JPH04246409A - New energy ray-curable resin composition - Google Patents
New energy ray-curable resin compositionInfo
- Publication number
- JPH04246409A JPH04246409A JP1193091A JP1193091A JPH04246409A JP H04246409 A JPH04246409 A JP H04246409A JP 1193091 A JP1193091 A JP 1193091A JP 1193091 A JP1193091 A JP 1193091A JP H04246409 A JPH04246409 A JP H04246409A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- energy ray
- curable resin
- resin composition
- 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
- 239000011342 resin composition Substances 0.000 title claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000000466 oxiranyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 description 33
- 239000011347 resin Substances 0.000 description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- -1 monocarboxylic acid compound Chemical class 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BRTHMFXKGHIZAM-UHFFFAOYSA-N 2-hydroxy-1-phenylheptan-1-one Chemical compound CCCCCC(O)C(=O)C1=CC=CC=C1 BRTHMFXKGHIZAM-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 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
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- FGOSBCXOMBLILW-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 FGOSBCXOMBLILW-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical class C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 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
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は新規にして有用なるエネ
ルギー線硬化型樹脂組成物に関する。さらに詳細には、
本発明は有効成分として、特定の構造のオキシラン環含
有化合物と、特定のオキシラン環含有基と反応する官能
基と不飽和二重結合とを併せ有する化合物との反応によ
って得られるエネルギー線硬化型樹脂を含んで成る、エ
ネルギー線硬化型樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new and useful energy ray curable resin composition. In more detail,
The present invention is an energy ray-curable resin obtained by reacting, as an active ingredient, an oxirane ring-containing compound with a specific structure and a compound having both a functional group that reacts with the specific oxirane ring-containing group and an unsaturated double bond. An energy beam curable resin composition comprising:
【０００２】そして、かかる本発明のエネルギー線硬化
型樹脂組成物は、コーティング材、印刷インキならびに
接着剤などの広範なる用途に適した、極めて有用なる、
紫外線や電子線などの、いわゆるエネルギー線により硬
化可能な樹脂組成物である。The energy ray-curable resin composition of the present invention is extremely useful and suitable for a wide range of uses such as coating materials, printing inks, and adhesives.
It is a resin composition that can be cured by so-called energy rays such as ultraviolet rays and electron beams.
【０００３】0003
【従来の技術】エネルギー線で硬化可能、就中、ラジカ
ル重合反応により硬化する樹脂は、不飽和ポリエステル
樹脂、ビニルエステル樹脂（エポキシ−アクリレート）
、各種オリゴアクリレートおよびジアリルフタレートプ
レポリマーなどの各種のものがあり、それぞれの用途分
野で特徴が活かされ、広く用いられている。[Prior Art] Resins that can be cured by energy rays, especially by radical polymerization reactions, include unsaturated polyester resins and vinyl ester resins (epoxy-acrylates).
, various oligoacrylates, and diallyl phthalate prepolymers, each of which has its own characteristics and is widely used in its application field.
【０００４】しかし、近年、その用途が広がるに伴って
、益々、その性能に対する要求が高まっているが、すべ
ての諸性能を満足させ得るような、エネルギー線によっ
て硬化可能なる樹脂、そして樹脂組成物は、未だに、得
られていないというのが現状である。[0004] However, in recent years, as its uses have expanded, demands for its performance have been increasing.However, there is a need for resins and resin compositions that can be cured by energy rays and can satisfy all the various performances. The current situation is that it has not been obtained yet.
【０００５】[0005]
【発明が解決しようとする課題】本発明者らは、前述し
た如き諸情勢に鑑みて、既存の樹脂では、決して、満足
できないような用途に対しても用いることの出来る、耐
水性、耐溶剤性、耐薬品性、耐熱性ならびに硬化性など
に優れたラジカル硬化型樹脂の合成について、鋭意、研
究を開始した。[Problems to be Solved by the Invention] In view of the various situations described above, the present inventors have developed a water-resistant and solvent-resistant material that can be used for applications that cannot be satisfied with existing resins. We have begun intensive research into the synthesis of radical-curing resins with excellent properties such as hardness, chemical resistance, heat resistance, and hardening properties.
