JPH07206775A - New photopolymerization initiator and photocurable polymer composition containing it - Google Patents
New photopolymerization initiator and photocurable polymer composition containing itInfo
- Publication number
- JPH07206775A JPH07206775A JP17383594A JP17383594A JPH07206775A JP H07206775 A JPH07206775 A JP H07206775A JP 17383594 A JP17383594 A JP 17383594A JP 17383594 A JP17383594 A JP 17383594A JP H07206775 A JPH07206775 A JP H07206775A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- epoxy
- photopolymerization initiator
- formula
- 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.)
- Granted
Links
- 239000003999 initiator Substances 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 title claims description 26
- 229920000642 polymer Polymers 0.000 title claims description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- -1 benzoin alkyl ether Chemical class 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 7
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 11
- 244000028419 Styrax benzoin Species 0.000 abstract description 3
- 235000000126 Styrax benzoin Nutrition 0.000 abstract description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 abstract description 3
- 229960002130 benzoin Drugs 0.000 abstract description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 abstract description 3
- 235000019382 gum benzoic Nutrition 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000016 photochemical curing Methods 0.000 description 13
- 230000000977 initiatory effect Effects 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000003085 diluting agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- IKVYTYOJOZRXOK-UHFFFAOYSA-N CC(C)COC(CCN=C=O)(C1=CC=CC=C1)C(=O)C2=CC=CC=C2 Chemical compound CC(C)COC(CCN=C=O)(C1=CC=CC=C1)C(=O)C2=CC=CC=C2 IKVYTYOJOZRXOK-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、新規な光重合開始化合
物及びこれを含有する光硬化性重合体組成物に関する。
更に具体的に言えば、本発明はベンゾインアルキルエー
テル（以下「ＢＡＥ」と表記する）がエポキシプレポリ
マー又はエポキシアクリル酸エステルプレポリマーに結
合している新規な光重合開始化合物及びこれを含有する
光硬化性重合体組成物に関するものである。FIELD OF THE INVENTION The present invention relates to a novel photopolymerization initiator compound and a photocurable polymer composition containing the same.
More specifically, the present invention provides a novel photopolymerization initiator compound in which a benzoin alkyl ether (hereinafter referred to as “BAE”) is bonded to an epoxy prepolymer or an epoxy acrylate prepolymer, and a photopolymerization compound containing the same. It relates to a curable polymer composition.
【０００２】[0002]
【従来の技術】一般的に、光硬化性重合体組成物に低分
子量の光重合開始剤を用いる場合、この低分子化合物は
組成物中に含有されている他の成分、例えば感光性プレ
ポリマー、単量体希釈剤、添加剤、色素等のような成分
との相溶性に劣り、光硬化効率も低いので多くの問題点
がある。特に、他成分との相溶性の不足は光硬化反応を
阻害して反応物質が未反応状態で残るだけでなく、光重
合開始剤自体も低分子物質のまま残るので、光硬化され
た重合体組成物の物理的性質に悪い影響を及ぼす。ま
た、低分子光重合開始剤は光硬化反応の前後に組成物か
ら離脱され易いので、毒性、悪臭、脱色等の問題を起こ
す。2. Description of the Related Art Generally, when a low molecular weight photopolymerization initiator is used in a photocurable polymer composition, the low molecular weight compound is used as another component contained in the composition, for example, a photosensitive prepolymer. However, it has poor compatibility with components such as a monomer diluent, an additive, and a dye, and has a low photocuring efficiency, which causes many problems. In particular, the lack of compatibility with other components not only inhibits the photocuring reaction and leaves the reactants in an unreacted state, but also the photopolymerization initiator itself remains as a low molecular weight substance, so the photocured polymer It adversely affects the physical properties of the composition. In addition, the low-molecular-weight photopolymerization initiator easily separates from the composition before and after the photocuring reaction, which causes problems such as toxicity, malodor, and decolorization.
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは前記低分
子光重合開始化合物の短所を解決するため鋭意研究を重
ねた結果、従来の低分子光重合開始化合物をエポキシプ
レポリマーに結合させて得た新規な光重合開始化合物
が、光硬化性重合体組成物中の他成分との相溶性がよ
く、光硬化効率も優れている事実を発見して、本発明を
完成するに至った。DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted extensive studies to solve the disadvantages of the low molecular weight photopolymerization initiating compound, and as a result, the conventional low molecular weight photopolymerization initiating compound was bonded to the epoxy prepolymer. The present inventors have completed the present invention by discovering the fact that the obtained novel photopolymerization initiating compound has good compatibility with other components in the photocurable polymer composition and excellent photocuring efficiency.
