JPS63101377A - Cyclic acrylic acid esters - Google Patents
Cyclic acrylic acid estersInfo
- Publication number
- JPS63101377A JPS63101377A JP24498186A JP24498186A JPS63101377A JP S63101377 A JPS63101377 A JP S63101377A JP 24498186 A JP24498186 A JP 24498186A JP 24498186 A JP24498186 A JP 24498186A JP S63101377 A JPS63101377 A JP S63101377A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylic acid
- reaction
- formula
- cyclic
- 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
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 8
- -1 acrylic ester Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical group 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical group C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012374 esterification agent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は接着剤、粘着剤、塗料、印刷インキ等の原料と
して有用な新規の環状（メタ）アクリル酸エステルに関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel cyclic (meth)acrylic acid ester useful as a raw material for adhesives, pressure-sensitive adhesives, paints, printing inks, and the like.
（従来の技術）
一般に紫外線硬化型あるいは電子線硬化型の接着剤ある
いは塗料には反応性モノマーとして多くの種類の（メタ
）アクリル酸ニスデルが使用されている。しかしこれら
の中には悪臭がある、粘度が高い、単体での紫外ａ！硬
化性が不十分である、等の短所をもつものが多く改良が
望まれる。(Prior Art) Generally, many kinds of nisdel (meth)acrylates are used as reactive monomers in ultraviolet curable or electron beam curable adhesives or paints. However, some of these have bad odor, high viscosity, and UV a! Many of them have shortcomings, such as insufficient curability, and improvements are desired.
（発明が解決しようとする問題点）
本発明の目的は、紫外線又は電子線硬化性に優れた、低
臭気かつ低粘度の（メタ）アクリル酸エステルを提供す
ることにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a (meth)acrylic acid ester having excellent ultraviolet or electron beam curability, low odor, and low viscosity.
（問題点を解決するための手段）
本発明者らは研究の結果、下記一般式（Ｉ）で表わされ
る環状（メタ）アクリル酸エステルである２−（４−メ
チル−１，３−ジオキサン−４−イル）−エチル（メタ
）アクリレートが、紫外線又は電子線硬化性に優れ、か
つ架橋剤としての機能も有することを光見し本発明に至
った。(Means for Solving the Problems) As a result of research, the present inventors found that 2-(4-methyl-1,3-dioxane- The inventors have discovered that 4-yl)-ethyl (meth)acrylate has excellent UV or electron beam curability and also functions as a crosslinking agent, leading to the present invention.
（以下余白）
１−１３０ ＣＩ−（２−ＣＩ−１３（Ｒは水素原子
又はメチル基を表わす）更に詳しく説明するならば、本
光明の環状（メタ）アクリル酸エステルは下記一般式（
ｎ）で示される２−（４−メチル−１，３−ジオキサン
−４−イル）−エチルアルコールをエステル化すること
により得られるものである。(Space below) 1-130 CI- (2-CI-13 (R represents a hydrogen atom or a methyl group)) To explain in more detail, the cyclic (meth)acrylic acid ester of this Komei has the following general formula (
It is obtained by esterifying 2-(4-methyl-1,3-dioxan-4-yl)-ethyl alcohol represented by n).
エステル化の方法としては、例えば（メタ）アクリル酸
による脱水エステル化、（メタ）アクリル酸クロライド
による脱塩酸反応、（メタ）アクリル酸エステルによる
エステル交換反応などによることができるが反応条件あ
るいは経済性などの点でエステル交換法によるのが適し
ている。エステル交換触媒としては硫酸、各種スルホン
酸などの酸性触媒、水酸化カリウム、アルカリ金属アル
コラードなどの塩基性触媒が一般に知られている。Esterification methods include, for example, dehydration esterification with (meth)acrylic acid, dehydrochlorination reaction with (meth)acrylic acid chloride, transesterification reaction with (meth)acrylic ester, etc., but depending on the reaction conditions or economic efficiency. The transesterification method is suitable for these reasons. As transesterification catalysts, acidic catalysts such as sulfuric acid and various sulfonic acids, and basic catalysts such as potassium hydroxide and alkali metal alcoholades are generally known.
