JPH02127418A - Ultraviolet-and heat-curable epoxy resin composition - Google Patents
Ultraviolet-and heat-curable epoxy resin compositionInfo
- Publication number
- JPH02127418A JPH02127418A JP28086288A JP28086288A JPH02127418A JP H02127418 A JPH02127418 A JP H02127418A JP 28086288 A JP28086288 A JP 28086288A JP 28086288 A JP28086288 A JP 28086288A JP H02127418 A JPH02127418 A JP H02127418A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- ultraviolet
- resin composition
- heat
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 39
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract 2
- 150000002460 imidazoles Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-O 2-methyl-1h-imidazol-3-ium Chemical compound CC=1NC=C[NH+]=1 LXBGSDVWAMZHDD-UHFFFAOYSA-O 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 125000005591 trimellitate group Chemical group 0.000 abstract 2
- PJGMVHVKKXYDAI-UHFFFAOYSA-O 2-(2-undecyl-1h-imidazol-1-ium-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=C[NH+]1C(C)C#N PJGMVHVKKXYDAI-UHFFFAOYSA-O 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 abstract 1
- -1 aromatic diazonium salts Chemical class 0.000 description 19
- 238000001723 curing Methods 0.000 description 19
- 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 9
- 239000004593 Epoxy Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 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 6
- 125000003277 amino group Chemical group 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000976 ink Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 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
- 150000001768 cations Chemical group 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 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
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- SUDVPELGFZKOMD-UHFFFAOYSA-N 1,2-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C(C)C)C(C(C)C)=CC=C3SC2=C1 SUDVPELGFZKOMD-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-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
- NDBJTKNWAOXLHS-UHFFFAOYSA-N 4-methoxybenzenediazonium Chemical compound COC1=CC=C([N+]#N)C=C1 NDBJTKNWAOXLHS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、紫外線の照射および熱によって硬化するエポ
キシ樹脂組成物に関し、特に、プリント配線基板用レジ
スト材料として有用なものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an epoxy resin composition that is cured by ultraviolet irradiation and heat, and is particularly useful as a resist material for printed wiring boards.
〈従来の技術〉
近年、紫外線の照射により樹脂を硬化する方法が各種の
分野で用いられている。 特に、プリント配線基板の加
工分野においては、永久保護膜として使用されるメツキ
用レジスト材料、ソルダーレジストインキにおいて、紫
外線硬化型樹脂への転換が進められている。<Prior Art> In recent years, methods of curing resins by irradiating them with ultraviolet light have been used in various fields. In particular, in the field of processing printed wiring boards, a shift to ultraviolet curing resins is being made in plating resist materials and solder resist inks used as permanent protective films.
現在までに、各種の紫外線硬化型樹脂組成物や、紫外線
硬化型樹脂が知られているが、−例をあげると、特開昭
５７−１７２９１５号公報に開示されているウレタン（
メタ）アクリレートとアクリレートモノマーを含有する
樹脂組成物や、特開昭６２−３３３６５１号公報に開示
されているエポキシ（メタ）アクリレート樹脂があり、
各種のエポキシ樹脂が芳香族ジアゾニウム塩等の紫外線
重合開始剤で硬化することも知られている（特公昭５２
−１４２７８号公報、特開昭５６−２６９２７号公報、
特開昭５９−１９９７１４号公報）。To date, various types of ultraviolet curable resin compositions and ultraviolet curable resins have been known. For example, urethane (
There are resin compositions containing meth)acrylate and acrylate monomers, and epoxy (meth)acrylate resins disclosed in JP-A-62-333651.
It is also known that various epoxy resins can be cured with ultraviolet polymerization initiators such as aromatic diazonium salts (Japanese Patent Publication No. 52
-14278 publication, JP-A-56-26927 publication,
(Japanese Unexamined Patent Publication No. 199714/1983).
