JPS6341508A - Ultraviolet-curing composition - Google Patents
Ultraviolet-curing compositionInfo
- Publication number
- JPS6341508A JPS6341508A JP18627286A JP18627286A JPS6341508A JP S6341508 A JPS6341508 A JP S6341508A JP 18627286 A JP18627286 A JP 18627286A JP 18627286 A JP18627286 A JP 18627286A JP S6341508 A JPS6341508 A JP S6341508A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- photopolymerization initiator
- acrylate
- radical polymerization
- compound
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- -1 alkyl disulfide Chemical compound 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
- 150000002019 disulfides Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- IMPRSCUWYGENLJ-UHFFFAOYSA-N 1-(2-hydroxyethoxy)butan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCC(O)COCCO IMPRSCUWYGENLJ-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- JRJNSEMUYTUGLA-UHFFFAOYSA-N 3-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC1=CC=CC=C1 JRJNSEMUYTUGLA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
章清」−の利用分野
本発明は紫外線硬化性組成物、更に詳しくは、特にガラ
スに対する接着力、特に耐水性に優れ、塗料や接着剤と
して有用な紫外線硬化性組成物に関する。Detailed Description of the Invention Field of Application of Akisei The present invention relates to ultraviolet curable compositions, and more particularly, to ultraviolet curable compositions that have excellent adhesion to glass, especially water resistance, and are useful as paints and adhesives. relating to things.
畦技術と角そ紅）−□ぐ（」１νＪ都草−□σヌ、従来
より、紫外線硬化性組成物として、不飽和ポリエステル
系やアクリル系のラジカル重合型紫外線硬化性樹脂（二
重結合を有するモノマー、オリゴマー等）に光重合開始
剤（たとえばカルボニル系、スルフィド系、キノン系、
アゾ系、スルホクロリド系など）および必要に応じて光
増感剤を配合したものが知られている。これら公知の組
成物は紫外線照射により重合硬化を起こし、印刷インキ
、塗料、接着剤などに多用されているが、最近、下地に
対してより優れた接着力、付着力のイ【］与が望まれつ
つある。Traditionally, unsaturated polyester and acrylic radical polymerizable ultraviolet curable resins (with no double bonds) have been used as ultraviolet curable compositions. photopolymerization initiators (e.g. carbonyl type, sulfide type, quinone type,
Azo type, sulfochloride type, etc.) and those containing a photosensitizer as necessary are known. These known compositions are polymerized and cured by ultraviolet irradiation and are widely used in printing inks, paints, adhesives, etc., but recently there has been a demand for better adhesion and adhesion to the substrate. It is becoming rare.
そこで本発明者らは、かかる要望に応えて鋭ひ検削を進
めたところ、紫外線照射によりラジカルを発生ずる光重
合開始剤として、アルコキンノリル基を有するジスルフ
ィドもしくはテ］・ラスルフィト化合物を用いれば、従
来の硬化特性を損なうことなく、下地、特にガラスに対
する接着力か顕晋に向」ニジうろことを見出し、本発明
を完成させるに至った。In response to this request, the present inventors carried out in-depth examination and found that it is possible to use a disulfide or te]-lasulfite compound having an alkokenolyl group as a photopolymerization initiator that generates radicals upon irradiation with ultraviolet rays. They discovered that the adhesive strength to substrates, especially glass, can be improved without impairing the conventional curing properties, leading to the completion of the present invention.
弁明の一構−婢六勢里−
すなわち、本発明は、ラジカル重合型紫外線硬化性樹脂
および光重合開始剤としてヒス１０′ルコキシノリル）
アルキル］ジスルフィドもしくはテトラスルフィド化合
物から成ることを特徴とする特外線硬化性組成物を提供
するものである。Part of the defense - Urokuseri - That is, the present invention uses a radical polymerizable ultraviolet curable resin and a photopolymerization initiator containing His-10'lukoxynoryl).
The present invention provides an extra-radiation curable composition comprising an alkyl disulfide or tetrasulfide compound.
本発明にお（ｊるシソカル重合型紫外線硬化性樹脂（Ｊ
、ラジカル反応性有機化合物から成る。According to the present invention (J)
, consisting of radically reactive organic compounds.