しかし、これらの触媒は、触媒がエステル化反応の原料
および生成物に対して５５１反応をひき起こすような反
応系に対しては使用することができない。However, these catalysts cannot be used for reaction systems where the catalyst causes a 551 reaction on the raw materials and products of the esterification reaction.
本発明の（メタ）アクリル酸エステルにおいても、酸性
触媒を用いるとジオキサン環の分解がおきて数多くのｍ
」生物を生成し、また塩基性触媒を用いると、触媒活性
が反応開始後すぐに低下してしまう等の欠点がある。Also in the (meth)acrylic ester of the present invention, when an acidic catalyst is used, the dioxane ring decomposes and many m
However, if a basic catalyst is used, there are disadvantages such as the catalyst activity decreasing immediately after the reaction starts.
本発明者らは、本発見の環状（メタ）アクリル酸エステ
ルの合成に有効な触媒を探索した結果、本出願人の出願
（特開昭５５−１４３７３５号）による、Ｎ、Ｎ’−ビ
ス（サリチリデン）−エチレンジアミンの鉄錯体が非常
に有効であることを見出した。これらの鉄錯体触媒の使
用量は、原料アルコール（ＩＩ）に対して０．２〜２．
０重里％の範囲で使用するのが好ましい。As a result of searching for a catalyst effective for the synthesis of the cyclic (meth)acrylic ester of the present invention, the present inventors found that N,N'-bis( The iron complex of salicylidene)-ethylenediamine has been found to be very effective. The amount of these iron complex catalysts used is 0.2 to 2.
It is preferable to use it within a range of 0%.
また、エステル交換反応におけるエステル化剤としては
、反応時、適切な温度で遠流し、離脱するアルコールが
除去し易い低沸点のものであることが好ましく、例えば
メタクリル酸メチル、メタクリル酸エチル、アクリル酸
メチル、アクリル酸エチルなどを用いることができる。In addition, the esterification agent used in the transesterification reaction is preferably one with a low boiling point that allows easy removal of the alcohol separated by distant flow at an appropriate temperature during the reaction, such as methyl methacrylate, ethyl methacrylate, acrylic acid, etc. Methyl, ethyl acrylate, etc. can be used.
これらの原料（メタ）アクリル酸エステルは一般式（Ｉ
）のアルコールに対し１．５〜１０倍モル、好ましくは
２〜４＠モルの割合で使用する。反応は７０〜１３０℃
の反応温度、常圧又は減圧下で加熱し、生成したアルコ
ールを原料エステルとともに系外に除くことにより本発
明の環状（メタ）アクリル酸エステルを製造することが
できる。These raw material (meth)acrylic esters have the general formula (I
) is used in a ratio of 1.5 to 10 times the mole of alcohol, preferably 2 to 4@mol. Reaction is 70-130℃
The cyclic (meth)acrylic ester of the present invention can be produced by heating at a reaction temperature of , normal pressure or reduced pressure, and removing the generated alcohol from the system together with the raw material ester.
エステル交換反応に際しては重合禁止剤、例えば、ハイ
ドロキノン、ハイドロキノンモノメチルエーテル、ベン
ゾキノンなどをアルコール１モル当り０．１！７〜１．
０ｇの割合で加えることが望ましい。During the transesterification reaction, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, etc. is added in an amount of 0.1!7-1.
It is desirable to add at a rate of 0g.
（本発明の効果）
本発明の環状くメタ）アクリル酸エステルは１．３−ジ
オキサン環をもつことにより極性を有し、接着剤、粘着
剤、塗料、印刷インキなどのビヒクルとして好適である
。また、紫外線、電子線により重合させることができ、
例えば紫外線硬化型接着剤として用いた場合、優れた硬
化速度及び接着強度を示す。(Effects of the present invention) The cyclic meth)acrylic acid ester of the present invention has polarity due to having a 1,3-dioxane ring, and is suitable as a vehicle for adhesives, pressure-sensitive adhesives, paints, printing inks, and the like. In addition, it can be polymerized by ultraviolet rays and electron beams,
For example, when used as an ultraviolet curable adhesive, it exhibits excellent curing speed and adhesive strength.