【０００６】本発明が解決しようとする課題は、このよ
うに、とりわけ、耐水性、耐溶剤性、耐薬品性、耐熱性
ならびに硬化性などに優れたラジカル硬化型樹脂を見い
出すことであり、そして、かかる特徴を有するラジカル
硬化型樹脂を含んで成るエネルギー線硬化型樹脂組成物
を提供することである。[0006] The problem to be solved by the present invention is thus to find a radical curable resin that is particularly excellent in water resistance, solvent resistance, chemical resistance, heat resistance, and curability, and An object of the present invention is to provide an energy ray-curable resin composition comprising a radical-curable resin having such characteristics.
【０００７】[0007]
【課題を解決するための手段】そこで、本発明者らは、
上述した如き発明が解決しようとする課題に照準を合わ
せて、鋭意、検討を重ねた結果、特定の構造を有する多
官能のオキシラン環含有化合物と、このオキシラン環含
有基と反応する官能基と不飽和二重結合とを併せ有する
化合物との反応によって得られるエネルギー線硬化型樹
脂が、上述したような塗膜の諸性能を満足させることが
出来ることを知るに及んで、本発明を完成するに到った
。[Means for solving the problem] Therefore, the present inventors
As a result of intensive studies aimed at the problems to be solved by the invention as described above, we have discovered that a polyfunctional oxirane ring-containing compound having a specific structure, a functional group that reacts with the oxirane ring-containing group, and an inorganic group have been developed. Upon learning that an energy ray-curable resin obtained by reaction with a compound having saturated double bonds can satisfy the various properties of the coating film described above, it was difficult to complete the present invention. It has arrived.
【０００８】すなわち、本発明は基本的には、特定の構
造の多官能オキシラン環含有化合物と、このオキシラン
環含有基と反応する官能基と不飽和二重結合とを骨格中
に有する化合物との反応によって得られるエネルギー線
硬化型樹脂を、必須の皮膜形成性成分として含んで成る
、極めて有用性の高いエネルギー線硬化型樹脂組成物を
提供するものである。That is, the present invention basically consists of a polyfunctional oxirane ring-containing compound having a specific structure and a compound having a functional group that reacts with the oxirane ring-containing group and an unsaturated double bond in its skeleton. The object of the present invention is to provide an extremely useful energy ray curable resin composition comprising an energy ray curable resin obtained by reaction as an essential film-forming component.
【０００９】そして具体的には、一般式Specifically, the general formula
【００１０】0010
【化６】[C6]
【００１１】［ただし、式中のＷ、Ｘ、ＹおよびＺは、
それぞれ、同一であっても異なっていてもよい、水素原
子または式[However, W, X, Y and Z in the formula are
Hydrogen atoms or formulas, each of which may be the same or different
【００１２】0012
【化７】[C7]
【００１３】で示される基を表わすものとするが、Ｗ、
Ｘ、ＹまたはＺのすべてが水素原子である場合は除くも
のとする。］
で示される化合物の少なくとも一つのオキシラン環含有
基と、このオキシラン環含有基と反応する基と不飽和二
重結合とを併せ有する化合物との反応物を含有すること
を特徴とする、エネルギー線硬化型樹脂組成物を提供す
るものである。represents a group represented by W,
The case where all of X, Y or Z are hydrogen atoms shall be excluded. ] An energy beam characterized by containing a reaction product of at least one oxirane ring-containing group of the compound represented by the above, and a compound having both a group that reacts with the oxirane ring-containing group and an unsaturated double bond. A curable resin composition is provided.
【００１４】ここにおいて、上述した通りのエネルギー
線硬化型樹脂〔以下、樹脂（Ａ）ともいう。〕とは、前
掲した一般式〔１〕で示されるような特定の構造を有す
るオキシラン環含有化合物と不飽和モノカルボン酸とを
反応させたものを指称する。Here, the energy ray curable resin as described above [hereinafter also referred to as resin (A)] is used. ] refers to a compound obtained by reacting an oxirane ring-containing compound having a specific structure as shown in the above-mentioned general formula [1] with an unsaturated monocarboxylic acid.