〈発明が解決しようとする課題〉
紫外線の照射による樹脂の硬化方法は、熱硬化方法と比
べ、
■硬化時間が短い、
■低温での硬化が可能である、
■溶剤を必要としないか、または少量でよいため、省資
源であり、かつ環境汚染が少ない等の利点を有する。<Problems to be solved by the invention> Compared to thermal curing methods, the method of curing resin by irradiating ultraviolet rays has the following advantages: ■ Shorter curing time; ■ Curing at low temperatures; ■ Does not require a solvent; Since only a small amount is required, it has advantages such as resource saving and less environmental pollution.
しかし、紫外線が到達しない部位は硬化しないので、硬
化させようとする樹脂組成物にタルク等の無機充填剤が
多量に配合されていたり、樹脂組成物の層が厚い（数１
００μ以上）場合、深部硬化を達成し得ないという欠点
も有する。However, since areas that UV rays do not reach do not harden, the resin composition to be cured may contain a large amount of inorganic filler such as talc, or the resin composition layer may be thick (several 1
00μ or more), it also has the disadvantage that deep hardening cannot be achieved.
本発明は、上記の事実に鑑みてなされたものであり、紫
外線の照射、熱のいずれによっても硬化する紫外線硬化
型エポキシ樹脂組成物の提供を目的とする。The present invention has been made in view of the above facts, and aims to provide an ultraviolet curable epoxy resin composition that can be cured by both ultraviolet irradiation and heat.
く課題を解決するための手段〉
本願発明者は、エポキシ樹脂の熱重合型硬化剤のうち、
−級アミノ基を有しないイミダゾール化合物のうちのあ
る種のものが、紫外線重合開始剤の作用を阻害しないと
の知見を得、本発明を完成したものである。Means for Solving the Problems The inventors of the present application have discovered that among thermopolymerizable curing agents for epoxy resins,
The present invention was completed based on the finding that certain imidazole compounds that do not have -grade amino groups do not inhibit the action of ultraviolet polymerization initiators.
本発明は、エポキシ樹脂１００重量部に対し、紫外線重
合開始剤０．５〜１０重量部と、−酸アミノ基を有しな
いイミダゾリウム・メリット酸塩、２−メチルイミダゾ
リウムト
リ
イ
ソシアヌル酸塩、
（ただし、
ｎは正の整数である）
および
より選ばれるｔｆ１以上のイミダゾール系化合物０．５
〜１０重量部とを含有することを特徴とする紫外線およ
び熱硬化型エポキシ樹脂組成物を提供するものである。The present invention comprises 100 parts by weight of an epoxy resin, 0.5 to 10 parts by weight of an ultraviolet polymerization initiator, imidazolium mellitic acid salt having no -acid amino group, 2-methylimidazolium triisocyanurate, ( (where n is a positive integer) and an imidazole compound of tf1 or higher selected from 0.5
The present invention provides an ultraviolet ray and thermosetting epoxy resin composition characterized in that it contains 10 parts by weight.
以下に、本発明の詳細な説明する。The present invention will be explained in detail below.
はじめに、本発明の必須構成成分について説明する。First, the essential components of the present invention will be explained.
本発明で用いるエポキシ樹脂とは、エポキシ樹脂金てを
含む。 即ち、ビスフェノールＡ型、ノボラック型、ビ
スフェノールＦ型、臭素化ビスフェノールＡ型等のグリ
シジルエーテル系エポキシ樹脂の他、環式脂肪族、グリ
シジルエステル系、グリシジルアミン系、複素環式等の
特殊なエポキシ樹脂や、各種の変性エポキシ樹脂を含む
。The epoxy resin used in the present invention includes epoxy resin metal. That is, in addition to glycidyl ether type epoxy resins such as bisphenol A type, novolac type, bisphenol F type, and brominated bisphenol A type, special epoxy resins such as cycloaliphatic, glycidyl ester type, glycidylamine type, and heterocyclic type. and various modified epoxy resins.
エポキシ樹脂は、旭化成工業■、旭電化工業■、日本チ
バガイギー■、三井石油化学工業■、大日本インキ化学
工業■、住友化学工業■、油化シェルエポキシ■等から
多種類市販されているので、これらを用いればよい。Many types of epoxy resins are commercially available from Asahi Kasei Kogyo ■, Asahi Denka Kogyo ■, Nippon Ciba Geigy ■, Mitsui Petrochemicals ■, Dainippon Ink & Chemicals ■, Sumitomo Chemical ■, Yuka Shell Epoxy ■, etc. You can use these.