【０００４】従って、本発明の目的は、光硬化性重合体
組成物中の他成分との相溶性が優れ、従来の低分子光重
合開始化合物を用いることにより生じた諸問題を解決す
るのみならず、光硬化効率も高い新規な光重合開始化合
物を提供することである。Therefore, the object of the present invention is that the compatibility with other components in the photocurable polymer composition is excellent and only the problems caused by using the conventional low molecular weight photopolymerization initiating compound are solved. And to provide a novel photopolymerization initiating compound having high photocuring efficiency.
【０００５】本発明の他の目的は、前記新規な光重合開
始化合物を含有する光硬化性重合体組成物を提供するこ
とである。Another object of the present invention is to provide a photocurable polymer composition containing the novel photopolymerization initiator compound.
【０００６】[0006]
【課題を解決するための手段】かかる本発明の目的は、
低分子光重合開始剤であるＢＡＥをエポキシプレポリマ
ー又はエポキシアクリル酸エステルプレポリマーに化学
結合させて得た、新規な化合物によって達することがで
きる。The object of the present invention is as follows.
It can be achieved by a novel compound obtained by chemically bonding a low molecular weight photoinitiator BAE to an epoxy prepolymer or an epoxy acrylate prepolymer.
【０００７】本発明の化合物は、下記の一般式（Ｉ）及
び（III)で示される化合物を含む。The compounds of the present invention include compounds represented by the following general formulas (I) and (III).
【０００８】[0008]
【化６】 [Chemical 6]
【０００９】（式中、Ｒは炭素数１〜５のアルキル基で
あり、Ｙは、エポキシ樹脂におけるグリシジル基に結合
し、酸素又は窒素原子を介して連結している多官能性芳
香族又は脂肪族炭化水素基であり、Ｐｈはフェニル基で
あり、ｘは１〜５である。）(In the formula, R is an alkyl group having 1 to 5 carbon atoms, and Y is a polyfunctional aromatic or aliphatic group bonded to a glycidyl group in the epoxy resin and linked via an oxygen or nitrogen atom. It is a group hydrocarbon group, Ph is a phenyl group, and x is 1 to 5.)
【００１０】その代表的な例として、下記の一般式（I
I）、（IV）及び（Ｖ）で示される化合物が挙げられ
る。As a typical example thereof, the following general formula (I
Examples thereof include compounds represented by I), (IV) and (V).
【００１１】[0011]
【化７】 [Chemical 7]
【００１２】以下に、本発明の化合物の製造方法を説明
する。The method for producing the compound of the present invention will be described below.
【００１３】先ず、ＢＡＥにカルボキシ基又はイソシア
ネート基を導入し、下記一般式（ＶＩ）の化合物を製造
する（Ｊ． Ｐｈｏｔｏｐｏｌｙｍ． Ｓｃｉ． Ｔｅ
ｃｈｎｏｌ．， 第3 号、137 頁、1990年）。First, a carboxy group or an isocyanate group is introduced into BAE to produce a compound represented by the following general formula (VI) (J. Photopolym. Sci. Te).
chnol. , No. 3, p. 137, 1990).
【００１４】[0014]
【化８】 [Chemical 8]
【００１５】（前記式中、Ｒは炭素数１〜５のアルキル
基であり、Ｐｈはフェニル基であり、ＸはＣＯＯＨ基又
はＮＣＯ基である）。(In the above formula, R is an alkyl group having 1 to 5 carbon atoms, Ph is a phenyl group, and X is a COOH group or an NCO group).
【００１６】ＢＡＥにカルボキシ官能基を導入すると、
前記式（VI）においてＸがＣＯＯＨ基であるα−（２−
カルボキシエチル）ベンゾインアルキルエーテル（以
下、「ＣＥＢＡＥ」と表記する）が生成し、イソシアネ
ート官能基を導入すると、式（VI）においてＸがＮＣＯ
基であるα−（２−イソシアネートエチル）ベンゾイン
アルキルエーテル（以下、「ＩＥＢＡＥ」と表記する）
が生成する。When a carboxy functional group is introduced into BAE,
In the formula (VI), X is a COOH group α- (2-
When carboxyethyl) benzoin alkyl ether (hereinafter referred to as “CEBAE”) is produced and an isocyanate functional group is introduced, X is NCO in the formula (VI).