【００１５】当該樹脂（Ａ）としては、勿論、上述した
ような各種の化合物を反応せしめたものであれば、いず
れも使用することが出来るが、それらのうちでも特に代
表的なもののみを例示するに留めれば、まず、前掲の一
般式〔１〕で示されるような特定の構造の多官能エポキ
シ化合物〔以下、これを（ａ−１）として扱うものとす
る。〕と、この化合物（ａ−１）の少なくとも１つオキ
シラン環含有基と反応しうる不飽和モノカルボン酸化合
物〔以下、これを（ａ−２）として扱うものとする。〕
とから得られる特定の反応物〔以下、これを（ａ−３）
として扱うものとする。〕などである。As the resin (A), of course, any resin can be used as long as it is made by reacting the various compounds mentioned above, but only the most representative ones are exemplified. In other words, first, a polyfunctional epoxy compound having a specific structure as shown in the above-mentioned general formula [1] [hereinafter, this will be treated as (a-1)]. ] and an unsaturated monocarboxylic acid compound capable of reacting with at least one oxirane ring-containing group of this compound (a-1) [hereinafter, this shall be treated as (a-2). ]
A specific reaction product obtained from [hereinafter referred to as (a-3)]
shall be treated as such. ] etc.
【００１６】そのうち、上記の（ａ−３）を調製するた
めに用いられる、前記特定の構造の多官能エポキシ化合
物（ａ−１）として特に代表的なもののみを挙げるにと
どめれば、２，７−ジヒドロキシナフタレンの単独、あ
るいは、それにβ−ナフトールをも併用し、その２量化
物を経て、オキシラン環含有化物とした形のものなどで
ある。Among them, only the most representative polyfunctional epoxy compounds (a-1) having the above-mentioned specific structure used to prepare the above-mentioned (a-3) are 2, These include 7-dihydroxynaphthalene alone or a combination of β-naphthol and its dimerized product to form an oxirane ring-containing product.
【００１７】前掲の一般式〔１〕で示される化合物のＷ
、Ｘ、ＹおよびＺが、それぞれ、グリシジルエーテル基
または水素原子となっている形の化合物（ただし、Ｗ、
Ｘ、ＹおよびＺが、悉く、水素原子となっているものは
除かれる。）などである。W of the compound represented by the above general formula [1]
, X, Y and Z are each a glycidyl ether group or a hydrogen atom (however, W,
Those in which X, Y and Z are all hydrogen atoms are excluded. ) etc.
【００１８】他方、前記オキシラン環含有基と反応する
不飽和モノカルボン酸類（ａ−２）として特に代表的な
もののみを例示するにとどめれば、アクリル酸、メタク
リル酸、クロトン酸または桂皮酸などであり、これらは
２種以上の混合使用によってもよいが、特に、アクリル
酸の使用が望ましい。On the other hand, typical examples of the unsaturated monocarboxylic acids (a-2) that react with the oxirane ring-containing group include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. Although two or more of these may be used in combination, it is particularly desirable to use acrylic acid.
【００１９】かくして得られるエネルギー線硬化型樹脂
は、それ自体が、高感度のものであり、硬化後において
は、耐水性、耐溶剤性、耐薬品性ならびに耐熱性などに
優れた皮膜を与えるものとなる。The energy ray-curable resin thus obtained is itself highly sensitive, and after curing, provides a film with excellent water resistance, solvent resistance, chemical resistance, heat resistance, etc. becomes.
