JPH0491B2 - - Google Patents
Info
- Publication number
- JPH0491B2 JPH0491B2 JP14055683A JP14055683A JPH0491B2 JP H0491 B2 JPH0491 B2 JP H0491B2 JP 14055683 A JP14055683 A JP 14055683A JP 14055683 A JP14055683 A JP 14055683A JP H0491 B2 JPH0491 B2 JP H0491B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- compound
- active energy
- 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.)
- Expired
Links
- -1 aromatic sulfonium salt Chemical class 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000011342 resin composition Substances 0.000 claims description 10
- 239000002841 Lewis acid Substances 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- 125000004069 aziridinyl group Chemical group 0.000 claims description 5
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 238000000576 coating method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000004593 Epoxy Substances 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
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VUBUXALTYMBEQO-UHFFFAOYSA-N 2,2,3,3,3-pentafluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)C(F)(F)C(=O)C1=CC=CC=C1 VUBUXALTYMBEQO-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 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 2
- 238000000034 method Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WYFRCNZIOOYQHH-UHFFFAOYSA-N N1(CC1)[PH2]=O Chemical compound N1(CC1)[PH2]=O WYFRCNZIOOYQHH-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052781 Neptunium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
本発明は、得られる硬化物の基材との密着性が
優れた、コーテイング及び電気・電子材料として
有用な活性エネルギー線硬化型樹脂組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an active energy ray-curable resin composition useful as coatings and electrical/electronic materials, which has excellent adhesion to substrates in the resulting cured product.
従来から、コーテイング及び電気・電子材料と
して、耐食性・電気特性等の観点からエポキシ樹
脂が使用されているが、その硬化方法としては、
酸無水物、アミン等の硬化剤を加え、加熱硬化あ
るいは常温硬化せしめる方法が主である。これに
対して、近年、省資源・省エネルギーの観点から
常温短時間硬化を目的として、紫外線及び電子線
等の活性エネルギー線を照射せしめる硬化方法、
即ち、活性エネルギー線硬化型組成物が提案され
ている。活性エネルギー線硬化型組成物は、通
常、ラジカル反応を用いた方法によつて硬化され
る。したがつて、エポキシ樹脂にラジカル硬化能
を付与するためには、エポキシ樹脂をアクリレー
ト変性又はメタクリレート変性させる必要があ
る。 Epoxy resins have traditionally been used as coatings and electrical/electronic materials due to their corrosion resistance and electrical properties, but their curing methods include:
The main method is to add a curing agent such as an acid anhydride or amine, and then heat or cure at room temperature. On the other hand, in recent years, from the viewpoint of saving resources and energy, curing methods that involve irradiation with active energy rays such as ultraviolet rays and electron beams have been developed for the purpose of short-time curing at room temperature.
That is, active energy ray curable compositions have been proposed. Active energy ray-curable compositions are usually cured by a method using a radical reaction. Therefore, in order to impart radical curing ability to an epoxy resin, it is necessary to modify the epoxy resin with acrylate or methacrylate.
しかしながら、エポキシ樹脂をアクリレート変
性又はメタクリレート変性せしめた、所謂、エポ
キシポリアクリレートを活性エネルギー線硬化せ
しめた硬化物は、耐食性・電気特性等が優れる反
面、基材、例えば、金属板等への密着性が劣ると
いう欠点を有している。 However, cured products obtained by acrylate-modified or methacrylate-modified epoxy resins, so-called epoxy polyacrylates cured with active energy rays, have excellent corrosion resistance and electrical properties, but have poor adhesion to substrates, such as metal plates. It has the disadvantage of being inferior.
そこで、最近、エポキシ樹脂を変性することな
く、常温で短時間硬化が可能な活性エネルギー線
硬化型樹脂組成物の提案がなされているが、得ら
れた硬化物が充分な密着性を有する組成物は、未
だ認められず、密着性に優れた硬化物を与えるエ
ネルギー線硬化型樹脂組成物の出現が強く望まれ
ている。 Therefore, recently, proposals have been made for active energy ray-curable resin compositions that can be cured in a short time at room temperature without modifying the epoxy resin, but the resulting cured product has sufficient adhesion. has not yet been recognized, and there is a strong desire for the emergence of energy ray-curable resin compositions that provide cured products with excellent adhesion.