Group α- (2-isocyanatoethyl) benzoin alkyl ether (hereinafter referred to as "IEBAE")
Is generated.
【００１７】次いで、前記一般式（VI）の化合物をエポ
キシプレポリマー又はエポキシアクリル酸エステルプレ
ポリマーに化学結合させて新規な化合物を合成する。エ
ポキシプレポリマーに結合させる方法の具体例を下記反
応式（１）に示す。この方法ではエポキシ樹脂（以下、
「ＥｐＹ」と表記する）にＣＥＢＡＥを反応させて本発
明の一般式（Ｉ）のオリゴマー型化合物であるＥｐＹ−
ＢＡＥを合成する。Then, the compound of the general formula (VI) is chemically bonded to the epoxy prepolymer or the epoxy acrylate prepolymer to synthesize a novel compound. A specific example of the method of bonding to the epoxy prepolymer is shown in the following reaction formula (1). In this method, epoxy resin (hereinafter,
(Denoted as "EpY") is reacted with CEBAE to obtain EpY- which is an oligomeric compound of the general formula (I) of the present invention.
Synthesize BAE.
【００１８】反応式（１）Reaction formula (1)
【化９】 [Chemical 9]
【００１９】エポキシアクリル酸エステルプレポリマー
（ＥｐＹ−Ａ）にＩＥＢＡＥを反応させる方法の具体例
を下記反応式（２）に示す。A specific example of the method of reacting IEBAE with the epoxy acrylate prepolymer (EpY-A) is shown in the following reaction formula (2).
【００２０】反応式（２）Reaction formula (2)
【化１０】 [Chemical 10]
【００２１】この方法によると、先ずＥｐＹにアクリル
酸を反応させてエポキシ樹脂のアクリル酸エステルプレ
ポリマー（ＥｐＹ−Ａ）を得た後、ここにＩＥＢＡＥを
反応させると、ＥｐＹ−Ａの水酸基とＩＥＢＡＥのイソ
シアネート基とが反応してウレタン構造を形成し、本発
明の一般式（III)の化合物であるＥｐＹ−Ａ−ＢＡＥを
合成する。According to this method, EpY is first reacted with acrylic acid to obtain an acrylic acid ester prepolymer (EpY-A) of an epoxy resin, and then IEBAE is reacted therewith, whereby hydroxyl groups of EpY-A and IEBAE are reacted. Reacts with the isocyanate group to form a urethane structure to synthesize EpY-A-BAE which is the compound of the general formula (III) of the present invention.
【００２２】前記の方法に用いられるＥｐＹとしては、
市販されている任意の多官能性エポキシ樹脂が用いられ
る。かかるＥｐＹの例としては、２官能性エポキシ基を
有するビスフェノールＡ、ビスフェノールＦ、テトラブ
ロモビスフェノールＡ、水添ビスフェノールＡ；４官能
性エポキシ基を有するテトラフェニロールエタン；３官
能性エポキシ基を有するフェーノルノボラック、ｏ−ク
レゾールノボラック；２官能性エポキシ基を有するポリ
プロピレングリコール、２官能性エポキシ基を有するヘ
キサヒドロ無水フタル酸、４官能性エポキシ基を有する
ジアミノフェニルメタン、３官能性エポキシ基を有する
イソシアヌル酸、２官能性エポキシを有するヒダントイ
ン、３官能性エポキシ基を有するｐ−アミノフェノー
ル、２官能性基エポキシ基を有するｐ−オキシ安息香酸
等が挙げられる。As EpY used in the above method,
Any commercially available multifunctional epoxy resin is used. Examples of such EpY include bisphenol A having a bifunctional epoxy group, bisphenol F, tetrabromobisphenol A, hydrogenated bisphenol A; tetraphenylolethane having a tetrafunctional epoxy group; Nornovolak, o-cresol novolac; polypropylene glycol having a bifunctional epoxy group, hexahydrophthalic anhydride having a bifunctional epoxy group, diaminophenylmethane having a tetrafunctional epoxy group, isocyanuric acid having a trifunctional epoxy group Examples thereof include hydantoin having a bifunctional epoxy, p-aminophenol having a trifunctional epoxy group, and p-oxybenzoic acid having a bifunctional epoxy group.
【００２３】下記反応式（３）に本発明の代表的な化合
物の製造方法を示す。この方法によると、ＣＥＢＡＥと
エポキシプレポリマー（以下、「Ｅｐ」と表記する）と
を反応させて一般式（II）のＥｐ−ＢＡＥを製造するこ
とができる。The following reaction formula (3) shows a method for producing a representative compound of the present invention. According to this method, CEBAE and an epoxy prepolymer (hereinafter referred to as “Ep”) can be reacted to produce Ep-BAE of the general formula (II).