更に本発明の環状（メタ）アクリル酸エステルは、紫外
線又は電子線照射により（メタ）アクリロイル基の重合
と伴せて１．３−ジオキサン環の開環による架橋反応も
同時におきるため、架橋剤等を仕込まなくてもそれ自体
で溶剤に不溶なポリマーを与えるものである。このこと
も接着剤、塗料の原料として用いる上で優れた性質であ
る。Furthermore, in the cyclic (meth)acrylic ester of the present invention, when irradiated with ultraviolet rays or electron beams, a crosslinking reaction by ring opening of the 1,3-dioxane ring occurs simultaneously with the polymerization of the (meth)acryloyl group. It provides a polymer that is insoluble in solvents by itself without the need for adding. This is also an excellent property for use as a raw material for adhesives and paints.
（実施例）
次に実施例により、本発明を更に詳しく説明する。実施
例１
サリチルアルデヒド５ｇ、エチレンジアミン２．５ｇ、
および、硫酸第一鉄７水和物６ｇを７０−の水に溶かし
加温したところ黒褐色の反応生成物が析出した。これを
吸引！ＡＬ、乾燥した後熱ピリジンに溶かし、濾過した
濾液にエタノールを加えた。ここで、析出した褐色の結
晶を乾燥して触媒（以下５ａｌｅｎ−Ｆｅと記す）とし
た。(Example) Next, the present invention will be explained in more detail with reference to Examples. Example 1 5 g of salicylaldehyde, 2.5 g of ethylenediamine,
Then, when 6 g of ferrous sulfate heptahydrate was dissolved in 70% water and heated, a blackish brown reaction product was precipitated. Inhale this! After AL was dried, it was dissolved in hot pyridine and ethanol was added to the filtered filtrate. Here, the precipitated brown crystals were dried to form a catalyst (hereinafter referred to as 5alen-Fe).
攪拌装置、蒸溜塔、乾燥空気導入管、温度計を備えた３
１の３ツロフラスコに２−（４−メチル−１，３ジオキ
サン−４−イル）−エチルアルコール５８４ｇ、メタク
リル酸メチル１２００ｇ。3 equipped with a stirring device, distillation tower, dry air introduction pipe, and thermometer.
584 g of 2-(4-methyl-1,3 dioxan-4-yl)-ethyl alcohol and 1200 g of methyl methacrylate in a 3-meter flask.
Ｓａ Ｉ ｅｎ−Ｆｅ４ｇ、Ａイドロキノン２ｇを仕込
み、小爪の空気を吹込みながら攪拌しつつ系内を１００
〜１２０℃に加熱する。反応の進行につれて生成するメ
タノールを蒸溜塔の頂部から徐々に抜き出し、６時間で
反応を完結した。冷却後、１０％硝酸水溶液、５％苛性
ソーダ水溶液、蒸溜水の順で洗浄し、油層にハイドロキ
ノンモノメチルエーテルを０．０３５ｇ加えて減圧下、
過剰のメタクリル酸メチルを留去してほとんど無臭で、
粘度１２ＣＤＳの液体８４（１（収率９８．０％）をｔ
７た。前記の液体についての’Ｈ−ＮＭＲ，赤外吸収に
よる結果を次に示す。Add 4g of SaIen-Fe and 2g of A hydroquinone, and stir while blowing air into the system to 100%
Heat to ~120°C. Methanol produced as the reaction progressed was gradually extracted from the top of the distillation column, and the reaction was completed in 6 hours. After cooling, the oil layer was washed with 10% nitric acid aqueous solution, 5% caustic soda aqueous solution, and distilled water in this order, and 0.035 g of hydroquinone monomethyl ether was added to the oil layer under reduced pressure.
