JPH0345115B2 - - Google Patents
Info
- Publication number
- JPH0345115B2 JPH0345115B2 JP61307301A JP30730186A JPH0345115B2 JP H0345115 B2 JPH0345115 B2 JP H0345115B2 JP 61307301 A JP61307301 A JP 61307301A JP 30730186 A JP30730186 A JP 30730186A JP H0345115 B2 JPH0345115 B2 JP H0345115B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- meth
- epoxy resin
- acrylate
- 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 - Lifetime
Links
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- -1 methacryloyl Chemical group 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 229920003986 novolac Polymers 0.000 claims description 4
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 description 34
- 239000000853 adhesive Substances 0.000 description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 239000000203 mixture Substances 0.000 description 16
- 238000001723 curing Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000193 polymethacrylate Polymers 0.000 description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 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 5
- 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
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000001678 irradiating effect Effects 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
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-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
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】
技術分野
本発明は粘接着剤組成物に関し、特に初期には
液状であり、放射線照射により粘着性を示して粘
着剤となり、加熱すると硬化して接着剤として機
能し、貯蔵安全性に優れると共にその硬化物が耐
熱性に優れる粘接着剤組成物に関する。
従来技術とその問題点
粘接着剤は、粘着剤で仮粘着し、その後硬化を
行ない接着するものであるが、従来の粘接着剤に
は下記の欠点があつた。
一般に、粘接着剤は初期の段階では高粘度の粘
着物質であるので、基材への塗布を容易にするた
めに、勇気用材で希釈した溶液型である。このよ
うな溶液型粘接着剤は、塗布後、有機溶剤を蒸発
させるのに乾燥工程として長時間を必要とする。
この場合使用される有機溶剤は揮発性であり、燃
えやすく、人体に悪影響を及ぼすものが多く、そ
の使用がしばしば火災発生の原因となつたり、
種々の公害問題を引きおこしたりしている。
また、経済的見地、並びに上記公害防止上の観
点から溶剤回収装置の設置が不可避とされるが、
この装置は一般に高価であつて、かつ設備的に大
きな場所を必要とする。
このため本出願人は、特願昭61−154360合にお
いて、初期には液状であり、紫外線または電子線
を照射する粘着性を示し粘着剤となり、その後加
熱すると硬化し接着剤として機能する「粘接着剤
組成物」についてすでに出願した。
しかしながら、前述の出願で開示した粘接着剤
組成物には貯蔵安定性及びその硬化物の耐熱性に
おいて問題があつた。
発明の目的
本発明の目的は、初期には液状であり、塗布時
に有機溶剤による希釈の必要がなく、紫外線また
は放射線を照射すると粘着性を示し粘着性となり
その後加熱すると硬化し、接着剤として機能可能
であり特に耐熱性及び貯蔵安定性にすぐれる粘接
着剤組成物を提供しようとするにある。
発明の具体的構成
本発明は、下記と一般式〔Ａ〕で示される単官
能アクリル系（メタクリル系を含む）モノマー10
〜50重量部と、
１分子中に少なくとも２個以上のアクリロイル
基（メタクリロイル基を含む）をもつ化合物0.01
〜10重量部と、
トリフエニルメタントリグリシジルエーテル、
レゾルシンジグリシジルエーテル、フエノールノ
ボラツク型エポキシ樹脂、ヒドロキシエチルイソ
トシアヌレートトリグリシジルエーテルおよび下
記の一般式〔Ｂ〕で示されるエポキシ樹脂から選
択される耐熱性エポキシ樹脂20〜80重量部と、
イミダゾール化合物0.1〜20重量部（上記４成
分の合計を100重量部とする）とを含有し、紫外
線または放射線の照射によつて粘着性を示す程度
まで硬化し、その後の加熱によつてさらに硬化す
ることを特徴とする粘接着剤組成物。
ただし：
ｎ＝１〜３の整数
R1＝Ｈ、CH3
R2＝CH2、C2H4、C3H6
R3：アルキル基、DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a pressure-sensitive adhesive composition, and particularly to a pressure-sensitive adhesive composition that is initially liquid, exhibits tackiness and becomes a pressure-sensitive adhesive when irradiated with radiation, and hardens when heated to function as an adhesive. , relates to an adhesive composition which has excellent storage safety and whose cured product has excellent heat resistance. Prior Art and its Problems Adhesives are used to temporarily adhere and then cure to bond, but conventional adhesives have the following drawbacks. In general, since adhesives are high viscosity adhesive substances in the initial stage, they are in the form of solutions diluted with adhesives to facilitate application to substrates. Such solution-type adhesives require a long drying process to evaporate the organic solvent after being applied.