本発明者らは、鋭意研究した結果、分子中に１
個以上のエポキシ基を有する化合物、分子中に２
個以上のアジリジニル基を有する化合物及び活性
エネルギー線照射下にルイス酸を発生する化合物
を一定の配合割合で含有せしめた組成物が、基材
に対し著しく良好な密着性を示す硬化物を与える
ことを見出し、本発明を完成するに至つた。 As a result of intensive research, the present inventors found that 1 in the molecule.
Compounds with more than 2 epoxy groups in the molecule
A composition containing a compound having two or more aziridinyl groups and a compound that generates a Lewis acid upon irradiation with active energy rays in a certain proportion provides a cured product exhibiting extremely good adhesion to a substrate. They discovered this and completed the present invention.
即ち、本発明の活性エネルギー線硬化型樹脂組
成物は、
(a) 分子中に１個以上のエポキシ基を有する化合
物１〜99.5重量部、
(b) 分子中に２個以上のアジリジニル基を有する
化合物0.5〜99重量部
並びに
(c) 活性エネルギー線照射下にルイス酸を発生す
る化合物；前記(a)成分及び(b)成分の合計100重
量部に対して0.1〜10重量部
からなることを特徴とするものである。 That is, the active energy ray-curable resin composition of the present invention contains (a) 1 to 99.5 parts by weight of a compound having one or more epoxy groups in the molecule, (b) having two or more aziridinyl groups in the molecule. 0.5 to 99 parts by weight of the compound; and (c) a compound that generates a Lewis acid upon irradiation with active energy rays; 0.1 to 10 parts by weight per 100 parts by weight of the total of components (a) and (b). This is a characteristic feature.
本発明に(a)成分として用いるエポキシ化合物
は、分子中に１個以上のエポキシ基を有するもの
であれば、如何なるものでもよいが、好ましく
は、（）２個のエホキシシクロアルキル基を有
するエポキシドエステル；（）ビスフエノール
Ａ、ビスフエノールＦ、ビスフエノールＳのジグ
リシジルエーテル；（）ポリエポキシ化フエノ
ールノボラツク樹脂又はクレゾールノボラツク樹
脂；（）多価アルコールのポリグリシジルエー
テル；（）シクロアルキル系炭化水素、アルキ
ルシクロアルキル系炭化水素又はエーテルのジエ
ポキシド、及び（）前記の任意の混合物、が挙
げられる。 The epoxy compound used as component (a) in the present invention may be any compound as long as it has one or more epoxy groups in the molecule, but preferably has () two epoxycycloalkyl groups. Epoxide ester; () diglycidyl ether of bisphenol A, bisphenol F, bisphenol S; () polyepoxidized phenol novolak resin or cresol novolak resin; () polyglycidyl ether of polyhydric alcohol; () cycloalkyl diepoxides of hydrocarbons, alkylcycloalkyl hydrocarbons or ethers, and mixtures of any of the foregoing.
これらのうち、商業的に入手し得る前記エポキ
シドエステルとしては、３，４−エポキシシクロ
ヘキシルメチル、３，４−エポキシシクロヘキサ
ンカルボキシレート（ユニオンカーバイド社
ERL−4221；チバガイギー社CY−179）、ビス
（３，４−エポキシ−６−メチルシクロヘキシル
メチル）アジペート（ユニオンカーバイド社
ERL−4289）及びビス（３，４−エポキシシク
ロヘキシルメチル）アジペート（ユニオンカーバ
イド社ERL−4299）等が挙げられ、ビスフエノ
ールＡのジグリシジルエーテルとしては、チバガ
イギー社のアラルダイト6010、ダウケミカル社の
DER331及びシエル化学社のエポン828が挙げら
れる。 Among these, the commercially available epoxide esters include 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexane carboxylate (Union Carbide Co., Ltd.)
ERL-4221; Ciba Geigy CY-179), bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate (Union Carbide)
ERL-4289) and bis(3,4-epoxycyclohexylmethyl) adipate (Union Carbide ERL-4299), etc. Diglycidyl ether of bisphenol A includes Ciba Geigy's Araldite 6010, Dow Chemical's
Examples include DER331 and Epon 828 from Ciel Chemical Co., Ltd.
ポリエポキシ化フエノールノボラツク樹脂は、
ダウケミカル社DEN−431及び438等として、ま
た、ポリエポキシ化クレゾールノボラツク樹脂
は、チバガイギー社アダルダイト538等として入
手可能である。 Polyepoxidized phenol novolak resin is
Polyepoxidized cresol novolak resins are available as DOW Chemical Company DEN-431 and 438, etc., and polyepoxidized cresol novolak resins are available as Adaldite 538, Ciba Geigy Company, etc.
