている。
このようなベンゾオキサジン化合物は、絶縁基板用材料として利用可能な成形体(特許文献1)、液晶配向剤(特許文献2)、半導体封止用樹脂組成物(特許文献3、4)等の原料として利用されている。
従来公知のベンゾオキサジン化合物として、非特許文献1には、下記構造のベンゾオキサジン化合物(a)を硬化させた硬化物が記載されている。
また、特許文献4には、下記構造のベンゾオキサジン化合物(b)を含む樹脂組成物から硬化物を得ることが記載されている。
Such a benzoxazine compound is a raw material for a molded product (Patent Document 1), a liquid crystal alignment agent (Patent Document 2), a resin composition for semiconductor encapsulation (Patent Documents 3 and 4) and the like that can be used as a material for an insulating substrate. It is used as.
As a conventionally known benzoxazine compound, Non-Patent Document 1 describes a cured product obtained by curing a benzoxazine compound (a) having the following structure.
Further, Patent Document 4 describes that a cured product is obtained from a resin composition containing a benzoxazine compound (b) having the following structure.
本発明は、耐熱性等の性能が改良された、ベンゾオキサジン化合物を含有する樹脂組成物及びその硬化物を提供することを課題とする。 An object of the present invention is to provide a resin composition containing a benzoxazine compound and a cured product thereof, which have improved performance such as heat resistance.
本発明者は、上述の課題解決のために鋭意検討した結果、ベンゾオキサジン化合物の化学構造を、ジフェニルエーテル基の3,4’−位にベンゾオキサジン環を有する構造とすることにより、耐熱性に優れた樹脂を得ることができることを見出し、本発明を完成した。 As a result of diligent studies to solve the above-mentioned problems, the present inventor has excellent heat resistance by making the chemical structure of the benzoxazine compound a structure having a benzoxazine ring at the 3,4'-position of the diphenyl ether group. The present invention has been completed by finding that a resin can be obtained.
本発明は以下の通りである。
1.一般式(I)で表されるベンゾオキサジン化合物を含有することを特徴とする、ベンゾオキサジン樹脂組成物。
1. 1. A benzoxazine resin composition comprising a benzoxazine compound represented by the general formula (I).
本発明により、ジフェニルエーテル基の3,4’−位にベンゾオキサジン環を有するベンゾオキサジン化合物を含有する新規なベンゾオキサジン樹脂組成物及びその硬化物が提供される。この新規なベンゾオキサジン樹脂組成物は熱硬化性を有し、これを硬化させた硬化物は、従来知られているベンゾオキサジン化合物を含有する樹脂組成物を硬化させた硬化物に比べて、特にガラス転移温度が高く、耐熱性に極めて優れている。従って各種基材に塗布可能なワニス、ワニスを含浸させたプリプレグ、プリント回路基板、電子部品の封止剤、電気・電子成型部品、自動車部品、積層材、塗料、レジストインク等の樹脂原料として好適に用いることができる。 INDUSTRIAL APPLICABILITY The present invention provides a novel benzoxazine resin composition containing a benzoxazine compound having a benzoxazine ring at the 3,4'-position of a diphenyl ether group and a cured product thereof. This novel benzoxazine resin composition has thermosetting property, and the cured product obtained by curing the novel benzoxazine resin composition is particularly compared with a cured product obtained by curing a resin composition containing a conventionally known benzoxazine compound. The glass transition temperature is high and the heat resistance is extremely excellent. Therefore, it is suitable as a resin raw material for varnishes that can be applied to various substrates, prepregs impregnated with varnishes, printed circuit boards, sealants for electronic parts, electric / electronic molded parts, automobile parts, laminates, paints, resist inks, etc. Can be used for.