Excess methyl methacrylate is distilled off, making it almost odorless.
t of liquid 84 (1 (yield 98.0%)) with a viscosity of 12 CDS
7. The results of 'H-NMR and infrared absorption for the above liquid are shown below.
（以下余白）
（１） ’Ｈ−ＮＭＲ（スペク１〜ルを第１図に示す
。）（２）赤外吸収（第２図に赤外吸収スペクトルを示
す。）以上により、得られた液体は２−（４−メチル−
１，３−ジオキサン−４−イル）−エチルメタクリレー
トであることが同定できた。(Left below) (1) 'H-NMR (Spectra 1 to 1 are shown in Figure 1.) (2) Infrared absorption (Infrared absorption spectrum is shown in Figure 2.) The liquid obtained by the above is 2-(4-methyl-
It was identified as 1,3-dioxan-4-yl)-ethyl methacrylate.
実施例２
実施例１で得られた環状メタクリル酸エステル１０．０
ｇに、紫外線重合開始剤として、２−ヒドロキシ−２−
メチル−１−フェニル−１−プロパン−１−オン０．３
ｇを加え更に安定剤どして、１．４−ベンゾキノン０．
００２ｇ（２００ｐｐｌ′Ｍ）を加えたものを紫外４！
重合組成物とする。この組成物０．２ｄをテフロン製シ
ャーレにとり、３０Ｗケミ力ル螢光ランプ２本により窒
素気流下で２０αの距離から紫外線を照射したところ４
分間で硬化組成物を得た。硬化物は、クロロホルム、ジ
オキサン等の有機溶媒に不溶の架橋ポリマーであった。Example 2 Cyclic methacrylic acid ester obtained in Example 1 10.0
g, 2-hydroxy-2- as an ultraviolet polymerization initiator
Methyl-1-phenyl-1-propan-1-one 0.3
g of 1,4-benzoquinone was added, and the stabilizer was further added.
002g (200ppl'M) added to UV 4!
A polymer composition is prepared. When 0.2 d of this composition was placed in a Teflon petri dish and irradiated with ultraviolet rays from a distance of 20α under a nitrogen stream using two 30W chemical fluorescent lamps, the result was 4.
A cured composition was obtained in minutes. The cured product was a crosslinked polymer insoluble in organic solvents such as chloroform and dioxane.
実施例３
実施例２と同様の紫外線重合組成物１０．（１にウレタ
ンアクリレート（大阪有機化学工業＠Ｊ製、商品名ビス
コート８１３）２．０ｇおよびアクリルＲ０，３９を加
えて紫外ｌＡ硬化型接着剤とした。Example 3 Ultraviolet polymerization composition similar to Example 2 10. (2.0 g of urethane acrylate (manufactured by Osaka Organic Chemical Industry @ J, trade name: Viscoat 813) and acrylic R0.39 were added to (1) to prepare an ultraviolet 1A curable adhesive.
この接着剤を紫外線を透過するアクリル樹脂片（１００
間×２５闇Ｘ３市）に一端に塗布しその上から同寸法の
樹脂片を６ｍｘＸ２５ｍＩｎの接着面積になるように重
ね合わせ、実施例２と同様の条件で１０分間紫外線照射
した。固着後、接着片の引張り剪断強度を測定した結果
４１ 、６Ｋｆｌ／ｃｉの接着強度であった。Add this adhesive to a piece of acrylic resin that transmits ultraviolet light (100
A resin piece of the same size was placed on top of it to give an adhesion area of 6 m x 25 mIn, and ultraviolet rays were irradiated for 10 minutes under the same conditions as in Example 2. After fixing, the tensile shear strength of the adhesive piece was measured and the result was 41,6 Kfl/ci.
実施例４
実施例３で添加したウレタンアクリレートの代りにエポ
キシアクリレート（昭和高分子＠製、商品名リポキシ５
Ｐ−１５０９）２．０！？を加える１以外は実施例３と
同様に調整し、測定した紫外線硬化型接着剤の接着強度
は４０ 、５ Ｋｇ／ｃｍであった。Example 4 Instead of the urethane acrylate added in Example 3, epoxy acrylate (manufactured by Showa Kobunshi @, trade name Lipoxy 5) was used.