【００２４】反応式（３）Reaction formula (3)
【化１１】 [Chemical 11]
【００２５】下記の反応式（４）に示す通り、光硬化性
プレポリマーとして広く用いられている市販のエポキシ
ジアクリレートプレポリマー（以下「ＥｐＡ」と表記す
る）とＩＥＢＡＥとを反応させて一般式（IV）のＥｐＡ
−ＢＡＥを製造することができる。As shown in the following reaction formula (4), a commercially available epoxy diacrylate prepolymer (hereinafter referred to as “EpA”) widely used as a photocurable prepolymer is reacted with IEBAE to give a general formula. (IV) EpA
-BAE can be produced.
【００２６】反応式（４）Reaction formula (4)
【化１２】 [Chemical 12]
【００２７】本発明の他の実施態様を下記反応式（５）
に示す。この方法によれば、市販のテトラグリシジルジ
アミノフェニルメタン（以下、「ＴＧＡＭ」と表記す
る）とアクリル酸とを反応させてアクリル酸エステルＴ
ＧＡＭ−Ａを得た後、これにＩＥＢＡＥを反応させて次
いでＴＧＡＭ−Ａの水酸基とＩＥＢＡＥとを反応させる
ことにより、一般式（Ｖ）のＴＧＡＭ−Ａ−ＢＡＥを製
造することができる。Another embodiment of the present invention is a reaction formula (5) below.
Shown in. According to this method, a commercially available tetraglycidyldiaminophenylmethane (hereinafter referred to as “TGAM”) is reacted with acrylic acid to form an acrylic ester T.
After obtaining GAM-A, IEBAE is reacted therewith, and then the hydroxyl group of TGAM-A is reacted with IEBAE, whereby TGAM-A-BAE of the general formula (V) can be produced.
【００２８】反応式（５）Reaction formula (5)
【化１３】 [Chemical 13]
【００２９】本発明によって製造したエポキシプレポリ
マーに結合している光重合開始化合物の光硬化性能を評
価するために、本発明の化合物にアクリレートプレポリ
マー及びアクリレート単量体を希釈剤として添加して光
硬化性重合体組成物を製造する。この時、光硬化性重合
体組成物内の全反応性アクリレート基に対して０．１〜
１５モル％の量で本発明の光重合開始化合物を含有させ
ることができる。In order to evaluate the photocuring performance of the photopolymerization initiator compound bound to the epoxy prepolymer prepared according to the present invention, an acrylate prepolymer and an acrylate monomer were added to the compound of the present invention as a diluent. A photocurable polymer composition is produced. At this time, 0.1 to 0.1% of all reactive acrylate groups in the photocurable polymer composition.
The photopolymerization initiator compound of the present invention can be contained in an amount of 15 mol%.
【００３０】[0030]
【実施例】以下に、本発明を実施例により詳しく説明す
る。しかし、これらの実施例は例示の目的で提供するも
のであって、本発明の範囲を制限するものではない。EXAMPLES The present invention will be described in detail below with reference to examples. However, these examples are provided for purposes of illustration and do not limit the scope of the invention.
【００３１】実施例１ ＥｐＡ−ＢＡＥの合成 α−（２−イソシアネートエチル）ベンゾインイソブチ
ルエーテル（以下、「ＩＥＢＩＢＥ」と表記する）１
６．７g(５０mmol）をクロロホルム１００ml中に溶解し
た後、この溶液にＥｐＡ１２．１g(２５mmol）を加えて
６０℃で１０時間反応させた。反応終了後、溶液を濾過
し、濾液中の溶媒を蒸発させて粘性の一般式（IV）の光
重合開始剤ＥｐＡ−ＢＡＥを得た。Example 1 Synthesis of EpA-BAE α- (2-isocyanatoethyl) benzoin isobutyl ether (hereinafter referred to as "IEBIBE") 1
After 6.7 g (50 mmol) was dissolved in 100 ml of chloroform, 12.1 g (25 mmol) of EpA was added to this solution and reacted at 60 ° C. for 10 hours. After completion of the reaction, the solution was filtered and the solvent in the filtrate was evaporated to obtain a viscous photopolymerization initiator EpA-BAE of the general formula (IV).