The organic solvents used in this case are volatile, easily flammable, and often have an adverse effect on the human body, and their use often causes fires.
It is causing various pollution problems. Additionally, installation of solvent recovery equipment is considered unavoidable from an economic standpoint as well as from the standpoint of preventing the above-mentioned pollution.
This equipment is generally expensive and requires a large amount of space. Therefore, in Japanese Patent Application No. 154,360/1982, the present applicant proposed a "viscous adhesive" that is initially liquid, exhibits tackiness when exposed to ultraviolet rays or electron beams, becomes an adhesive, and then hardens when heated to function as an adhesive. We have already filed an application for ``Adhesive Composition''. However, the pressure-sensitive adhesive composition disclosed in the above-mentioned application had problems in storage stability and heat resistance of its cured product. Purpose of the Invention The object of the present invention is that it is initially in liquid form, does not require dilution with an organic solvent during application, becomes sticky when exposed to ultraviolet rays or radiation, and then hardens when heated, and functions as an adhesive. The object of the present invention is to provide a pressure-sensitive adhesive composition that is possible and particularly has excellent heat resistance and storage stability. Specific Structure of the Invention The present invention relates to a monofunctional acrylic (including methacrylic) monomer 10 represented by the following general formula [A].
~50 parts by weight and 0.01 of a compound having at least two acryloyl groups (including methacryloyl groups) in one molecule
~10 parts by weight, triphenylmethane triglycidyl ether,
20 to 80 parts by weight of a heat-resistant epoxy resin selected from resorcin diglycidyl ether, phenol novolak type epoxy resin, hydroxyethyl isotocyanurate triglycidyl ether, and an epoxy resin represented by the following general formula [B]; and an imidazole compound. 0.1 to 20 parts by weight (the total of the above four components is 100 parts by weight), and is cured to the extent that it exhibits tackiness by irradiation with ultraviolet rays or radiation, and further cured by subsequent heating. An adhesive composition characterized by: However: n = integer from 1 to 3 R 1 = H, CH 3 R 2 = CH 2 , C 2 H 4 , C 3 H 6 R 3 : alkyl group,
【式】または[expression] or
【式】
R4＝水素、アルキル基
R5＝水素、アルキル基
R6＝アルキル基
以下に本発明の構成について詳述する。
(1) 本発明で用いる単官能（メタ）アクリル系モ
ノマーは、下記の一般式Ａで示される。
ただし：ｎ＝１〜３
R1＝Ｈ、CH3
R2＝CH2、C2H4、C3H6
R3：アルキル基、[Formula] R 4 = hydrogen, alkyl group R 5 = hydrogen, alkyl group R 6 = alkyl group The configuration of the present invention will be explained in detail below. (1) The monofunctional (meth)acrylic monomer used in the present invention is represented by the following general formula A. However: n=1-3 R1 =H, CH3R2 = CH2 , C2H4 , C3H6R3 : alkyl group ,
【式】または[expression] or
【式】
R4，R5＝水素、アルキル基
R6＝アルキル基
上述一般式〔Ａ〕で示される（メタ）アクリ