多価アルコールのポリグリシジルエーテルとし
ては、ブタン−１，４−ジオールに由来するもの
として、チバガイギー社アラルダイトRD−２等
が、また、グリセリンに由来するものとして、シ
エル化学社エポン812等が入手可能である。 As polyglycidyl ethers of polyhydric alcohols, those derived from butane-1,4-diol such as Ciba Geigy's Araldite RD-2 are available, and those derived from glycerin such as Siel Kagaku Epon 812 are available. It is.
更に、アルキルシクロアルキル系炭化水素のジ
エポキシドは、ビニルシクロヘキセンジオキシド
（ユニオンカーバイド社ERL−4206）として、ま
た、シクロアルキルエーテルのジエポキシドは、
ビス（２，３−エポキシシクロペンチル）エーテ
ル（ユニオンカーバイド社ERL−0400）として
入手可能である。 Furthermore, diepoxides of alkylcycloalkyl hydrocarbons are vinylcyclohexene dioxide (Union Carbide ERL-4206), and diepoxides of cycloalkyl ethers are
It is available as bis(2,3-epoxycyclopentyl)ether (Union Carbide ERL-0400).
本発明の(b)成分である分子中に２個以上のアジ
リジニル基を有する化合物としては、テトラメチ
レンビス−Ｎ，Ｎ−エチレン尿素、ヘキサメチレ
ンビス−Ｎ，Ｎ−エチレン尿素、トリス（１−ア
ジリジニル）ホスフインオキシド、ω−アジリジ
ニルプロピオン酸−２，２−ジヒドロキシメチル
ブタノール−トリエステル等が挙げられるが、特
にω−アジリジニルプロピオン酸−２，２−ジヒ
ドロキシメチルブタノール−トリエステルが好適
である。 Examples of compounds having two or more aziridinyl groups in the molecule which are component (b) of the present invention include tetramethylenebis-N,N-ethyleneurea, hexamethylenebis-N,N-ethyleneurea, tris(1- (aziridinyl) phosphine oxide, ω-aziridinylpropionic acid-2,2-dihydroxymethylbutanol-triester, etc., but in particular ω-aziridinylpropionic acid-2,2-dihydroxymethylbutanol-triester. suitable.
本発明の(c)成分である活性エネルギー線照射下
にルイス酸を発生する化合物としては、
次式（）：
［RaR1bX］+c・［MX1d］-(d-e) （）
（式中、Ｒは１価の芳香族有機基；R1は２価の
芳香族有機基；Ｘ及びX1は、それぞれ、Ｉ、Br、
Cl、Ｆ等のハロゲン元素；Ｍは、Sb、Fe、Sn、
Bi、Al、Ga、In、Ti、Zr、Sc、Ｖ、Cr、Mn、
Cs等の遷移金属元素、La、Ce、Pr、Nd等のラ
ンタニド元素、Th、Pa、Ｕ、Np等のアクチニ
ド元素、Ｂ、Ｐ、As等の元素；ａは０又は２の
整数；ｂは０又は１の整数；ｅは２〜７の整数で
あるＭの原子価；ｄはｅより大きな８までの整
数；をそれぞれ表わし、ａ＋ｂは２又はＸの原子
価であり、ｃ＝ｄ−ｅの関係にあり；［MX1d］-(d
−ｅ）で示される錯陰イオンの例としては、BF4 -、
PF6 -、AsF6 -、SbF6 -、FeCl4 2-、SnCl6 2-、
SbCl6 -、BiCl5 2-等が挙げられる）
で示される芳香族ハロニウム塩、
次式（）：
（式中、Ｍ、X1、ｃ、ｄ、ｅは前記と同義であ
り；Ｙは、ニトロ基、ハロゲン元素、Ｎ−モルホ
リノ基、アルキル基、アルコキシ基、アリール
基、アミノ基、アリールアミノ基、アルキルアミ
ノ基、アリールメルカプト基等を表わす）
で示される芳香族ジアゾニウム塩及び錯ハロゲン
化物の芳香族スルホニウム塩等が挙げられるが、
錯ハロゲン化物の芳香族スルホニウム塩が発泡等
の欠点がなく好適である。 The compound (c) of the present invention, which generates a Lewis acid under active energy ray irradiation, has the following formula (): [RaR 1 bX] +c・[MX 1 d] -(de) () (Formula where R is a monovalent aromatic organic group; R 1 is a divalent aromatic organic group; X and X 1 are I, Br,
Halogen elements such as Cl and F; M is Sb, Fe, Sn,
Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn,
Transition metal elements such as Cs, lanthanide elements such as La, Ce, Pr, Nd, actinide elements such as Th, Pa, U, Np, elements such as B, P, As; a is an integer of 0 or 2; b is an integer an integer of 0 or 1; e is the valence of M which is an integer from 2 to 7; d is an integer up to 8 that is larger than e; a+b is the valence of 2 or X, and c=d-e The relationship is; [MX 1 d] -(d
Examples of complex anions represented by -e) include BF 4 - ,
PF 6 - , AsF 6 - , SbF 6 - , FeCl 4 2- , SnCl 6 2- ,
SbCl 6 - , BiCl 5 2-, etc.) Aromatic halonium salt represented by the following formula (): ( wherein M, , alkylamino group, arylmercapto group, etc.) and aromatic sulfonium salts of complex halides.