本発明の樹脂組成物が含有するベンゾオキサジン化合物は下記一般式(I)で表される。
本発明の実施において使用される一般式(I)で表されるベンゾオキサジン化合物の製造方法については、その製造における出発原料、製造方法について特に制限はなく、例えば、特開2006−335671号公報に記載のように、溶媒の存在下に一級アミン化合物とフェノール化合物及びホルマリン類を撹拌混合し、加温下に脱水縮合反応させる等のベンゾオキサジン化合物を製造するための公知の方法を任意に採用することができる。中でも、ジアミノジフェニルエーテル化合物とフェノール化合物との混合溶液を、ホルムアルデヒドと脱水縮合反応させて環化し、ベンゾオキサジン化合物とする製造方法が好ましい。 The method for producing the benzoxazine compound represented by the general formula (I) used in the practice of the present invention is not particularly limited with respect to the starting material and the production method in the production thereof. As described, a known method for producing a benzoxazine compound, such as stirring and mixing a primary amine compound with a phenol compound and formarines in the presence of a solvent and causing a dehydration condensation reaction under heating, is optionally adopted. be able to. Above all, a production method in which a mixed solution of a diaminodiphenyl ether compound and a phenol compound is dehydrated and condensed with formaldehyde to be cyclized to obtain a benzoxazine compound is preferable.
以下に、一般式(I)で表されるベンゾオキサジン化合物の製造方法について、反応式で例示する。
この製造方法に使用する原料化合物について説明すると、ジアミノジフェニルエーテル化合物は、詳しくは3,4’−ジアミノジフェニルエーテルである。また、フェノール化合物は、下記一般式(II)で表される化合物である。この一般式(II)で表されるフェノール化合物としては、フェノール、p−クレゾール、o−クレゾール、m−クレゾールを挙げることができる。
ジアミノジフェニルエーテル化合物、フェノール化合物及びホルムアルデヒドの脱水縮合反応において、それぞれの添加モル比(ジアミノジフェニルエーテル化合物/フェノール化合物/ホルムアルデヒド)は、通常1.0/1.6/3.6〜1.0/4.0/4.4の範囲であり、好ましくは1.0/2.0/4.0〜1.0/2.5/4.2の範囲である。
Explaining the raw material compound used in this production method, the diaminodiphenyl ether compound is specifically 3,4'-diaminodiphenyl ether. The phenol compound is a compound represented by the following general formula (II). Examples of the phenol compound represented by the general formula (II) include phenol, p-cresol, o-cresol, and m-cresol.
In the dehydration condensation reaction of the diaminodiphenyl ether compound, the phenol compound and formaldehyde, the respective addition molar ratios (diaminodiphenyl ether compound / phenol compound / formaldehyde) are usually 1.0 / 1.6 / 3.6 to 1.0 / 4. The range is 0 / 4.4, preferably 1.0 / 2.0 / 4.0 to 1.0 / 2.5 / 4.2.
反応は通常、溶媒の存在下に行われる。溶媒としては、反応を阻害しないものであれば特に制限はないが、トルエン、キシレン、酢酸エチル、酢酸ブチル、クロロホルム、ジクロロメタン、THF、ジオキサン等が好ましく挙げられる。これらの溶媒は単独又は組み合わせて用いることができる。また、溶媒の使用量は反応に支障なければ特に制限はないが、通常、ジアミノジフェニルエーテル化合物に対し3〜10重量倍の範囲、好ましくは4〜6重量倍の範囲で用いられる。
反応温度は通常、70〜120℃の範囲である。反応圧力は常圧条件下で行ってもよく、また、加圧下でも、或は減圧下で行ってもよい。
反応を促進するための触媒は特に必要はないが、必要に応じて、酸触媒または塩基触媒を使用することができる。この場合、使用できる酸触媒として、濃塩酸、塩酸ガス、トリフルオロ酢酸、メタンスルホン酸、p−トルエンスルホン酸、安息香酸およびそれらの混合物等が挙げられ、使用できる塩基触媒としては、水酸化ナトリウム、炭酸ナトリウム、トリエチルアミン、トリエタノールアミンおよびそれらの混合物等が挙げられるが、これらに限定されるものではない。
別の態様として、反応中に生成した水を系外に除去する手順を含むことができる。反応溶液から生成した水を除去する手順は特に制限されず、生成した水を反応溶液中の溶媒系と共沸的に蒸留することにより行うことができる。生成した水は、例えばコックを備えた等圧滴下漏斗、ジムロート冷却器、ディーンスターク装置等の使用により反応系外に除去することができる。
このようにして得られた反応終了混合物は、反応終了後、公知の方法によりこの混合物から一般式(I)で表されるベンゾオキサジン化合物を得ることができる。例えば、反応後、反応混合物から残存原料や溶媒を留去することにより残液として目的物を得ることができる。また、残液を貧溶媒に添加して沈殿させたり、反応混合物に溶媒を添加して晶析し、ろ過することにより粉体若しくは粒状の目的物を得ることも考えられる。残存原料がフェノールの場合には、必要に応じて水と分離する溶媒を加え、アルカリ水溶液で洗浄することにより除去することができる。上記方法により、取り出されたベンゾオキサジン化合物は、例えば、溶媒や水での洗浄や再結晶等の通常の精製手段により、高純度品とすることができる。
The reaction is usually carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but toluene, xylene, ethyl acetate, butyl acetate, chloroform, dichloromethane, THF, dioxane and the like are preferable. These solvents can be used alone or in combination. The amount of the solvent used is not particularly limited as long as it does not interfere with the reaction, but is usually used in the range of 3 to 10 times by weight, preferably 4 to 6 times by weight, that of the diaminodiphenyl ether compound.