ル系モノマーとしては、例えばメトキシエチル
（メタ）アクリレート、メトキシプロピル（メ
タ）アクリレート、エトキシエチル（メタ）ア
クリレート、エトキシプロピル（メタ）アクリ
レート、ブトキシエチル（メタ）アクリレー
ト、ブトキシプロピル（メタ）アクリレート、
フエノキシエチル（メタ）アクリレート、フエ
ノキシプロピル（メタ）アクリレート、ノニル
フエノキシエチル（メタ）アクリレート、ノニ
ルフエノキシプロピル（メタ）アクリレートが
利用可能である。
(2) １分子中に少なくとも２個以上の（メタ）ア
クリロイル基をもつ化合物としては、構造的に
特に限定されるものではないが、例えばポリオ
ールポリ（メタ）アクリレート変性ポリオール
ポリ（メタ）アクリレート、ポルエステルポリ
（メタ）アクリレート、エポキシポリ（メタ）
アクリレート、ウレタンポリ（メタ）アクリレ
ート等が有効に利用される。
ポリオールポリ（メタ）アクリレートには、
ポリエチレングリコールジ（メタ）アクリレー
ト、ポリプロピレングリコール（メタ）アクリ
レート、ネオペンチルグリコール（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、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、ジペンタエリス
リトールヘキサ（メタ）アクリレートなどがあ
る。
変性ポリオールポリ（メタ）アクリレートに
は、トリメチロールプロパンのプロピレンオキ
シド付加物のトリ（メタ）アクリレート、ビス
フエノールＡのエチレンオキシド付加物のジ
（メタ）アクレートなどがある。
(3) 本発明で使用される耐熱性エポキシ樹脂は、
一般式〔Ａ〕で示されるアクリル系モノマーと
相溶し、かつ紫外線または放射線照射時にアク
リル化合物の硬化をさまたげないものでなけれ
ばならない。
また、加熱硬化後の耐熱性をあげるため、使
用するエポキシ樹脂も耐熱性を有するものでな
ければならない。従つて、本発明では、以下に
示す５種類のエポキシ樹脂のうちの１種以上を
用いる。
トリフエニルメタントリグリシジルエーテル
レゾルシンジグリシンジルエーテル
フエノールノボラツク型エポキシ樹脂
ヒドロキシエチルイソシアヌレートトリグリ
シジルエーテル
例えばダイセル化学社製EHPL−3150
上記のエポキシ樹脂は、一般式〔Ａ〕で示され
るアクリルモノマー系との相溶性にすぐれ、また
紫外線照射時にアクリル化合物の硬化を阻害しな
い。また、その硬化物は耐熱性にすぐれる。一般
に使用されるエポキシ樹脂では、貯蔵安定性にす
ぐれるものの、その硬化物の耐熱性が十分ではな
い。
(4) エポキシ樹脂の硬化剤は、短時間で硬化可能
でかつ貯蔵安定性に優れるものでなければなら
ない。特に、イミダゾール化合物が上記特性に
すぐれる。なかでも、キユアゾール2MZ−
AZINE（四国化成）、キユアゾール2P4MHz
（四国化成）が有効に利用できる。
(5) さらに、本発明の組成物には、その性能を変
えない範囲内で上記(1)〜(4)以外の他の添加剤を
加えることができる。この添加剤は、例えば、
（メタ）アクリル酸のアルキルエステルモノマ
ー、光開始剤、光増感剤、重合禁止剤、充填
剤、顔料、タレ防止剤、分散剤、老化防止剤等
である。
（メタ）アクリル酸のアルキルエステルモノ
マーとしては、（メタ）アクリル酸ｎ−ブチル、
（メタ）アクリル酸−２−エチルヘキシル（メ
タ）アクリル酸ドデシル等が添加可能である。
(6) 本発明の組成物は、放射線硬化の際は不要で
あるが、紫外線硬化を行なうときには、光開始
剤を必要とする。光開始剤としては、開裂タイ
プのもの、水素引き抜きタイプのものが有効に
使用される。
開裂タイプのものとしては、例えば、ベンゾ
インエチルエーテル、ジエトキシアセトフエノ
ン、ベンジルジメチルケタール、２−ヒドロキ
シ−２−メチルプロピオフエノン、１−ヒドロ
キシシクロヘキシルフエニルケトン等が挙げら
れる。
水素引き抜きタイプのものとしては、ベンジ
ル、ベンゾフエノン、２，４−ジエチルチオキ
サントン等が有効である。
光開始剤の使用量は組成物に対して好ましく
は0.001〜10wt％、さらに好ましくは0.01〜5wt
％範囲である。
(7) 本発明の組成物中の各成分の配合比におい
て、一般式〔Ａ〕ので示される単官能（メタ）
アクリルモノマー系の配合量が多いほど、紫外
線照射後の粘着性にすぐれるが、その後、加熱
硬化を行なうためには、単官能（メタ）アクリ
ルモノマー系の配合量が10〜60重量部、エポキ
シ樹脂が40〜80重量部が適当である。しかしな
がら、加熱硬化後の耐熱性が必要な本発明の組
成物の場合には、単官能（メタ）アクリルモノ
マー系の配合量が10〜50重量部、エポキシ樹脂
が50〜80重量部が有効である。
また、１分子中に少なくとも２個以上の（メ
タ）アクリロイル基をもつ化合物の配合量は、
（メタ）アクリロイル基の数やこの化合物の分
子量によつて異なるが、0.01〜10重量部が好ま
しい。
エポキシ樹脂の潜存性硬化剤であるイミダゾ
ール化合物は、配合量が多いほど加熱時の硬化
時間が短くなるが、反応にポツトライフが短く
なるので、0.1〜20重量部が好適である。
以上の４成分の合計を100重量部とし、これ
らの必須成分以外に前述の他の成分を加えても
よい。
実施例
以下に実施例及び比較例を挙げて本発明を具体
的に説明する。
粘着力、接着力、貯蔵安定性の測定は次の方法
で行なつた。
(1) 粘着力
50μｍのポリエステルフイルムの片面に、粘
接着剤の厚さが約100μｍになるように粘接着
剤を塗布した後、紫外線硬化用高圧水銀ランプ
（8W／cm）のランプ下15cmの位置で10秒間紫外
線を照射し、粘着シートを作製した。該粘着シ
ートをアルミ板（Ａ−1050P）に貼り付け、
180度引き剥がし粘着力を測定した。
(2) 接着力
アルミ板（Ａ−1050P）の片面に、粘接着剤
の厚さが約100μ、広さが25mm×25mmになるよ
うに粘接着剤を塗布し、紫外線硬化用高圧水銀
ランプ（80W／cm）のランプ下15cmの位置で10
秒間紫外線を照射した後、別のアルミ板（Ａ−
1050P）に貼り付け、150℃のオーブン内で20
分間加熱硬化させた。このテストピースを使
い、せん断接着がを25℃（常温）と150℃（高
温）で測定した。
(3) 貯蔵安定性
粘度が初期の２倍となる日数をポツトラフト
とした。[Formula] R 4 , R 5 = hydrogen, alkyl group R 6 = alkyl group As the (meth)acrylic monomer represented by the above general formula [A], for example, methoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate , ethoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, butoxyethyl (meth)acrylate, butoxypropyl (meth)acrylate,
Phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, and nonylphenoxypropyl (meth)acrylate are available. (2) Compounds having at least two (meth)acryloyl groups in one molecule are not particularly limited structurally, but include, for example, polyol poly(meth)acrylate modified polyol poly(meth)acrylate, Polyester poly(meth)acrylate, epoxy poly(meth)
Acrylate, urethane poly(meth)acrylate, etc. are effectively used. Polyol poly(meth)acrylate has
Polyethylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, neopentyl glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate, etc. Examples of the modified polyol poly(meth)acrylate include tri(meth)acrylate, which is an adduct of trimethylolpropane with propylene oxide, and di(meth)acrylate, which is an ethylene oxide adduct of bisphenol A. (3) The heat-resistant epoxy resin used in the present invention is
It must be compatible with the acrylic monomer represented by general formula [A] and must not hinder the curing of the acrylic compound when irradiated with ultraviolet rays or radiation. Furthermore, in order to increase the heat resistance after heat curing, the epoxy resin used must also have heat resistance. Therefore, in the present invention, one or more of the five types of epoxy resins shown below are used. Triphenylmethane triglycidyl ether Resorcin diglycindyl ether Phenol novolac type epoxy resin Hydroxyethyl isocyanurate triglycidyl ether For example, EHPL-3150 manufactured by Daicel Chemical Co., Ltd. The above epoxy resin has excellent compatibility with the acrylic monomer system represented by the general formula [A], and does not inhibit the curing of the acrylic compound when irradiated with ultraviolet rays. Moreover, the cured product has excellent heat resistance. Although commonly used epoxy resins have excellent storage stability, their cured products do not have sufficient heat resistance. (4) The curing agent for epoxy resin must be able to cure in a short time and have excellent storage stability. In particular, imidazole compounds are excellent in the above properties. Among them, Kyuazol 2MZ−
AZINE (Shikoku Kasei), Kyuazol 2P4MHz
(Shikoku Kasei) can be used effectively. (5) Furthermore, other additives other than the above (1) to (4) can be added to the composition of the present invention within a range that does not change its performance. This additive is, for example,
These include (meth)acrylic acid alkyl ester monomers, photoinitiators, photosensitizers, polymerization inhibitors, fillers, pigments, anti-sagging agents, dispersants, anti-aging agents, and the like. As the alkyl ester monomer of (meth)acrylic acid, n-butyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, etc. can be added. (6) The composition of the present invention does not require a photoinitiator when curing with radiation, but does require a photoinitiator when curing with ultraviolet light. As the photoinitiator, cleavage type and hydrogen abstraction type are effectively used. Examples of the cleavage type include benzoin ethyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone. As the hydrogen abstracting type, benzyl, benzophenone, 2,4-diethylthioxanthone, etc. are effective. The amount of photoinitiator used is preferably 0.001 to 10wt%, more preferably 0.01 to 5wt% based on the composition.