【００２０】かくして得られる本発明のエネルギー線硬
化型樹脂を、必須の成分として、含んで成るエネルギー
線硬化型樹脂組成物には、さらに必要に応じて、本発明
の目的を逸脱しない範囲内で、とりわけ、保存安定性な
らびに耐水性、耐溶剤性、耐薬品性および耐熱性などを
保持しうる範囲内で、公知慣用の添加剤、就中、他のタ
イプの反応性希釈剤や有機溶剤などを添加せしめること
を、決して、妨げるものではない。[0020] The energy ray curable resin composition comprising the energy ray curable resin of the present invention thus obtained as an essential component may further contain, if necessary, within the scope of the purpose of the present invention. In particular, known and commonly used additives, especially other types of reactive diluents and organic solvents, to the extent that storage stability and water, solvent, chemical and heat resistance can be maintained. This does not in any way prevent the addition of
【００２１】かかる反応性希釈剤としては、単官能性の
ものから多官能性のものまでが広く用いられるが、それ
らのうちでも特に代表的なもののみを例示するに留めれ
ば、２−ヒドロキシエチル（メタ）アクリレート、２−
ヒドロキシプロピル（メタ）アクリレート、２−エチル
ヘキシル（メタ）アクリレート、Ｎ−ビニルピロリドン
、１−ビニルイミダゾール、イソボルニル（メタ）アク
リレート、テトラヒドロフルフィリル（メタ）アクリレ
ート、カルビトール（メタ）アクリレート、フェノキシ
エチル（メタ）アクリレート、ジシクロペンタジエン（
メタ）アクリレート、１，３−ブタンジ（メタ）アクリ
レート、１，６−ヘキサンジオールジ（メタ）アクリレ
ート、ポリエチレングリコールジ（メタ）アクリレート
、ヒドロキシピバリン酸エステルネオペンチルグリコー
ルジ（メタ）アクリレート、トリメチロールプロパント
リ（メタ）アクリレートペンタエリスリトールトリ（メ
タ）アクリレート、ペンタエリスリトールテトラ（メタ
）アクリレートまたはジペンタエリスリトールヘキサ（
メタ）アクリレートなどである。[0021] As such reactive diluents, a wide range of monofunctional to polyfunctional ones are used, but among them, only the most representative ones are exemplified. Ethyl (meth)acrylate, 2-
Hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth)acrylate, tetrahydrofurphyryl (meth)acrylate, carbitol (meth)acrylate, phenoxyethyl ( meth)acrylate, dicyclopentadiene (
meth)acrylate, 1,3-butane di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, trimethylolpropane Tri(meth)acrylate Pentaerythritol Tri(meth)acrylate, Pentaerythritol Tetra(meth)acrylate or Dipentaerythritol Hexa(
(meth)acrylate, etc.
【００２２】また、溶剤として特に代表的なもののみを
例示するに止めれば、トルエンもしくはキシレンのごと
き芳香族炭化水素類；メチルエチルケトン、メチルイソ
ブチルケトンもしくはシクロヘキサノンの如きケトン類
；酢酸メチル、酢酸エチルもしくは酢酸ブチルの如きエ
ステル類；メタノール、エタノール、プロパノールもし
くはブタノールの如きアルコール類、ヘキサン、ヘプタ
ンの如き脂肪族炭化水素類をはじめ、セロソルブアセテ
ート、カルビトールアセテート、ジメチルホルムアミド
またはテトラヒドロフランなどである。[0022] Further, to exemplify only typical solvents, aromatic hydrocarbons such as toluene or xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; methyl acetate, ethyl acetate, or acetic acid; Esters such as butyl; alcohols such as methanol, ethanol, propanol or butanol, aliphatic hydrocarbons such as hexane, heptane, as well as cellosolve acetate, carbitol acetate, dimethylformamide or tetrahydrofuran.
【００２３】本発明でいう前記エネルギー線とは、電子
線、α線、β線、γ線、Ｘ線、中性子線、または紫外線
の如き、電離性放射線や光などを総称するものである。
本発明において、エネルギー線として紫外線を用いるこ
とによって本発明の樹脂組成物を硬化させる場合には、
波長が１，０００〜８，０００オングストロームなる紫
外線により解離してラジカルを発生するような光（重合
）開始剤を使用すべきであり、かかる光（重合）開始剤
としては公知慣用のものが、いずれも使用できるが、そ
のうちでも特に代表的な例を挙げるにとどめれば、アセ
トフェノン類、ベンゾフェノン、ミヒラーズケトン、ベ
ンジン、ベンゾイン・ベンゾエート、ベンゾイン、ベン
ゾインメチルエーテル類、ベンジル・ジメチルケタール
、α−アシロキシムエステル、チオキサントン類、アン
スラキノン類およびそれらの各種の誘導体などである。[0023] The energy ray as used in the present invention is a general term for ionizing radiation and light such as electron beams, α rays, β rays, γ rays, X rays, neutron beams, and ultraviolet rays. In the present invention, when the resin composition of the present invention is cured by using ultraviolet rays as energy rays,
A photo (polymerization) initiator that can be dissociated to generate radicals by ultraviolet light having a wavelength of 1,000 to 8,000 angstroms should be used, and known and commonly used photo (polymerization) initiators include: Any of them can be used, but the most representative examples are acetophenones, benzophenone, Michler's ketone, benzine, benzoin benzoate, benzoin, benzoin methyl ethers, benzyl dimethyl ketal, α-acyloxime ester. , thioxanthones, anthraquinones, and various derivatives thereof.