【００３２】実施例２ ＴＧＡＭ−Ａ−ＢＡＥの合成 ＴＧＡＭ５．０g(１２mmol）及びトリエチルベンジルア
ンモニウムクロリド０．５g を室温でクロロホルム５０
mlに溶解した。次いでアクリル酸３．６g(５０mmol）を
クロロホルム５０mlに溶解した溶液を滴下し、４時間還
流させた。溶媒を除去した後、残留物をエチルアセテー
ト及び塩化ナトリウム飽和溶液で４回抽出した。エチル
アセテート抽出液を無水硫酸マグネシウムで乾燥した
後、溶媒を蒸発させて粘性のＴＧＡＭ−Ａを得た。ＴＧ
ＡＭ−Ａ５．０g(７mmol）及びＩＥＢＩＢＥ９．４g(２
８mmol）をクロロホルム５０mlに溶解して６０℃で反応
させた。反応後、溶媒を蒸発させて粘性の一般式（Ｖ）
の光重合開始剤ＴＧＡＭ−Ａ−ＢＡＥを得た。Example 2 Synthesis of TGAM-A-BAE 5.0 g (12 mmol) of TGAM and 0.5 g of triethylbenzylammonium chloride were added to chloroform 50 at room temperature.
dissolved in ml. Then, a solution prepared by dissolving 3.6 g (50 mmol) of acrylic acid in 50 ml of chloroform was added dropwise, and the mixture was refluxed for 4 hours. After removing the solvent, the residue was extracted 4 times with ethyl acetate and saturated sodium chloride solution. The ethyl acetate extract was dried over anhydrous magnesium sulfate and the solvent was evaporated to obtain viscous TGAM-A. TG
AM-A 5.0 g (7 mmol) and IEBIBE 9.4 g (2
8 mmol) was dissolved in 50 ml of chloroform and reacted at 60 ° C. After the reaction, the solvent is evaporated to give a viscous compound of general formula (V)
To obtain TGAM-A-BAE as a photopolymerization initiator.
【００３３】実施例３ 光硬化性組成物の光硬化効率評
価 前記実施例１及び２で製造した本発明の光重合開始化合
物にアクリレートプレポリマー及び場合によって多官能
性アクリレート単量体を添加して、本発明による光硬化
性重合体組成物を製造した。この時、組成物内の全ての
反応性アクリレート基に対して光重合開始剤を３モル％
量含有させる。Example 3 Evaluation of Photocuring Efficiency of Photocurable Composition An acrylate prepolymer and optionally a polyfunctional acrylate monomer were added to the photopolymerization initiation compound of the present invention prepared in Examples 1 and 2 above. A photocurable polymer composition according to the present invention was prepared. At this time, 3 mol% of the photopolymerization initiator was added to all the reactive acrylate groups in the composition.
Amount is included.
【００３４】光重合開始化合物として従来の低分子光重
合開始化合物であるベンゾインイソブチルエーテルを用
いて前記の通り、対照用光硬化性重合体組成物を製造し
た。A photocurable polymer composition for control was prepared as described above using benzoin isobutyl ether, which is a conventional low molecular weight photopolymerization initiating compound, as the photopolymerization initiating compound.
【００３５】これらの光硬化性重合体組成物をスピンコ
ータを用いて岩塩板に約５ミクロンの厚さで塗布してフ
ィルムを形成させた後、高圧水銀灯（５００W 、波長３
６５nmにおける光強度４５．０mW/cm2）で光照射し、次
いで、露光量により光硬化反応程度を、赤外線吸収スペ
クトルで炭素−炭素二重結合に基づいた１，４０５cm-1
吸収バンドの強度の減少を測定して評価した。These photocurable polymer compositions were applied to a rock salt plate at a thickness of about 5 μm using a spin coater to form a film, and then a high pressure mercury lamp (500 W, wavelength 3) was used.
It was irradiated with light having a light intensity of 45.0 mW / cm 2 at 65 nm, and then the degree of photocuring reaction was determined by the amount of exposure and 1,405 cm −1 based on the carbon-carbon double bond in the infrared absorption spectrum.
The decrease in the intensity of the absorption band was measured and evaluated.
【００３６】その結果、実施例１及び２で製造した本発
明の光重合開始化合物を含有する光硬化性重合体組成物
は、ベンゾインイソブチルエーテルを含有する対照用光
硬化性重合体組成物に比べて、２倍以上高い光硬化速度
を示した。As a result, the photocurable polymer composition containing the photopolymerization initiating compound of the present invention prepared in Examples 1 and 2 was compared with the control photocurable polymer composition containing benzoin isobutyl ether. And showed a photo-curing rate that was more than twice as high.