The reaction temperature is usually in the range of 70-120 ° C. The reaction pressure may be carried out under normal pressure conditions, under pressure or under reduced pressure.
A catalyst for accelerating the reaction is not particularly required, but an acid catalyst or a base catalyst can be used if necessary. In this case, examples of the acid catalyst that can be used include concentrated hydrochloric acid, hydrochloric acid gas, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid and a mixture thereof, and examples of the base catalyst that can be used include sodium hydroxide. , Sodium carbonate, triethylamine, triethanolamine and mixtures thereof and the like, but are not limited thereto.
As another embodiment, a procedure for removing the water produced during the reaction from the system can be included. The procedure for removing the water produced from the reaction solution is not particularly limited, and the water produced can be distilled azeotropically with the solvent system in the reaction solution. The generated water can be removed from the reaction system by using, for example, an isobaric dropping funnel equipped with a cock, a Dimroth condenser, a Dean Stark apparatus, or the like.
After the reaction is completed, the reaction-terminated mixture thus obtained can obtain a benzoxazine compound represented by the general formula (I) from this mixture by a known method. For example, after the reaction, the target product can be obtained as a residual liquid by distilling off the residual raw material or solvent from the reaction mixture. It is also conceivable to add the residual liquid to a poor solvent for precipitation, or to add a solvent to the reaction mixture for crystallization and filtration to obtain a powder or granular target product. When the residual raw material is phenol, it can be removed by adding a solvent that separates from water, if necessary, and washing with an alkaline aqueous solution. The benzoxazine compound taken out by the above method can be made into a high-purity product by ordinary purification means such as washing with a solvent or water or recrystallization.
本発明の樹脂組成物は、上記の一般式(I)で表されるベンゾオキサジン化合物を必須成分として含有し、その他の高分子材料を含有してもよい。
本発明の樹脂組成物を構成する高分子材料としては、特に制限はないが、エポキシ樹脂、フェノール樹脂、ビスマレイミド樹脂それぞれの原料を含有することができる。このエポキシ樹脂としては、オルソクレゾール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセンジヒドリド型エポキシ樹脂、臭素化ノボラック型エポキシ樹脂等が挙げられる。このフェノール樹脂としては、ノボラック型フェノール樹脂、ビスフェノール樹脂等を、このビスマレイミド樹脂としては、下記構造を有するビスマレイミド樹脂の原料等が挙げられる。
The polymer material constituting the resin composition of the present invention is not particularly limited, but may contain raw materials of each of an epoxy resin, a phenol resin, and a bismaleimide resin. Examples of this epoxy resin include orthocresol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, anthracendihydride type epoxy resin, brominated novolac type epoxy resin and the like. Examples of the phenol resin include a novolak type phenol resin and a bisphenol resin, and examples of the bisphenol resin include a raw material of a bisphenol resin having the following structure.