本発明で用いる紫外線重合開始剤とは、芳香族ジアゾニ
ウム塩、芳香族ヨードニウム塩、芳香族スルフオニウム
塩、芳香族セレニウム塩等のカチオン性化合物をいう。The ultraviolet polymerization initiator used in the present invention refers to cationic compounds such as aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and aromatic selenium salts.
これらの紫外線重合開始剤は、いずれも紫外線によって
分解し、ルイス酸を放出し、このルイス酸がエポキシ基
を重合する。All of these ultraviolet polymerization initiators are decomposed by ultraviolet light and release Lewis acids, which polymerize epoxy groups.
具体的には、カチオン部分は、
等であり、対応するアニオンは、５ｂＦ６ＡｓＦ６−
、 ＰＦ、−、ＢＦ ４− 、 ｐｅｃ
１４− 、 ５ｎＣ１ａＳｂＣ１６−１ＢｉＣ１，”
−等である。Specifically, the cation moiety is and the corresponding anion is 5bF6AsF6-
, PF,-, BF4-, pec
14-, 5nC1aSbC16-1BiC1,”
- etc.
より具体的には、Ｐ−クロロベンゼンジアゾニウム・ヘ
キサフロロフォスフエイト、Ｐ−メトキシベンゼンジア
ゾニウム・ヘキサフロロフォスフエイト、ジフェニルヨ
ードニウム・へキサフロロフォスフェート、トリフェニ
ルスルフオニウム
あげられる。More specific examples include P-chlorobenzenediazonium hexafluorophosphate, P-methoxybenzenediazonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and triphenylsulfonium.
これらの紫外線重合開始剤の分解に有効な波長は、主に
カチオンの化学構造に依存して変わる。 また、硬化速
度は、主にアニオンの種類と硬化するエポキシ樹脂の種
類によって変わるので、用途により適当なものを選択す
ればよい。The effective wavelength for the decomposition of these ultraviolet polymerization initiators varies primarily depending on the chemical structure of the cation. Furthermore, since the curing speed varies mainly depending on the type of anion and the type of epoxy resin to be cured, an appropriate one may be selected depending on the application.
本発明のエポキシ樹脂組成物は、上記のエポキシ樹脂お
よび紫外線重合開始剤の他に、熱重合型硬化剤として、
−級アミノ基を有しないイミダゾール化合物のうちのあ
る種のものを含有する。 即ち、一般アミノ基を有しな
いイミダゾリウム・トリメリット酸塩、２−メチルイミ
ダゾリウム・インシアヌル酸塩、
（ただし、
ｎは正の整数である）
および
より選ばれる１種以上のイミダゾール系化合物である。In addition to the above-mentioned epoxy resin and ultraviolet polymerization initiator, the epoxy resin composition of the present invention contains, as a thermally polymerizable curing agent,
Contains certain imidazole compounds that do not have -grade amino groups. That is, one or more imidazole compounds selected from imidazolium trimellitate, 2-methylimidazolium incyanurate (where n is a positive integer), and which do not have a general amino group. .
−級アミノ基を有しないイミダゾリウム・トリメリッ
ト酸塩としては、１−シアンエチル−２−ウンデシルイ
ミダゾリウム・トリメリット酸塩、１−シアノエチル−
２−フェニルイミダゾリウム・トリメリット酸塩等が例
示できる。Examples of imidazolium trimellitate having no -class amino group include 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-
Examples include 2-phenylimidazolium trimellitate.
一般に、熱重合型硬化剤は、紫外線重合開始剤の作用を
阻害し、アニオン重合型硬化剤であるイミダゾール系化
合物もその例にもれない。Generally, thermally polymerizable curing agents inhibit the action of ultraviolet polymerization initiators, and imidazole compounds, which are anionic polymerizable curing agents, are no exception.