% range. (7) In the blending ratio of each component in the composition of the present invention, the monofunctional (meta) represented by the general formula [A]
The greater the amount of acrylic monomer blended, the better the adhesiveness after UV irradiation, but in order to perform heat curing afterwards, the amount of monofunctional (meth)acrylic monomer blended is 10 to 60 parts by weight, and the epoxy A suitable amount of resin is 40 to 80 parts by weight. However, in the case of the composition of the present invention which requires heat resistance after heat curing, it is effective to mix 10 to 50 parts by weight of the monofunctional (meth)acrylic monomer and 50 to 80 parts by weight of the epoxy resin. be. In addition, the amount of compound having at least two (meth)acryloyl groups in one molecule is as follows:
Although it varies depending on the number of (meth)acryloyl groups and the molecular weight of the compound, it is preferably 0.01 to 10 parts by weight. The higher the amount of the imidazole compound, which is a latent curing agent for epoxy resins, the shorter the curing time during heating, but since the pot life of the reaction will be shorter, the amount is preferably 0.1 to 20 parts by weight. The total of the above four components is 100 parts by weight, and other components mentioned above may be added in addition to these essential components. Examples The present invention will be specifically described below with reference to Examples and Comparative Examples. Adhesive strength, adhesive strength, and storage stability were measured by the following methods. (1) Adhesive strength After applying adhesive to one side of a 50 μm polyester film so that the thickness of the adhesive is approximately 100 μm, it was placed under a high-pressure mercury lamp (8W/cm) for UV curing. An adhesive sheet was prepared by irradiating ultraviolet light for 10 seconds at a position of 15 cm. Attach the adhesive sheet to an aluminum plate (A-1050P),
The adhesive strength was measured after 180 degree peeling. (2) Adhesive strength Apply adhesive to one side of an aluminum plate (A-1050P) so that the thickness of the adhesive is approximately 100 μ and the area is 25 mm x 25 mm, and apply high pressure mercury for UV curing. 10 at a position 15cm below the lamp (80W/cm)
After irradiating with ultraviolet light for seconds, another aluminum plate (A-
1050P) and put it in the oven at 150℃ for 20 minutes.
It was heated and cured for a minute. Using this test piece, shear adhesion was measured at 25°C (room temperature) and 150°C (high temperature). (3) Storage stability The number of days when the viscosity becomes twice its initial value was defined as the pot raft.