P-1509) 2.0! ? The adhesive strength of the ultraviolet curable adhesive prepared and measured in the same manner as in Example 3 except that 1 was added was 40.5 Kg/cm.
第１図は本発明の２−（４−メチル−１，３−ジオキサ
ンー４−イル）−エチルメタクリレートの’ ｌ−（−
Ｎ Ｍ Ｒスペクトル、また、第２図は赤外吸収スペク
トルである。
特許出願人 協和ガス化学工業株式会社手 続 補
正 書（方式） ６昭和
６２年２月１７日Figure 1 shows the 'l-(-
The NMR spectrum and FIG. 2 are the infrared absorption spectra. Patent Applicant: Kyowa Gas Chemical Industry Co., Ltd. Procedure Amendment (Method) 6 February 17, 1986
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24498186A JPS63101377A (en) | 1986-10-15 | 1986-10-15 | Cyclic acrylic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24498186A JPS63101377A (en) | 1986-10-15 | 1986-10-15 | Cyclic acrylic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63101377A true JPS63101377A (en) | 1988-05-06 |
Family
ID=17126818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24498186A Pending JPS63101377A (en) | 1986-10-15 | 1986-10-15 | Cyclic acrylic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63101377A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154223A (en) * | 1998-06-25 | 2000-06-06 | Hydro Quebec | Crosslinked polymer |
-
1986
- 1986-10-15 JP JP24498186A patent/JPS63101377A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154223A (en) * | 1998-06-25 | 2000-06-06 | Hydro Quebec | Crosslinked polymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020101245A4 (en) | A Benzophenone Derivative Containing Aromatic Ester Group and Preparation Method and Application Thereof | |
| CN108586639A (en) | A kind of thioxanthone photo initiator and preparation method of the amine containing aided initiating of photopolymerization | |
| CN111138290B (en) | Aromatic ring-containing benzophenone derivative and preparation method and application thereof | |
| TW201736333A (en) | Preparing method of (meth)acrylate group-containing benzophenone for optical adhesive use and optical adhesive composition | |
| CN113913104A (en) | Low-volume-shrinkage photocureable coating material and preparation method and application thereof | |
| CN110950977B (en) | Acylphosphine oxide photoinitiator and synthesis method thereof | |
| CN110452191B (en) | Modified acrylate, preparation method and application of conductive adhesive | |
| CN115710457B (en) | Ultraviolet light curing composition and preparation method and application thereof | |
| CN103408464A (en) | Low-viscosity high-reactivity low-volume-contraction modified dipentaerythritol acrylate and preparation method thereof | |
| JPS63101377A (en) | Cyclic acrylic acid esters | |
| CN112939779A (en) | Terephthaloyl formate type photoinitiator suitable for UV-LED deep photopolymerization and preparation method thereof | |
| JPH03120263A (en) | Preparation of (meth)acrylate compound | |
| JP3315562B2 (en) | Curable resin composition | |
| JPH04283575A (en) | Production of epoxidized (meth)acrylate compound | |
| JPH09235321A (en) | New ester and its use | |
| JPH0449266A (en) | (meth)acrylic ester and its production | |
| JPH02193958A (en) | Methacrylic acid ester and production thereof | |
| JP2515586B2 (en) | Novel (meth) acrylate compound | |
| JPH0369337B2 (en) | ||
| JPH0475904B2 (en) | ||
| JP2615605B2 (en) | Method for producing polyester acrylate | |
| JP3312806B2 (en) | Method for producing tetrahydrobenzyl (meth) acrylate | |
| JPS60142990A (en) | Novel acrylate and methacrylate esters | |
| JPS61221152A (en) | Methacrylate compound and production thereof | |
| JPH0797351A (en) | Novel (meth)acrylate compound and its production |