しかし、上記の本発明で用いるイミダゾール系化合物は
、エポキシ樹脂と紫外線重合開始剤とを含有するエポキ
シ樹脂組成物に所定の範囲で配合すると、紫外線重合開
始剤の作用を阻害せず、かつ熱重合型硬化剤として有効
に働く 。However, when the imidazole compound used in the present invention is blended within a predetermined range into an epoxy resin composition containing an epoxy resin and an ultraviolet polymerization initiator, it does not inhibit the action of the ultraviolet polymerization initiator and can be thermally polymerized. Works effectively as a mold hardening agent.
本発明では、上記の各必須成分を、各々単独で、または
２ｆ！以上混合して使用することができる。In the present invention, each of the above essential components may be used alone or 2f! The above can be used in combination.
次に、本発明の必須構成成分の配合割合について述べる
。Next, the blending ratio of the essential constituent components of the present invention will be described.
紫外線重合開始剤は、エポキシ樹脂１００重量部に対し
、０．５〜１０重量部含有させる。The ultraviolet polymerization initiator is contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the epoxy resin.
０．５重量部未満では、エポキシ樹脂を十分に光重合さ
せることが出来ず、１０重量部超では、効果が飽和し、
これ以上加えても硬化速度は向上しない。If it is less than 0.5 parts by weight, the epoxy resin cannot be sufficiently photopolymerized, and if it exceeds 10 parts by weight, the effect is saturated,
Adding more than this will not improve the curing speed.
イミダゾール系化合物は、エポキシ樹脂１００重量部に
対し、０．５〜１０重量部含有させる。 ０．５重量
部未満では、エポキシ樹脂を十分に熱重合させることが
出来ず、１０重量部超では、紫外線重合開始剤の作用を
阻害する。The imidazole compound is contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the epoxy resin. If it is less than 0.5 parts by weight, the epoxy resin cannot be thermally polymerized sufficiently, and if it exceeds 10 parts by weight, the action of the ultraviolet polymerization initiator is inhibited.
本発明のエポキシ樹脂組成物は、上記の必須成分を含有
するが、この他、２−クロルチオキサントン、２，４−
ジイソプロピルチオキサントン、２，４−ジメチルチオ
キサントン、ベンシフξノン等の光増感助剤、ト・リエ
チルアミン、ト・リエタノールアミン、２−ジメチルア
ミノエタノール、トリフェニルフォスフイン、β−チオ
ジグリコール等の光増感促進剤、さらには、充填剤、増
粘剤、可塑剤、安定剤、粘着性付与剤等を含有させるこ
とは差し支えない。The epoxy resin composition of the present invention contains the above-mentioned essential components, but also contains 2-chlorothioxanthone, 2,4-
Photosensitizing aids such as diisopropylthioxanthone, 2,4-dimethylthioxanthone, bensifnone, tri-ethylamine, tri-triethanolamine, 2-dimethylaminoethanol, triphenylphosphine, β-thiodiglycol, etc. There is no problem in containing a photosensitizer, as well as fillers, thickeners, plasticizers, stabilizers, tackifiers, and the like.
また、必要に応じ、少量の溶剤を含有させてもよい。Additionally, a small amount of solvent may be included if necessary.
本発明の樹脂組成物は、その含有成分を攪拌、混合する
ことで得られる。 そして、冷暗所に保存する。The resin composition of the present invention can be obtained by stirring and mixing its components. Then, store it in a cool dark place.
本発明の樹脂組成物の硬化は、紫外線の照射および／ま
たは熱によっ０行なわれる。 硬化に際し、紫外線の照
射による硬化と熱による硬化を同時に行ってもよいし、
紫外線の照射による硬化の前および／または後に、熱に
よる硬化を行ってもよいが、紫外線の照射によって一次
硬化を行なった後、熱による二次硬化を行うと、より完
全な硬化が達成され、好ましい。The resin composition of the present invention is cured by ultraviolet irradiation and/or heat. When curing, curing by ultraviolet irradiation and heat curing may be performed simultaneously,
Although heat curing may be performed before and/or after curing by ultraviolet irradiation, more complete curing is achieved by performing primary curing by ultraviolet irradiation and then performing secondary curing by heat. preferable.