Aromatic sulfonium salts of complex halides are preferred since they do not have drawbacks such as foaming.
錯ハロゲン化物の芳香族スルホニウム塩として
は、トリフエニルスルホニウムテトラフルオロボ
レート、トリフエニルスルホニウムヘキサフルオ
ロアンチモネート、５−フエニルジベンゾチオフ
エニウムフルオロボレート、フエナシルテトラメ
チレンスルホニウムヘキサフルオロアルセネー
ト、トリフエニルスルホニウムヘキサフルオロア
ルセネート等が挙げられる。 Examples of aromatic sulfonium salts of complex halides include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 5-phenyldibenzothiophenium fluoroborate, phenacyltetramethylenesulfonium hexafluoroarsenate, triphenylsulfonium Examples include hexafluoroarsenate.
本発明の樹脂組成物において、(a)成分として用
いるエポキシ化合物と(b)成分として用いるアジリ
ジニル化合物との配合割合は、重量比で１〜
99.5：0.5〜99であることが必要である。エポキ
シ化合物の配合割合が前記上限を超えると、配合
物の貯蔵安定性が悪くなり、前記下限未満である
と、得られる塗膜の密着性が不充分となる。ま
た、(c)成分として用いる活性エネルギー線照射下
にルイス酸を発生する化合物の配合割合は、前記
(a)成分及び(b)成分の合計100重量部に対して0.1〜
10重量部であることが必要である。この配合割合
が前記上限を超えると、配合物の貯蔵安定性が悪
くなり、前記下限未満であると、配合物の硬化が
不充分となる。 In the resin composition of the present invention, the blending ratio of the epoxy compound used as component (a) and the aziridinyl compound used as component (b) is 1 to 1 by weight.
99.5: Must be between 0.5 and 99. If the blending ratio of the epoxy compound exceeds the above upper limit, the storage stability of the blend will deteriorate, and if it is below the above lower limit, the resulting coating film will have insufficient adhesion. In addition, the blending ratio of the compound that generates Lewis acid under active energy ray irradiation used as component (c) is as described above.
0.1 to 100 parts by weight of component (a) and component (b)
It is necessary that the amount is 10 parts by weight. If this blending ratio exceeds the above upper limit, the storage stability of the blend will deteriorate, and if it is below the above lower limit, the blend will not be sufficiently cured.
本発明の組成物には、上述した化合物以外に通
常使用される添加剤、開始剤、着色剤、可塑剤、
無機充填剤、重合禁止剤等の任意成分を含めるこ
とができる。 In addition to the above-mentioned compounds, the composition of the present invention includes commonly used additives, initiators, colorants, plasticizers,
Optional components such as inorganic fillers and polymerization inhibitors can be included.
また、本発明の組成物を硬化させる活性エネル
ギー線としては、γ線、紫外線、電子線、Ｘ線等
が使用できるが、好ましくは紫外線、電子線が挙
げられる。 Further, as active energy rays for curing the composition of the present invention, gamma rays, ultraviolet rays, electron beams, X-rays, etc. can be used, and preferably ultraviolet rays and electron beams are used.
本発明の活性エネルギー線硬化型樹脂組成物か
ら得られた硬化物は、従来のものに比し、極めて
優れた密着性を有する。 The cured product obtained from the active energy ray-curable resin composition of the present invention has extremely excellent adhesion compared to conventional products.