【００２４】また、こうした光（重合）開始剤には、公
知慣用の光増感剤をも併用することができるが、かかる
光増感剤として特に代表的なもののみを例示するにとど
めれば、アミン類、尿素類、含硫黄化合物、含燐化合物
、含塩素化合物またはニトリル類もしくはその他の含窒
素化合物などである。[0024]Although known and commonly used photosensitizers can also be used in combination with such photo(polymerization) initiators, only particularly representative photosensitizers are exemplified. , amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.
【００２５】本発明のエネルギー線硬化型樹脂を含んで
成るエネルギー線硬化型樹脂組成物は、通常は、そのま
ま、上掲した如きエネルギー源を用いることにより、放
射線ないしは活性エネルギー線を照射させて硬化せしめ
ればよい。The energy ray curable resin composition comprising the energy ray curable resin of the present invention is usually cured as it is by irradiation with radiation or active energy rays using the energy sources listed above. Just force it.
【００２６】[0026]
【実施例】次に、本発明を実施例および応用例により、
一層、具体的に説明する。以下において、部および％は
特に断りの無い限り、すべて重量基準であるものとする
。[Examples] Next, the present invention will be explained by examples and application examples.
This will be explained in more detail. In the following, all parts and percentages are based on weight unless otherwise specified.
【００２７】実施例１
温度計、攪拌機および還流冷却管を備えたフラスコに、
２，７−ジヒドロキシナフタレンを単独で使用し、ある
いは、これにβ−ナフトールを併用して、その２量化物
を経て得られた４官能のエポキシ化合物の５５６ｇとハ
イドロキノンモノメチルエーテルの１．３ｇとを加え、
さらに、アクリル酸の２８８ｇ、トリフェニルフォスフ
ィンの１２．８ｇをも加えて、エポキシ当量が１５００
０以上となるまで、１１０℃の温度で反応せしめて、反
応物（ａ−３−１）を得た。Example 1 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
Using 2,7-dihydroxynaphthalene alone or in combination with β-naphthol, 556 g of a tetrafunctional epoxy compound obtained through its dimerization product and 1.3 g of hydroquinone monomethyl ether were combined. In addition,
Furthermore, 288 g of acrylic acid and 12.8 g of triphenylphosphine were added, and the epoxy equivalent was 1500.
The reaction was carried out at a temperature of 110° C. until the temperature reached 0 or higher to obtain a reaction product (a-3-1).
【００２８】以下、これを樹脂（Ａ−１）と略記する。
実施例２
（ａ−３−１）を合成する際に、アクリル酸の１４４ｇ
を用いるように変更した以外は、実施例１と同様にして
、目的とするエネルギー線硬化樹脂（ａ−３−２）を得
た。Hereinafter, this will be abbreviated as resin (A-1). Example 2 When synthesizing (a-3-1), 144 g of acrylic acid
The target energy ray-cured resin (a-3-2) was obtained in the same manner as in Example 1, except that the resin was changed to use .
【００２９】以下、これを樹脂（Ａ−２）と略記する。
応用例１
実施例１で得られた樹脂（Ａ−１）に対して、下記する
如き各成分を配合し、充分に混合し、攪拌して塗料を調
製した。Hereinafter, this will be abbreviated as resin (A-2). Application Example 1 The following components were added to the resin (A-1) obtained in Example 1, thoroughly mixed, and stirred to prepare a paint.