紫外線の照射は、水銀ランプ、キセノンランプ、カーボ
ンアーク、メタルハライドランプ、太陽光等を紫外線照
射源として用い、１５０〜４５０ｎｍの紫外線を含む光
線を、空気中もしくは不活性ガス雰囲気中で照射すれば
よい。For UV irradiation, a mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, etc. may be used as the UV irradiation source, and a light beam containing UV rays of 150 to 450 nm may be irradiated in the air or in an inert gas atmosphere. .
空気中で照射する場合は、照射源としては高圧水銀灯が
好ましい。When irradiating in air, a high-pressure mercury lamp is preferred as the irradiation source.
熱は、加熱と硬化時の反応熱による発熱とを含む。 加
熱は、紫外線照射源による熱も利用できるが、通常はオ
ーブン等を使用する。The heat includes heating and heat generated by reaction heat during curing. Although heat from an ultraviolet irradiation source can be used for heating, an oven or the like is usually used.
本発明の樹脂組成物は、種々の材質に対して接着剤また
はコーティング剤等として使用しつるが、特に、電子部
品関連分野等で使用されているメツキ用レジスト材料、
ソルダーレジスト・インキとして有用である。The resin composition of the present invention can be used as an adhesive or a coating agent for various materials, but in particular, it can be used as a plating resist material used in fields related to electronic components, etc.
Useful as solder resist ink.
〈実施例〉 本発明を、実施例に基づき具体的に説明する。<Example> The present invention will be specifically explained based on examples.
表１に組成を示すエポキシ樹脂組成物を用意した。 こ
れらについて、下記の方法で、紫外線による硬化性と熱
による硬化性とを試験した。 結果は表１に示した。An epoxy resin composition whose composition is shown in Table 1 was prepared. These were tested for UV curability and heat curability using the methods described below. The results are shown in Table 1.
■紫外線による硬化性
エポキシ樹脂組成物を、ガラス板に３６０μｍ厚で塗布
し、ここに、メタルハライドランプで、２００〜４００
ｎｍの波長の光線を１０００ ｍＪ／ｃ＃照射した。■ Apply an epoxy resin composition curable by ultraviolet rays to a thickness of 360 μm on a glass plate, and apply a 200 to 400 μm thick epoxy resin composition using a metal halide lamp.
A light beam with a wavelength of nm was irradiated at 1000 mJ/c#.
硬化した膜厚を測定した。The cured film thickness was measured.
■熱による硬化性
エポキシ樹脂組成物を、１５０ｔ：のオーブンに入れ、
ゲル化に要する時間を測定した。■Put the heat-curable epoxy resin composition in a 150-ton oven,
The time required for gelation was measured.
（使用原料の説明）
（名 称）
エビクロン８５０Ｓ
（メーカー）
大日本インキ化学工業
スミエポキシＥＳＡ−０１１
スミエポキシＥＳへ−０１４
ＥＲＬ−４２０６
タラノックス
Ｐ−１７０
ＭＺ−ＯＫ
住人化学工業
住人化学工業
ユニオンカーバイド
Ｔｕｌｃｏ Ｉｎｃ
地主化工業
四国化成
２ＭＺ−ＣＮＳ
四国化成
（化学組成）
ビスフェノールＡ型エポキシ樹脂
エポキシ当量 １８０〜２００
ビスフェノールＡ型エポキシ樹脂
エポキシ当量 ４５０〜５００
ビスフェノールＡ型エポキシ樹脂
エポキシ当量 ９００〜１０００
ビニルシクロヘキセンジオキシド
微粉末シリカ
芳香族スルフオニウム塩
２ＰＺ−ＣＮＳ
２ＰＺ−ＯＫ
四
国
化
成
四
国
化
成
２Ｅ４ＭＺ−Ｂ Ｉ Ｓ
四
国
化
成
ＭＡ−ＯＫ
四
国
化
成
３Ｇ
２Ｅ４ＭＺ−ＣＮ
２ＭＺ
四
国
化
成
四
国
化
成
■
表１から明らかなように、熱重合型硬化剤として、本発
明で示したイミダゾール系化合物を本発明で示した範囲
で配合すると、エポキシ樹脂組成物は、紫外線の照射で
も加熱でも十分に硬化した。 しかし、他のイミダゾ
ール系化合物を配合すると、紫外線重合開始剤の作用を
阻害するため、エポキシ樹脂組成物は、紫外線の照射で