本発明の樹脂組成物は、上記一般式(I)で表されるベンゾオキサジン化合物を、通常50重量%以上100重量%以下の範囲で、好ましくは80重量%以上100重量%以下の範囲で、より好ましくは90重量%以上100重量%以下の範囲で含有する。また、本発明の樹脂組成物を構成する高分子材料であるエポキシ樹脂の原料は0重量%以上50重量%以下の範囲で、フェノール樹脂の原料は0重量%以上50重量%以下の範囲で、ビスマレイミド樹脂の原料は0重量%以上20重量%以下の範囲で含有することができる。
本発明の樹脂組成物は、上記一般式(I)で表されるベンゾオキサジン化合物を、その他必要に応じて前記高分子材料に添加することによって得られるが、かかる添加方法は特に限定されず、従来公知の方法を採用することができる。例えば、高分子材料の合成や重合中に添加する方法、高分子材料からなる樹脂を例えば溶融押出工程等において溶融した溶融樹脂に添加する方法、高分子材料からなる樹脂製品等に含浸する方法等を挙げることができる。
The resin composition of the present invention contains the benzoxazine compound represented by the general formula (I) in a range of usually 50% by weight or more and 100% by weight or less, preferably 80% by weight or more and 100% by weight or less. More preferably, it is contained in the range of 90% by weight or more and 100% by weight or less. The raw material of the epoxy resin, which is the polymer material constituting the resin composition of the present invention, is in the range of 0% by weight or more and 50% by weight or less, and the raw material of the phenol resin is in the range of 0% by weight or more and 50% by weight or less. The raw material of the bismaleimide resin can be contained in the range of 0% by weight or more and 20% by weight or less.
The resin composition of the present invention can be obtained by adding the benzoxazine compound represented by the general formula (I) to the polymer material as needed, but the addition method is not particularly limited. A conventionally known method can be adopted. For example, a method of adding a polymer material during synthesis or polymerization, a method of adding a resin made of a polymer material to a molten resin melted in, for example, a melt extrusion step, a method of impregnating a resin product made of a polymer material, etc. Can be mentioned.
続いて、本発明の硬化物について説明する。
本発明の硬化物は、上記一般式(I)で表されるベンゾオキサジン化合物を含有する樹脂組成物を硬化させて得ることができる。本発明の硬化物は、一般式(I)で表されるベンゾオキサジン化合物を1種のみ硬化させて得られる硬化物であってもよく、異なる2種以上の一般式(I)で表されるベンゾオキサジン化合物からなる混合物を硬化させて得られる硬化物であってもよい。さらに目的に応じて、上述のエポキシ樹脂、フェノール樹脂、ビスマレイミド樹脂それぞれの原料を使用して、本発明の硬化物を得ることもできる。
本発明の硬化物の製造方法としては、例えば、所定の温度まで加熱して硬化させる方法、加熱融解させて金型等に注ぎ金型を更に加熱して硬化成型させる方法、上記一般式(I)で表されるベンゾオキサジン化合物の溶融物を予め加熱された金型に注入して硬化させる方法等を挙げることができる。
本発明の樹脂組成物は、組成物中に残存溶媒を含んでいると硬化時に気泡が発生してしまうので、これを防ぐために前処理として真空脱気処理を行うことが好ましい。この真空脱気処理の温度は、本発明の樹脂組成物が溶融状態となる温度であれば特に制限されないが、硬化が進行せず、かつ、脱気がしやすいとの理由により140〜160℃の温度範囲が好適である。真空脱気処理の圧力は、特に制限はないが、低い(減圧度の高い)方がよく、空気中でも窒素置換雰囲気下中の何れで行ってもよい。この真空脱気処理は、気泡が目視で確認できなくなるまで行う。
Subsequently, the cured product of the present invention will be described.
The cured product of the present invention can be obtained by curing a resin composition containing a benzoxazine compound represented by the above general formula (I). The cured product of the present invention may be a cured product obtained by curing only one benzoxazine compound represented by the general formula (I), and may be represented by two or more different general formulas (I). It may be a cured product obtained by curing a mixture composed of a benzoxazine compound. Further, depending on the purpose, the cured product of the present invention can also be obtained by using the raw materials of each of the above-mentioned epoxy resin, phenol resin, and bismaleimide resin.
Examples of the method for producing a cured product of the present invention include a method of heating to a predetermined temperature to cure, a method of heating and melting and pouring into a mold or the like to further heat the mold to cure and mold, and the above general formula (I). ) Is injected into a preheated mold to cure the melt of the benzoxazine compound.