【表】【table】
【表】
（実施例および比較例）
第１表の配合に従い実施例および比較例の粘接
着剤組成物を作製し、上記の方法で粘着力及び接
着力を測定した。
測定結果を第１表に示した。
比較例１は、エポキシ樹脂にクレゾールノボラ
ツク型エポキシ樹脂を使用したものであるが、単
官能アクリルモノマー系に溶解せず本発明には不
適であつた。
比較例２は、エポキシ樹脂にグリシジルアミン
型エポキシ樹脂を使用したものである。単官能ア
クリルモノマーとの相溶性は良いが、紫外線照射
時に変化せず、粘着性を示さない。グリシジルア
ミン型エポキシ樹脂は、アクリル化合物の紫外線
硬化を阻害するので、本発明には適さなかつた。
比較例３は、エポキシ樹脂にビスフエノールＡ
型エポキシ樹脂を、その硬化剤に変性ポリアミン
系のものを使用したものである。粘着力、接着力
ともにすぐれていたが、耐熱性及び貯蔵安定性に
乏しい。
比較例４は、比較例３と同様の配合で硬化剤に
イミダゾール系のキユアゾール2M−AZINEを使
用したものである。比較例３に比較し、貯蔵安定
性に優れていた。
実施例１，２は、エポキシ樹脂硬化剤にキユア
ゾール2MZ−AZINEを、エポキシ樹脂にそれぞ
れ、トリフエニルメタントリグリシジルエーテル
とレゾルシンジクルシジルエーテルを使用したも
のである。粘着力、接着力ともにすぐれる。ま
た、貯蔵安定性、耐熱性にもすぐれていた。
実施例３は、エポキシ樹脂硬化剤にキユアゾー
ル2P4MHzを使用したものであるが、貯蔵安定性
はさらに良かつた。
発明の効果
本発明の粘接着剤組成物は、初期には液状であ
り紫外線または放射線を照射すると粘着性を示し
粘着剤となるため、塗布工程においては有機溶剤
で希釈する必要がなく、公害防止や省エネルギー
の観点いおいて有利である。
また、粘着性により、固定時の作業性が良く、
その後加熱硬化し、接着力や耐熱性にすぐれる。
さらに、２液硬化型のように硬化剤を混合する必
要がない１液型なので取り扱いが容易であり、か
つ貯蔵安定性にすぐれる。
特に粘接着テープに好適に利用できる。[Table] (Examples and Comparative Examples) Adhesive compositions of Examples and Comparative Examples were prepared according to the formulations shown in Table 1, and the adhesive strength and adhesive strength were measured using the methods described above. The measurement results are shown in Table 1. Comparative Example 1 used a cresol novolak type epoxy resin as the epoxy resin, but it was not soluble in the monofunctional acrylic monomer system and was unsuitable for the present invention. Comparative Example 2 uses a glycidylamine type epoxy resin as the epoxy resin. Although it has good compatibility with monofunctional acrylic monomers, it does not change upon irradiation with ultraviolet light and does not exhibit stickiness. Glycidylamine type epoxy resins are not suitable for the present invention because they inhibit ultraviolet curing of acrylic compounds. In Comparative Example 3, bisphenol A was added to the epoxy resin.
This type of epoxy resin uses a modified polyamine-based curing agent. Although it had excellent adhesive strength and adhesion, it had poor heat resistance and storage stability. Comparative Example 4 has the same formulation as Comparative Example 3 and uses imidazole-based Kyuazol 2M-AZINE as a curing agent. Compared to Comparative Example 3, the storage stability was excellent. Examples 1 and 2 use Cyuazol 2MZ-AZINE as the epoxy resin curing agent, and triphenylmethane triglycidyl ether and resorcin dicurcidyl ether as the epoxy resins, respectively. Excellent adhesive and adhesive strength. It also had excellent storage stability and heat resistance. In Example 3, Kyuazol 2P4MHz was used as the epoxy resin curing agent, but the storage stability was even better. Effects of the Invention The adhesive composition of the present invention is initially in a liquid state, and when irradiated with ultraviolet rays or radiation, it becomes sticky and becomes an adhesive, so it does not need to be diluted with an organic solvent during the coating process, and it does not cause pollution. This is advantageous from the viewpoint of prevention and energy conservation. In addition, due to its adhesive properties, it has good workability when fixing.