は硬化しなかった。(Description of raw materials used) (Name) Evicron 850S (Manufacturer) Dainippon Ink Chemical Industry Sumi Epoxy ESA-011 Sumi Epoxy ES-014 ERL-4206 Taranox P-170 MZ-OK Sumitomo Chemical Co., Ltd. Sumitomo Chemical Co., Ltd. Union Carbide Tulco Inc. Landlord Kakogyo Shikoku Kasei 2MZ-CNS Shikoku Kasei (Chemical composition) Bisphenol A type epoxy resin Epoxy equivalent weight 180-200 Bisphenol A type epoxy resin Epoxy equivalent weight 450-500 Bisphenol A type epoxy resin Epoxy equivalent weight 900-1000 Vinyl cyclohexene dioxide fine powder silica Aromatic sulfonium salt 2PZ-CNS 2PZ-OK Shikoku Kasei Shikoku Kasei 2E4MZ-B I S Shikoku Kasei MA-OK Shikoku Kasei 3G 2E4MZ-CN 2MZ Shikoku Kasei Shikoku Kasei■ As is clear from Table 1, it can be used as a thermopolymerizable curing agent. When the imidazole compound shown in the present invention was blended within the range shown in the present invention, the epoxy resin composition was sufficiently cured by both ultraviolet irradiation and heating. However, when other imidazole compounds are blended, the action of the ultraviolet polymerization initiator is inhibited, so the epoxy resin composition was not cured by ultraviolet irradiation.
〈発明の効果〉
本発明により、紫外線の照射と熱のいずれでも硬化する
エポキシ樹脂組成物が提供される。<Effects of the Invention> The present invention provides an epoxy resin composition that can be cured by both ultraviolet irradiation and heat.
従って、顔料等を含有する着色エポキシ樹脂組成物や数
１００μ以上の厚物が、紫外線照射と熱との併用により
、完全に硬化を行える。Therefore, colored epoxy resin compositions containing pigments and the like and thick objects of several hundred microns or more can be completely cured by combined use of ultraviolet irradiation and heat.
Claims (1)
始剤０．５〜１０重量部と、一級アミノ基を有しないイ
ミダゾリウム・トリメリット酸塩、２−メチルイミダゾ
リウム・イソシアヌル酸塩、 ▲数式、化学式、表等があります▼ （ただし、ｎは正の整数である） および ▲数式、化学式、表等があります▼ より選ばれる１種以上のイミダゾール系化合物 ０．５〜１０重量部とを含有することを特徴と する紫外線および熱硬化型エポキシ樹脂組成 物■(1) 100 parts by weight of epoxy resin, 0.5 to 10 parts by weight of ultraviolet polymerization initiator, imidazolium trimellitate, 2-methylimidazolium isocyanurate, which does not have a primary amino group, ▲Math. Contains 0.5 to 10 parts by weight of one or more imidazole compounds selected from ▼ (where n is a positive integer) and ▲ Numerical formulas, chemical formulas, tables, etc. ▼ An ultraviolet and thermosetting epoxy resin composition that is characterized by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28086288A JPH02127418A (en) | 1988-11-07 | 1988-11-07 | Ultraviolet-and heat-curable epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28086288A JPH02127418A (en) | 1988-11-07 | 1988-11-07 | Ultraviolet-and heat-curable epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02127418A true JPH02127418A (en) | 1990-05-16 |
Family
ID=17631003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28086288A Pending JPH02127418A (en) | 1988-11-07 | 1988-11-07 | Ultraviolet-and heat-curable epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02127418A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105082669A (en) * | 2015-09-23 | 2015-11-25 | 李会录 | Production method of epoxy glass fiber cloth copper-clad plate |
-
1988
- 1988-11-07 JP JP28086288A patent/JPH02127418A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105082669A (en) * | 2015-09-23 | 2015-11-25 | 李会录 | Production method of epoxy glass fiber cloth copper-clad plate |
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