If the resin composition of the present invention contains a residual solvent in the composition, bubbles are generated during curing. To prevent this, it is preferable to perform a vacuum degassing treatment as a pretreatment. The temperature of this vacuum degassing treatment is not particularly limited as long as the resin composition of the present invention is in a molten state, but is 140 to 160 ° C. because curing does not proceed and degassing is easy. The temperature range of is suitable. The pressure of the vacuum degassing treatment is not particularly limited, but it is better to be low (high degree of decompression), and it may be performed in air or in a nitrogen substitution atmosphere. This vacuum degassing process is performed until bubbles cannot be visually confirmed.
本発明の硬化物は、通常のベンゾオキサジンと同様の硬化条件にて、開環重合を行い硬化することができる。硬化温度は、通常140〜250℃の温度範囲であり、好ましくは160〜220℃の温度範囲であり、より好ましくは160〜200℃の温度範囲であるが、得られる硬化物の機械物性を良くするためには、特に180〜200℃の温度範囲とすることが好ましい。このような温度範囲において硬化を行う場合には、反応時間は2〜10時間程度であればよい。
本発明の樹脂組成物は、熱のみで硬化できるが、上記一般式(I)で表されるベンゾオキサジン化合物以外の成分やその含油量等によっては、硬化促進剤を用いた方が好ましい。使用できる硬化促進剤としては、特に限定されるものではなく、例えば、1,8−ジアザ−ビシクロ[5.4.0]ウンデセン−7、トリエチレンジアミン、トリス(2,4,6−ジメチルアミノメチル)フェノール等の第三級アミン類、2−エチル−4−メチルイミダゾール、2−メチルイミダゾール等のイミダゾール類、トリフェニルホスフィン、テトラフェニルホスホニウムブロマイド、テトラフェニルホスホニウムテトラフェニルボレート、テトラ−n−ブチルホスホニウム−o,o−ジエチルホスホロジチオエート等のリン化合物、4級アンモニウム塩、有機金属塩類、及びこれらの誘導体等が挙げられる。これらは単独で使用してもよく、あるいは、併用してもよい。これら硬化促進剤の中では、第三級アミン類、イミダゾール類及びリン化合物を用いることが好ましい。
The cured product of the present invention can be cured by ring-opening polymerization under the same curing conditions as ordinary benzoxazine. The curing temperature is usually in the temperature range of 140 to 250 ° C., preferably in the temperature range of 160 to 220 ° C., more preferably in the temperature range of 160 to 200 ° C., but the mechanical properties of the obtained cured product are good. In particular, the temperature range is preferably 180 to 200 ° C. When curing is performed in such a temperature range, the reaction time may be about 2 to 10 hours.
The resin composition of the present invention can be cured only by heat, but it is preferable to use a curing accelerator depending on the components other than the benzoxazine compound represented by the general formula (I) and the oil content thereof. The curing accelerator that can be used is not particularly limited, and is, for example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, tris (2,4,6-dimethylaminomethyl). ) Tertiary amines such as phenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium Examples thereof include phosphorus compounds such as -o and o-diethylphosphologithioate, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles and phosphorus compounds.
以下、実施例により、本発明をさらに具体的に説明する。
<合成例1>
化合物(1)の合成
フェノール176.3g、3,4’−ジアミノジフェニルエーテル150.0g、トルエン750.0gを2リッター四つ口フラスコに仕込み、撹拌下に内温65℃で35%ホルマリン水溶液257.1gを35分かけて滴下した。滴下終了後、常圧下85℃で単蒸留を行い、水、トルエンを留出させ、留出したトルエンはフラスコ内に戻した。さらにフェノール35.3gを追加後、還流下86℃で2時間反応させた。
反応終了後、内温を室温まで下げ、反応混合液に10%水酸化ナトリウム水溶液300gを加えて20分撹拌し、水層を分離除去した。得られた油層にトルエン200gを追加後、3.75%水酸化ナトリウム水溶液800gを加えて20分撹拌して、静置し、水層を分離除去した。
次いで得られた油層に水300gを加えて撹拌し、水層を除去する洗浄操作を6回繰り返した。洗浄した油層を減圧下でトルエンを留去し、樹脂状の化合物(1)185.1gを得た。この化合物のGPC分析による純度は60.4%であった。また、1H−NMR分析結果から目的化合物であることを確認した。
1H−NMR(400MHz)測定(溶媒:CDCl3):4.64(s,2H:a) , 4.66(s,2H:a’), 5.37(s,2H:b), 5.39(s,2H:b’), 6.53-6.55(ddd,1H:c), 6.81-7.35(m,15H:others).