It is then heat cured and has excellent adhesive strength and heat resistance.
Furthermore, since it is a one-component type that does not require mixing a curing agent unlike a two-component type, it is easy to handle and has excellent storage stability. In particular, it can be suitably used for adhesive tapes.
Claims (1)
ル系（メタクリル系を含む）モノマー10〜50重量
部と、 １分子中に少なくとも２個以上のアクリロイル
基（メタクリロイル基を含む）をもつ化合物0.01
〜10重量部と、 トリフエニルメタントリグリシジルエーテル、
レゾルシンジグリシジルエーテル、フエノールノ
ボラツク型エポキシ樹脂、ヒドロキシエチルイソ
シアヌレートトリグシジルエーテルおよび下記一
般式〔Ｂ〕で示されるエポキシ樹脂から選択され
る耐熱性エポキシ樹脂50〜80重量部とイミダゾー
ル化合物0.1〜20重量部（上記４成分の合計を100
重量部とする）とを含有し、 紫外線または放射線の照射によつて粘着性を示
す粘度まで硬化し、その後の加熱によつてさらに
硬化することを特徴とする粘耗着剤組成物。 ただし：ｎ＝１〜３の整数 R1＝Ｈ、CH3 R2＝CH2、C2H4、C3H6 R3：アルキル基、 【式】 （R4＝水素、アルキル基 R5＝水素、アルキル基） または 【式】（R6＝アルキル基） [Scope of Claims] 1 10 to 50 parts by weight of a monofunctional acrylic (including methacrylic) monomer represented by the following general formula [A], and at least two or more acryloyl groups (methacryloyl groups) in one molecule. 0.01
~10 parts by weight, triphenylmethane triglycidyl ether,
50 to 80 parts by weight of a heat-resistant epoxy resin selected from resorcin diglycidyl ether, phenol novolac type epoxy resin, hydroxyethyl isocyanurate trigcidyl ether, and an epoxy resin represented by the following general formula [B] and 0.1 to 0.1 parts by weight of an imidazole compound. 20 parts by weight (total of the above four components is 100 parts)
(parts by weight), which is cured to a viscosity exhibiting adhesiveness by irradiation with ultraviolet rays or radiation, and further cured by subsequent heating. However: n = integer from 1 to 3 R 1 = H, CH 3 R 2 = CH 2 , C 2 H 4 , C 3 H 6 R 3 : Alkyl group, [Formula] (R 4 = Hydrogen, Alkyl group R 5 = hydrogen, alkyl group) or [Formula] (R 6 = alkyl group)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30730186A JPS63159488A (en) | 1986-12-23 | 1986-12-23 | Tacky adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30730186A JPS63159488A (en) | 1986-12-23 | 1986-12-23 | Tacky adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63159488A JPS63159488A (en) | 1988-07-02 |
| JPH0345115B2 true JPH0345115B2 (en) | 1991-07-10 |
Family
ID=17967496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30730186A Granted JPS63159488A (en) | 1986-12-23 | 1986-12-23 | Tacky adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63159488A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5382971B2 (en) * | 2004-03-01 | 2014-01-08 | 住友ベークライト株式会社 | Resin composition and semiconductor device produced using resin composition |
| BE1017361A3 (en) * | 2006-11-06 | 2008-07-01 | Unibind Ltd | SHEET FOR COMPOSITION OF A PHOTO ALBUM AND A PHOTO ALBUM EQUIPPED WITH SUCH SHEET. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5865717A (en) * | 1981-10-15 | 1983-04-19 | Toyo Ink Mfg Co Ltd | Actinic ray-curable composition |
-
1986
- 1986-12-23 JP JP30730186A patent/JPS63159488A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5865717A (en) * | 1981-10-15 | 1983-04-19 | Toyo Ink Mfg Co Ltd | Actinic ray-curable composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63159488A (en) | 1988-07-02 |
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