」―記うジカル反応性有機化合物としては、ラジカル反
応性オリゴマー（両末端アクリロイルポリブタンエンオ
リゴマー、エボギノアクリルオリゴマー、ウレタンアク
リルオリゴマー、ポリエステルアクリルオリゴマー、ア
ルキッドアクリルオリゴマー、ノリコーンアクリルオリ
ゴマーなど）および架橋構造を付与する多官能（メタ）
アクリルモノマー［１−リメチロールプロパン）・す（
メタ）アクリレ−１−、ペンタ−トリアクリレート、エ
チレングリコールノ（メタ）アクリレート、テトラエチ
レングリコールジ（メタ）アクリレート、ポリエチレン
クリコールン（メタ）アクリレ−Ｉ・、１．４−ブタン
７オールン（メタ）アクリレ−１−１Ｉ、６−ヘキザン
ジオールジ（メタ）アクリレート、ネオペンヂルク゛リ
コールノ（メタ）アクリレ−１−、ジアクリロキソエヂ
ルフ］スフエートなどＪを必須とし、これに反応性希釈
モノマー１ビニルピロリドン、２−ヒドロキンエチル（
メタ）アクリレート、２−ヒドロキンプロピル（メタ）
アクリレート、テトラヒドロフルフリルアクリレート、
ブトキシエチルアクリレート、エチルジエチレングリコ
ールアクリレート、２−エチルへギシルアクリレー）・
、ノクロヘギシルアクリレ−１−、フェノキノエチルア
クリレート、２−ヒトロギシー３−フェニルオキシプロ
ピルアクリレート、ジシクロペンタノエンアクリレ−１
・など）を必要に応じて配合する。” - The radically reactive organic compounds described include radically reactive oligomers (double-terminated acryloyl polybutane oligomers, evogino acrylic oligomers, urethane acrylic oligomers, polyester acrylic oligomers, alkyd acrylic oligomers, noricone acrylic oligomers, etc.) and crosslinked acrylic oligomers. Multifunctional (meta) that gives structure
Acrylic monomer [1-limethylolpropane]
meth)acrylate-1-, penta-triacrylate, ethylene glycol-1-(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol-1-(meth)acrylate-I, 1,4-butane-7-olne(meth) ) acrylate-1-1I, 6-hexanediol di(meth)acrylate, neopendyl glycolno(meth)acrylate-1-, diacryloxoedyl sulfate, etc. J is essential, and reactive diluent monomer 1 is added to this. Vinylpyrrolidone, 2-hydroquinethyl (
meth)acrylate, 2-hydroquinepropyl(meth)
acrylate, tetrahydrofurfuryl acrylate,
butoxyethyl acrylate, ethyldiethylene glycol acrylate, 2-ethylhedyl acrylate)・
, Noklohegysylacryle-1-, Phenoquinoethyl acrylate, 2-Hydrogysy 3-phenyloxypropyl acrylate, Dicyclopentanoene acrylate-1
・etc.) are added as necessary.
本発明において光重合開始剤として用いるヒス［（アル
コキシシリル）アルキルコノスルフィドもしくはテトラ
スルフィト
造することができる。His[(alkoxysilyl)alkylconosulfide or tetrasulfite can be used as a photopolymerization initiator in the present invention.
たとえば、西独特許公開第２１４ １１５９および２１
４１１６０号公報には、式。For example, West German Patent Publication No. 214 1159 and 21
Publication No. 41160 describes the formula.
（ＲＯｈ−Ｓ ｉ＋ｃｌｌ 、−Ｓ − Ｓ−ｅｃｌＩ
、狗Ｓ ｉ（−ＯＲ）３（Ｒは炭素数Ｉ〜４のアルギ
ル）
で示されるジスルフィド化合物の生成と同時にトリもし
くはテトラスルフィドの混合物を製造する方法が記載さ
れている。また、特開昭５０−８４５３４号公報にも、
γーメルカプトプロピルトリアルコキノノランを塩化ス
ルフリルと反応さ且−で、ジスルフィド化合物を得る方
法か記載されてし）る。(ROh-S i+cll, -S-S-eclI
, Si(-OR)3 (R is argyl having 1 to 4 carbon atoms) A method for simultaneously producing a mixture of tri- or tetrasulfides is described. Also, in Japanese Patent Application Laid-Open No. 50-84534,
A method for obtaining disulfide compounds by reacting γ-mercaptopropyltrialcoquinonolane with sulfuryl chloride is described.