13C−NMR(400MHz)測定(溶媒:CDCl3):50.28(A),50.36(A’),79.21(B),80.14(B’),108.15(H),110.60(I),112.23(J),114.69(C),117.06(K),120.20(L),120.96(M),126.85(N),126.85(N),127,97(O),128.33(P),129.14(Q),130.20(R),149.90(D),151.27(E),154.38(F),159.06(G)
Hereinafter, the present invention will be described in more detail with reference to Examples.
<Synthesis example 1>
Synthesis of compound (1) 176.3 g of phenol, 150.0 g of 3,4'-diaminodiphenyl ether, and 750.0 g of toluene were placed in a 2-liter four-necked flask, and a 35% formalin aqueous solution 257 at an internal temperature of 65 ° C. under stirring. 1 g was added dropwise over 35 minutes. After completion of the dropping, simple distillation was performed at 85 ° C. under normal pressure to distill water and toluene, and the distilled toluene was returned to the flask. After adding 35.3 g of phenol, the reaction was carried out at 86 ° C. for 2 hours under reflux.
After completion of the reaction, the internal temperature was lowered to room temperature, 300 g of a 10% aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was stirred for 20 minutes to separate and remove the aqueous layer. After adding 200 g of toluene to the obtained oil layer, 800 g of a 3.75% sodium hydroxide aqueous solution was added, the mixture was stirred for 20 minutes, allowed to stand, and the aqueous layer was separated and removed.
Next, 300 g of water was added to the obtained oil layer and stirred, and the washing operation for removing the water layer was repeated 6 times. Toluene was distilled off from the washed oil layer under reduced pressure to obtain 185.1 g of the resinous compound (1). The purity of this compound by GPC analysis was 60.4%. In addition, it was confirmed that it was the target compound from the 1 H-NMR analysis result.
1 1 H-NMR (400MHz) measurement (solvent: CDCl 3 ): 4.64 (s, 2H: a), 4.66 (s, 2H: a'), 5.37 (s, 2H: b), 5.39 (s, 2H: b) '), 6.53-6.55 (ddd, 1H: c), 6.81-7.35 (m, 15H: others).
13 C-NMR (400MHz) measurement (solvent: CDCl 3 ): 50.28 (A), 50.36 (A'), 79.21 (B), 80.14 (B'), 108.15 (H), 110.60 (I), 112.23 (J) ), 114.69 (C), 117.06 (K), 120.20 (L), 120.96 (M), 126.85 (N), 126.85 (N), 127,97 (O), 128.33 (P), 129.14 (Q), 130.20 (R), 149.90 (D), 151.27 (E), 154.38 (F), 159.06 (G)
<実施例1>
上記合成例1で合成した樹脂状の化合物(1)63.2gを200mlビーカーに仕込み、140℃に溶融し、真空脱気処理を行った。
真空脱気処理した化合物(1)をシリコン製の注型に流し込み、140℃で2時間、150℃で2時間、160℃で2時間、180℃で2時間、200℃で2時間加熱して硬化物を得た。
<Example 1>
63.2 g of the resinous compound (1) synthesized in Synthesis Example 1 was charged in a 200 ml beaker, melted at 140 ° C., and subjected to vacuum degassing treatment.
The vacuum degassed compound (1) is poured into a silicon casting and heated at 140 ° C. for 2 hours, 150 ° C. for 2 hours, 160 ° C. for 2 hours, 180 ° C. for 2 hours, and 200 ° C. for 2 hours. A cured product was obtained.