【００３０】
樹脂（Ａ−１）
１００部 １−ヒ
ドロキシヘキシルフェニルケトン ３部
メチルエチルケトン
３０部次いで、かくして得られた
上記塗料を、水研ぎしたブリキ板に、２０μｍの厚さで
塗布した。Resin (A-1)
100 parts 1-hydroxyhexylphenyl ketone 3 parts
Methyl ethyl ketone
30 parts of the above-mentioned paint thus obtained was then applied to a wet-sanded tin plate to a thickness of 20 μm.
【００３１】しかるのち、８０℃の温風乾燥器中で３０
分間乾燥せしめ、次いで、これを８０Ｗの高圧水銀灯で
、１５ｃｍの高さから、６０秒間のあいだ紫外線を照射
し硬化させた。[0031] After that, it was heated for 30 minutes in a hot air dryer at 80°C.
After drying for minutes, this was then irradiated with ultraviolet rays for 60 seconds from a height of 15 cm using an 80 W high-pressure mercury lamp to cure it.
【００３２】その被覆板について行った性能評価試験の
結果を、第１表に示す。
応用例２
樹脂（Ａ−１）に替えて、実施例２で得られた樹脂（Ａ
−２）の同量を用いるように変更した以外は、応用例１
と同様にして塗料を得、塗布し、硬化させた。Table 1 shows the results of the performance evaluation test conducted on the coated plate. Application example 2 Resin (A-1) obtained in Example 2 was replaced with resin (A-1).
Application example 1 except that the same amount of -2) was used.
The paint was obtained, applied and cured in the same manner as described above.
【００３３】その被覆板についても同様の性能評価を行
った処、第１表に示されるような結果が得られた。
応用例３
実施例１で得られた樹脂（Ａ−１）に対して、下記のよ
うな各成分を配合し、充分に混合し、攪拌して塗料を調
製した。Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained. Application Example 3 The following components were added to the resin (A-1) obtained in Example 1, thoroughly mixed, and stirred to prepare a paint.
【００３４】
樹脂（Ａ−１）
１００部
１−ヒドロキシヘキシルフェニルケトン
３部 トリメチロールプロパントリアク
リレート ２０部 メチルエチルケト
ン ３０
部以後は、応用例１と同様にして塗料を得、塗布し、硬
化させた。Resin (A-1)
100 copies
1-hydroxyhexylphenyl ketone
3 parts Trimethylolpropane triacrylate 20 parts Methyl ethyl ketone 30 parts
After that, a paint was obtained, applied, and cured in the same manner as in Application Example 1.
【００３５】その被覆板についても同様の性能評価を行
った処、第１表に示されるような結果が得られた。
応用例４
樹脂（Ａ−１）に替えて、実施例２で得られた樹脂（Ａ
−２）の同量を用いるように変更した以外は、応用例３
と同様にして塗料を得、塗布し、硬化させた。Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained. Application example 4 Resin (A-1) obtained in Example 2 was replaced with resin (A-1).
Application example 3 except that the same amount of -2) was used.
The paint was obtained, applied and cured in the same manner as described above.
【００３６】その被覆板についても同様の性能評価を行
った処、第１表に示されるような結果が得られた。
比較例１
温度計、攪拌機および還流冷却管を備えたフラスコに、
エポキシ当量が１８８なる「エピクロン ８５０」〔
大日本インキ化学工業株式会社製のビスフェノールＡ型
エポキシ化合物〕の３７６ｇとハイドロキノンモノメチ
ルエーテルの１．３ｇとを加え、さらに、アクリル酸の
１４４ｇをも加えて、酸価が３以下となるまで、１１０
℃の温度で反応せしめて、反応物（ｃ−３−１）を得た
。Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained. Comparative Example 1 In a flask equipped with a thermometer, a stirrer, and a reflux condenser,
"Epicron 850" with an epoxy equivalent of 188 [
Add 376 g of bisphenol A type epoxy compound (manufactured by Dainippon Ink & Chemicals Co., Ltd.) and 1.3 g of hydroquinone monomethyl ether, and then add 144 g of acrylic acid.
The reaction was carried out at a temperature of 0.degree. C. to obtain a reaction product (c-3-1).