以下、実施例及び比較例により、本発明を更に
詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例 １
ビスフエノールＡジグリシジルエーテル樹脂
（シエル化学社製、エピコート828）80重量部とω
−アジリジニルプロピオン酸−２，２−ジヒドロ
キシメチルブタノール−トリエステル20重量部と
を混合し、これに、トリフエニルスルホニウムヘ
キサフルオロアンチモネート５重量部を添加し、
充分に撹拌・混合した後、バーコーターNo.22を用
いて軟綱板上に塗布した。この塗板を、80W／cm
の紫外線ランプを用いて15秒間照射したところ、
密着性の優れた鉛筆硬度2Hの塗膜が得られた。Example 1 80 parts by weight of bisphenol A diglycidyl ether resin (manufactured by Ciel Chemical Co., Ltd., Epicoat 828) and ω
- 20 parts by weight of aziridinylpropionic acid-2,2-dihydroxymethylbutanol-triester, and to this, 5 parts by weight of triphenylsulfonium hexafluoroantimonate,
After stirring and mixing thoroughly, the mixture was coated onto a soft steel board using bar coater No. 22. This coated plate is 80W/cm
When irradiated for 15 seconds using an ultraviolet lamp,
A coating film with a pencil hardness of 2H with excellent adhesion was obtained.
比較例 １
実施例１で使用したビスフエノールＡジグリシ
ジルエーテル樹脂100重量部に、単に、トリフエ
ニルスルホニウムヘキサフルオロアンチモネート
５重量部を添加し、その後、実施例１と同様にし
て軟綱板上に硬化塗膜を得た。しかし、密着性が
不充分であり、かつ、鉛筆硬度もHBと低い塗膜
が得られただけであつた。Comparative Example 1 5 parts by weight of triphenylsulfonium hexafluoroantimonate was simply added to 100 parts by weight of the bisphenol A diglycidyl ether resin used in Example 1, and then the resin was coated on a soft steel board in the same manner as in Example 1. A cured coating film was obtained. However, only a coating film with insufficient adhesion and a low pencil hardness of HB was obtained.
実施例 ２
３，４−エポキシシクロヘキシルメチル３，４
−エポキシシクロヘキサンカルボキシレート（ユ
ニオンカーバイド社、ERL−4221）40重量部と、
トリス（１−アジリジニルホスフインオキシド60
重量部とを混合し、これに、トリフエニルスルホ
ニウムヘキサフルオロアルセネート５重量部を添
加し、充分に撹拌・混合した後、バーコーターNo.
22を用いて軟綱板上に塗布した。この塗板を
80W／cmの紫外線ランプを用いて15秒間照射した
ところ、密着性の優れた鉛筆硬度3Hの塗膜が得
られた。Example 2 3,4-epoxycyclohexylmethyl 3,4
- 40 parts by weight of epoxycyclohexane carboxylate (Union Carbide, ERL-4221);
Tris(1-aziridinylphosphine oxide 60
After adding 5 parts by weight of triphenylsulfonium hexafluoroarsenate and stirring and mixing thoroughly, bar coater No.
22 was used to coat the soft rope board. This painted plate
When irradiated for 15 seconds using an 80 W/cm ultraviolet lamp, a coating film with a pencil hardness of 3H with excellent adhesion was obtained.
比較例 ２
実施例２で使用した３，４−エポキシシクロヘ
キシルメチル３，４−エポキシシクロヘキサンカ
ルボキシレート100重量部に、単に、トリフエニ
ルスルホニウムヘキサフルオロアルセネート５重
量部を添加し、その後、実施例２と同様にして、
軟綱板上に硬化塗膜を得た。しかし、密着性が不
充分な塗膜が得られただけであつた。Comparative Example 2 5 parts by weight of triphenylsulfonium hexafluoroarsenate was simply added to 100 parts by weight of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate used in Example 2, and then Example 2 Similarly,
A cured coating film was obtained on a soft steel board. However, only a coating film with insufficient adhesion was obtained.
実施例 ３
実施例１で用いた配合物を、同様に軟綱板上に
塗布し、電子線を空気中で5Mradとなるように
照射したところ、照射直後は、若干タツクがあつ
たが、24時間後にはタツクフリーになり、密着性
の優れた鉛筆硬度HBの塗膜が得られた。Example 3 The formulation used in Example 1 was similarly applied onto a soft steel board and irradiated with an electron beam at 5 Mrad in the air. After some time, it became tack-free and a coating film with pencil hardness HB with excellent adhesion was obtained.