<合成例2>
化合物(a)の合成
フェノール65.9g、4,4’−ジアミノジフェニルエーテル70.0g、パラホルム44.7g、トルエン350gを1リッター四つ口フラスコに仕込み、還流下で26時間反応させた。反応終了液を室温まで冷却後、n−ヘプタン700.0gを仕込んだ2リッター四つ口フラスコに滴下し沈殿を生成させた。生じた沈殿をろ過、減圧乾燥することによって、化合物(a)の粉体127.7gを得た。この化合物のGPC分析による純度は59.5%であった。
<Synthesis example 2>
Synthesis of Compound (a) 65.9 g of phenol, 70.0 g of 4,4'-diaminodiphenyl ether, 44.7 g of paraform and 350 g of toluene were placed in a 1-liter four-necked flask and reacted under reflux for 26 hours. After cooling the reaction completion liquid to room temperature, it was added dropwise to a 2-liter four-necked flask charged with 700.0 g of n-heptane to form a precipitate. The resulting precipitate was filtered and dried under reduced pressure to obtain 127.7 g of a powder of compound (a). The purity of this compound by GPC analysis was 59.5%.
<比較例1>
上記合成例2で合成した化合物(a)63.0gを200mlビーカーに仕込み、140℃に溶融し、真空脱気処理を行った。真空脱気処理した化合物(a)をシリコン製の注型に流し込み、140℃で2時間、150℃で2時間、160℃で2時間、180℃で2時間、200℃で2時間加熱して硬化物を得た。
<Comparative example 1>
63.0 g of the compound (a) synthesized in Synthesis Example 2 was charged in a 200 ml beaker, melted at 140 ° C., and subjected to vacuum degassing treatment. The vacuum degassed compound (a) is poured into a silicon casting and heated at 140 ° C. for 2 hours, 150 ° C. for 2 hours, 160 ° C. for 2 hours, 180 ° C. for 2 hours, and 200 ° C. for 2 hours. A cured product was obtained.
<比較例2>
四国化成工業株式会社製の化合物(b)73gを200mlビーカーに仕込み、150℃で溶融させ、真空脱気処理を行った。真空脱気処理した化合物(b)をシリコン製の注型に流し込み、180℃で2時間、200℃で2時間加熱して硬化物を得た。
<Comparative example 2>
73 g of compound (b) manufactured by Shikoku Kasei Kogyo Co., Ltd. was charged in a 200 ml beaker, melted at 150 ° C., and subjected to vacuum degassing treatment. The vacuum degassed compound (b) was poured into a silicon casting and heated at 180 ° C. for 2 hours and at 200 ° C. for 2 hours to obtain a cured product.
<ガラス転移温度(tanδ値)>
実施例1、比較例1、2により得られた硬化物について、動的粘弾性測定によりガラス転移温度(tanδ値)を測定し、得られた測定結果を表1に示す。
動的粘弾性測定条件は以下のとおりである。
動的粘弾性測定装置:Rheogel−E4000FZ(UBM Co.,Ltd)
昇温速度 :2℃/min
周波数 :1Hz
測定モード :曲げ
<Glass transition temperature (tan δ value)>
The glass transition temperature (tan δ value) of the cured products obtained in Examples 1 and Comparative Examples 1 and 2 was measured by dynamic viscoelasticity measurement, and the obtained measurement results are shown in Table 1.
The dynamic viscoelasticity measurement conditions are as follows.
Dynamic viscoelasticity measuring device: Rheogel-E4000FZ (UBM Co., Ltd)
Heating rate: 2 ° C / min
Frequency: 1Hz
Measurement mode: Bending
表1の結果より、本発明の硬化物は、従来公知のベンゾオキサジン樹脂組成物の硬化物より、高いガラス転移温度を有し、優れた耐熱性を有することが明らかとなった。
本発明のベンゾオキサジン樹脂組成物及びその硬化物が奏するこれらの効果は、本発明者が多くの実験を行い初めて確認した格別顕著な効果である。
From the results in Table 1, it was clarified that the cured product of the present invention had a higher glass transition temperature and excellent heat resistance than the cured product of the conventionally known benzoxazine resin composition.
These effects exhibited by the benzoxazine resin composition of the present invention and the cured product thereof are exceptionally remarkable effects confirmed for the first time by the present inventor through many experiments.
Claims (1)
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