【００３７】以下、これを樹脂（Ｃ−１）と略記する。
以後は、樹脂（Ａ−１）に替えて、比較例１で得られた
樹脂（Ｃ−１）の同量を用いるように変更した以外は、
応用例１と同様にして塗料を得、塗布し、硬化させた。Hereinafter, this will be abbreviated as resin (C-1). Thereafter, the same amount of resin (C-1) obtained in Comparative Example 1 was used instead of resin (A-1).
A paint was obtained, applied, and cured in the same manner as in Application Example 1.
【００３８】その被覆板についても同様の性能評価を行
った処、第１表に示されるような結果が得られた。Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained.
【００３９】[0039]
【表１】[Table 1]
【００４０】なお、各性能の評価は、次の用な要領で行
ったものである。
硬化性…………塗布した塗膜を８０℃の温風中で１５分
間乾燥させたのち、８０Ｗ／ｃｍ２ なる強度の高圧水
銀ランプの下、１５ｃｍなる位置を５０ｍ／分なる速度
で通過せしめ、硬化するまでの回数を測定した。[0040]Each performance was evaluated in the following manner. Curing property: After drying the applied coating film in hot air at 80°C for 15 minutes, it was passed through a 15cm position at a speed of 50m/min under a high-pressure mercury lamp with an intensity of 80W/cm2, The number of times it took to harden was measured.
【００４１】耐水性…………ガーゼにイオン交換水を浸
し、硬化塗膜を４０回擦ったのちの膜厚の減少度合いを
測定する。
◎：５μｍ未満
○：５μｍ〜１０μｍ未満
△：１０μｍ〜１５μｍ未満
×：１５μｍ以上
耐溶剤性………ガーゼにアセトンを浸し、硬化塗膜を４
０回擦ったのちの膜厚の減少度合いを測定する。評価基
準は、耐水性と同じ。Water resistance: Gauze is soaked in ion-exchanged water and the cured coating is rubbed 40 times, after which the degree of decrease in film thickness is measured. ◎: Less than 5 μm ○: 5 μm to less than 10 μm △: 10 μm to less than 15 μm
Measure the degree of decrease in film thickness after rubbing 0 times. The evaluation criteria are the same as for water resistance.
【００４２】耐アルカリ性…ガーゼに１０％水酸化ナト
リウム水溶液を浸し、硬化塗膜を４０回擦ったのちの膜
厚の減少度合いを測定する。評価基準は耐水と同じ。Alkali resistance: Gauze is immersed in a 10% aqueous sodium hydroxide solution and the cured coating is rubbed 40 times, after which the degree of decrease in film thickness is measured. The evaluation criteria are the same as for water resistance.
【００４３】耐熱性…………塗布した塗膜を８０℃の温
風中で１５分乾燥させたのち、８０Ｗ／ｃｍ２ なる強
度の高圧水銀ランプの下、１５ｃｍなる位置を５０ｍ／
分なる速度で１０回通過せしめた硬化塗膜を、２００℃
の加熱炉中に４０秒間置いてから直ちに塗膜面にガーゼ
を圧着させ、冷却後にガーゼを剥がして、塗膜の変化の
状態を目視により判定した。Heat resistance: After drying the applied coating film in hot air at 80°C for 15 minutes, it was heated at a distance of 15cm at a distance of 50m/cm under a high-pressure mercury lamp with an intensity of 80W/cm2.
The cured coating film was passed through the film 10 times at a speed of 200°C.
Immediately after placing the sample in a heating oven for 40 seconds, gauze was pressed onto the coating surface, and after cooling, the gauze was peeled off and the state of change in the coating film was visually determined.
【００４４】◎：全く変化が認められないもの○：表面
にガーゼの跡が、少々、付くもの×：塗膜が溶融してし
まい、ガーゼと共に剥がれるもの第１表の結果からも明
らかなように、本発明のエネルギー線硬化型樹脂組成物
は、常温で、あるいは、加熱下で、自由にエネルギー線
硬化させることが出来るし、しかも、特定のオキシラン
環含有化合物の構造に基ずいて得られる諸性能により、
硬化性にも優れるし、かつ、硬化塗膜が耐水、耐溶剤、
耐薬品性を有するし、耐熱性にも優れるものであって、
各種の用途に極めて有用なものである。◎: No change observed at all ○: Some traces of gauze left on the surface ×: The paint film melts and peels off along with the gauze As is clear from the results in Table 1. The energy ray-curable resin composition of the present invention can be freely cured with energy rays at room temperature or under heating, and can be cured with various types of resin based on the structure of a specific oxirane ring-containing compound. Depending on the performance,
It has excellent curability, and the cured coating film is water resistant, solvent resistant,
It has chemical resistance and excellent heat resistance,
It is extremely useful for various uses.