更に、反応試剤としてメルカプトアルキルアルコキシシ
ラン、ナトリウムアルコラードおよびヨウ素を使用し、
簡便かつ高収率で高純度のジスルフィド化合物を製造す
る方法などがある。具体的には、式：
［式中、Ｒ１およびＲ２は同一もしくは異なって炭素数
１〜４の低級アルキル、Ｒ３は炭素数１〜４の低級アル
キレン、およびｎは０、ｌまたは２である］
のメルカプトアルキルアルコキシシランを、式：％式％
［式中、Ｒ１は前記と同意義］
のナトリウムアルコラードと反応させ、次いでヨウ素と
反応させることにより、式
［式中、Ｒ’， Ｒ２，Ｒ３およびｎは面記と同意義］
で示されるビス［（アルコキンノリル）アルキルコシス
ルフィドが得られる。Furthermore, using mercaptoalkylalkoxysilane, sodium alcoholade and iodine as reaction reagents,
There are methods for producing high-purity disulfide compounds easily, with high yield, and the like. Specifically, the formula: [wherein R1 and R2 are the same or different and are lower alkyl having 1 to 4 carbon atoms, R3 is lower alkylene having 1 to 4 carbon atoms, and n is 0, 1 or 2] A mercaptoalkylalkoxysilane of the formula: % formula % [wherein R1 has the same meaning as above] is reacted with sodium alcoholade, and then with iodine to form a mercaptoalkylalkoxysilane of the formula [wherein R', R2, R3]. and n has the same meaning as face writing]
A bis[(alcoquinolyl)alkylcocysulfide represented by is obtained.
かかる光重合開始剤の使用型は通常、ラジカル反応性有
機化合物全量に対して０．５〜１０重量％の範囲で選定
すればよい。The type of photopolymerization initiator to be used may normally be selected within the range of 0.5 to 10% by weight based on the total amount of the radically reactive organic compound.
本発明に係る紫外線硬化性組成物は、」二記うノカル反
応性有機化合物および光重合開始剤としてのビス［（ア
ルコキシシリル）アルキルコシスルフィドもしくはテト
ラスルフィド化合物、更に必要に応じて通常の充填剤、
老化防止剤、重合禁止剤等を加えた系で構成される。The ultraviolet curable composition according to the present invention comprises a nocal-reactive organic compound, a bis[(alkoxysilyl)alkylcocysulfide or tetrasulfide compound as a photopolymerization initiator, and, if necessary, a conventional filler. ,
It is composed of a system containing anti-aging agents, polymerization inhibitors, etc.
次に実施例および比較例を挙げて、本発明をより具体的
に説明する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１．２および比較例１
表１に示す部数の各成分を配合して、紫外線硬化性組成
物を調製する。Example 1.2 and Comparative Example 1 A UV curable composition is prepared by blending each component in the parts shown in Table 1.
２枚のカラス板（厚み３ ｍｍ）に対し、上記紫外線硬
化性組成物を厚み５０μにて塗布し、重ね合せた後、こ
れにＩｌ、ａｍの距離から紫外線ランプ（８０Ｗ ／
ａｍ）を１０秒間照射して硬化させる。得られる積層板
を剪断接着試験に供し、結果を表１に示す。The above ultraviolet curable composition was applied to a thickness of 50μ on two glass plates (thickness 3 mm), and after superimposing them, an ultraviolet lamp (80 W /
am) for 10 seconds to cure. The resulting laminate was subjected to a shear adhesion test, and the results are shown in Table 1.
表１
注■）ビスフェノールＡのジグリソジルエーテル（油化
ンエルエボギシ社製、エピコート８２８）のジアクリレ
ートTable 1 Note ■) Diacrylate of diglysodylether of bisphenol A (manufactured by Yuka Ebogishi Co., Ltd., Epicote 828)
Claims (1)
剤としてビス［（アルコキシシリル）アルキル］ジスル
フィドもしくはテトラスルフィド化合物から成ることを
特徴とする紫外線硬化性組成物。1. An ultraviolet curable composition comprising a radically polymerizable ultraviolet curable resin and a bis[(alkoxysilyl)alkyl]disulfide or tetrasulfide compound as a photopolymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18627286A JPS6341508A (en) | 1986-08-07 | 1986-08-07 | Ultraviolet-curing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18627286A JPS6341508A (en) | 1986-08-07 | 1986-08-07 | Ultraviolet-curing composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6341508A true JPS6341508A (en) | 1988-02-22 |
Family
ID=16185390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18627286A Pending JPS6341508A (en) | 1986-08-07 | 1986-08-07 | Ultraviolet-curing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6341508A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1087675A (en) * | 1996-07-18 | 1998-04-07 | Degussa Ag | Organosilanepolysulfan mixture and production of rubber compound containing the same mixture |
| US8362134B2 (en) | 2005-08-19 | 2013-01-29 | Cryovac, Inc. | Film comprising silicate platelets of exfoliated from phospolipid-intercalated layered silicate |
-
1986
- 1986-08-07 JP JP18627286A patent/JPS6341508A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1087675A (en) * | 1996-07-18 | 1998-04-07 | Degussa Ag | Organosilanepolysulfan mixture and production of rubber compound containing the same mixture |
| US8362134B2 (en) | 2005-08-19 | 2013-01-29 | Cryovac, Inc. | Film comprising silicate platelets of exfoliated from phospolipid-intercalated layered silicate |
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