実施例 ４
ノボラツクタイプエポキシ樹脂であるエポン
152（シエル化学社製）90重量部とω−アジリジニ
ルプロピオン酸−２，２−ジヒドロキシメチルブ
タノール−トリエステル10重量部とを混合し、こ
れに、トリフエニルスルホニウムテトラフルオロ
ボレート５重量部を添加し、充分に撹拌・混合し
た後、バーコーターNo.22を用いて軟綱板上に塗布
した。この塗板を、80W／cmの紫外線ランプを用
いて、10秒間照射したところ、密着性の優れた鉛
筆硬度Ｈの塗膜が得られた。Example 4 Epon, a novolac type epoxy resin
152 (manufactured by Ciel Chemical Co., Ltd.) and 10 parts by weight of ω-aziridinylpropionic acid-2,2-dihydroxymethylbutanol-triester, and to this, 5 parts by weight of triphenylsulfonium tetrafluoroborate. After adding and thoroughly stirring and mixing, it was coated on a soft steel board using bar coater No. 22. When this coated plate was irradiated for 10 seconds using an 80 W/cm ultraviolet lamp, a coating film with excellent adhesion and a pencil hardness of H was obtained.
Claims (1)
化合物１〜99.5重量部、 (b) 分子中に２個以上のアジリジニル基を有する
化合物0.5〜99重量部 並びに (c) 活性エネルギー線照射下にルイス酸を発生す
る化合物；前記(a)成分及び(b)成分の合計100重
量部に対して0.1〜10重量部 からなることを特徴とする活性エネルギー線硬化
型樹脂組成物。 ２ 分子中に２個以上のアジリジニル基を有する
化合物が、ω−アジリジニルプロピオン酸−２，
２−ジヒドロキシメチルブタノール−トリエステ
ルである特許請求の範囲第１項記載の樹脂組成
物。 ３ 活性エネルギー線が、紫外線又は電子線であ
る特許請求の範囲第１項記載の樹脂組成物。 ４ 活性エネルギー線照射下にルイス酸を発生す
る化合物が、錯ハロゲン化物の芳香族スルホニウ
ム塩である特許請求の範囲第１項記載の樹脂組成
物。[Scope of Claims] 1 (a) 1 to 99.5 parts by weight of a compound having one or more epoxy groups in the molecule, (b) 0.5 to 99 parts by weight of a compound having two or more aziridinyl groups in the molecule, and ( c) A compound that generates a Lewis acid upon irradiation with active energy rays; an active energy ray-curable type characterized by comprising 0.1 to 10 parts by weight based on a total of 100 parts by weight of components (a) and (b). Resin composition. 2 A compound having two or more aziridinyl groups in the molecule is ω-aziridinylpropionic acid-2,
The resin composition according to claim 1, which is 2-dihydroxymethylbutanol-triester. 3. The resin composition according to claim 1, wherein the active energy ray is an ultraviolet ray or an electron beam. 4. The resin composition according to claim 1, wherein the compound that generates a Lewis acid upon irradiation with active energy rays is an aromatic sulfonium salt of a complex halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14055683A JPS6032822A (en) | 1983-08-02 | 1983-08-02 | Active energy ray-curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14055683A JPS6032822A (en) | 1983-08-02 | 1983-08-02 | Active energy ray-curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6032822A JPS6032822A (en) | 1985-02-20 |
| JPH0491B2 true JPH0491B2 (en) | 1992-01-06 |
Family
ID=15271423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14055683A Granted JPS6032822A (en) | 1983-08-02 | 1983-08-02 | Active energy ray-curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6032822A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9757789B2 (en) | 2011-09-30 | 2017-09-12 | Nisshin Steel Co., Ltd. | Method of manufacturing rectangular tube having stepped portion |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1106613B1 (en) * | 1999-12-07 | 2002-04-10 | Chinese Petroleum Corporation | Uretedione derivative, curable resin composition comprising the same, and process for producing the same |
-
1983
- 1983-08-02 JP JP14055683A patent/JPS6032822A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9757789B2 (en) | 2011-09-30 | 2017-09-12 | Nisshin Steel Co., Ltd. | Method of manufacturing rectangular tube having stepped portion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6032822A (en) | 1985-02-20 |
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