【００４５】[0045]
【発明の効果】本発明のエネルギー線硬化型樹脂樹脂組
成物は、それ自体が高感度のものであり、しかも、硬化
塗膜は耐水性および耐溶剤性ならびに耐薬品性および耐
熱性などにすぐれている処から、とりわけ、コーティン
グ剤、印刷インキならびに接着剤などとして、広範なる
用途において極めて有用なものである。Effects of the Invention The energy ray-curable resin composition of the present invention is highly sensitive in itself, and the cured coating film has excellent water resistance, solvent resistance, chemical resistance, heat resistance, etc. Because of this, it is extremely useful in a wide range of applications, particularly as coating agents, printing inks, and adhesives.
Claims (2)
一であっても異なっていてもよい、水素原子または式【
化２】 で示される基を表わすものとするが、Ｗ、Ｘ、Ｙまたは
Ｚのすべてが水素原子である場合は除くものとする。］
で示される化合物の少なくとも一つのオキシラン環含有
基と、このオキシラン環含有基と反応する基と不飽和二
重結合とを併せ有する化合物との反応物を含有すること
を特徴とする、エネルギー線硬化型樹脂組成物。Claim 1: General formula [Formula 1] [However, W, X, Y, and Z in the formula may each be the same or different, and each represents a hydrogen atom or a formula [
It represents a group represented by the following formula, except when all of W, X, Y or Z are hydrogen atoms. ]
Energy ray curing characterized by containing a reaction product of at least one oxirane ring-containing group of the compound represented by and a compound having both a group that reacts with the oxirane ring-containing group and an unsaturated double bond. mold resin composition.
一であっても異なっていてもい水素原子または式【化４
】 で示される基を表すものとするが、Ｗ、Ｘ、ＹおよびＺ
のすべてが水素原子である場合は除くものとする。］で
示される化合物の少なくとも一つのオキシラン含有基が
、一般式 【化５】 ［ただし、式中のＲ１ は水素原子またはメチル基を、
Ｒ２は水素原子、メチル基、シアノ基およびハロゲン原
子を表わすものとする。］ で示される基で置換されているものである、請求項１に
記載のエネルギー線硬化型樹脂組成物。[Claim 2] General formula [Formula 3] [However, W, X, Y, and Z in the formula may be the same or different, and each represents a hydrogen atom or a formula [Formula 4]
] represents a group represented by W, X, Y and Z
shall be excluded if all of them are hydrogen atoms. ] At least one oxirane-containing group of the compound represented by the general formula [Chemical formula 5] [wherein R1 is a hydrogen atom or a methyl group,
R2 represents a hydrogen atom, a methyl group, a cyano group, or a halogen atom. ] The energy ray-curable resin composition according to claim 1, which is substituted with a group represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3011930A JP3019424B2 (en) | 1991-02-01 | 1991-02-01 | Manufacturing method of new energy ray curable resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3011930A JP3019424B2 (en) | 1991-02-01 | 1991-02-01 | Manufacturing method of new energy ray curable resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04246409A true JPH04246409A (en) | 1992-09-02 |
| JP3019424B2 JP3019424B2 (en) | 2000-03-13 |
Family
ID=11791396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3011930A Expired - Fee Related JP3019424B2 (en) | 1991-02-01 | 1991-02-01 | Manufacturing method of new energy ray curable resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3019424B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7075538B2 (en) | 2019-03-26 | 2022-05-25 | 本田技研工業株式会社 | Internal combustion engine cooling structure |
-
1991
- 1991-02-01 JP JP3011930A patent/JP3019424B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3019424B2 (en) | 2000-03-13 |
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