【００３７】[0037]
【発明の作用、効果】本発明の光重合開始化合物は、Ｂ
ＡＥをプレポリマーに化学結合させた化合物であるた
め、プレポリマーを主成分とする光硬化性重合体組成物
の他成分との相溶性が優れ、一つの分子が光重合開始剤
としてかつ重合性単量体としての機能を共に有している
ので、光重合開始剤の貯蔵安定性及び光硬化効率を向上
させることができる。また、光照射によってプレポリマ
ーの重合が完了し、硬化された最終物質において、光重
合開始剤は高分子の分枝に結合されているので脱離せ
ず、毒性、悪臭、脱色等の問題を解決することができ
る。The action and effect of the present invention are as follows:
Since it is a compound in which AE is chemically bonded to a prepolymer, it has excellent compatibility with other components of the photocurable polymer composition containing the prepolymer as a main component, and one molecule serves as a photopolymerization initiator and is polymerizable. Since it has both the function as a monomer, the storage stability and the photocuring efficiency of the photopolymerization initiator can be improved. In addition, the photopolymerization initiator is bonded to the branches of the polymer in the final substance, which has been polymerized by the light irradiation and has been cured, so it does not detach and solves the problems of toxicity, malodor, and discoloration. can do.
【００３８】本発明による光硬化性組成物は、低分子Ｂ
ＡＥを光重合開始剤として用いて製造された光硬化性重
合体組成物に比べて、はるかに高い光硬化効率を示す。The photocurable composition according to the present invention comprises a low molecular weight B
Compared with the photocurable polymer composition produced using AE as a photopolymerization initiator, it exhibits a much higher photocuring efficiency.
【００３９】本発明の光硬化性重合体組成物が高い光硬
化効率を示す理由は、光硬化時の光反応により生成した
本発明の光重合開始化合物のラジカルが近接のアクリル
基と反応し易く、ラジカル間の相互結合程度が低いため
に、重合開始効率が高いこと並びに本発明の化合物と他
の組成物成分との高い相溶性により説明することができ
る。The reason why the photocurable polymer composition of the present invention exhibits high photocuring efficiency is that the radicals of the photopolymerization initiating compound of the present invention generated by the photoreaction during photocuring easily react with the adjacent acrylic group. The high degree of polymerization initiation due to the low degree of mutual coupling between radicals and the high compatibility of the compound of the present invention with other composition components can be explained.
Claims (7)
プレポリマー又はエポキシアクリル酸エステルプレポリ
マーに化学的に結合していることが特徴とする化合物。1. A compound characterized in that a benzoyl alkyl ether is chemically bonded to an epoxy prepolymer or an epoxy acrylate prepolymer.
ポキシ樹脂におけるグリシジル基に結合し、酸素又は窒
素原子を介して連結している多官能性芳香族又は脂肪族
炭化水素基であり、Ｐｈはフェニル基であり、ｘは１〜
５である。）で示される請求項１記載の化合物。2. The following formula: (In the formula, R is an alkyl group having 1 to 5 carbon atoms, Y is a polyfunctional aromatic or aliphatic hydrocarbon group bonded to a glycidyl group in the epoxy resin and linked via an oxygen or nitrogen atom. , Ph is a phenyl group, and x is 1 to
It is 5. ] The compound of Claim 1 shown by these.
フェニル基である）で示される請求項２記載の化合物。3. The following formula: The compound according to claim 2, wherein R is an alkyl group having 1 to 5 carbon atoms and Ph is a phenyl group.
ポキシ樹脂におけるグリシジル基に結合し、酸素又は窒
素原子を介して連結している多官能性芳香族又は脂肪族
炭化水素基であり、Ｐｈはフェニル基であり、ｘは１〜
５である）で示される請求項１記載の化合物。4. The following formula: (In the formula, R is an alkyl group having 1 to 5 carbon atoms, Y is a polyfunctional aromatic or aliphatic hydrocarbon group bonded to a glycidyl group in the epoxy resin and linked via an oxygen or nitrogen atom. , Ph is a phenyl group, and x is 1 to
The compound according to claim 1, which is represented by 5).
フェニル基である）で示される請求項４記載の化合物。5. The following formula: The compound according to claim 4, wherein R is an alkyl group having 1 to 5 carbon atoms and Ph is a phenyl group.
フェニル基である）で示される請求項４記載の化合物。6. The following formula: The compound according to claim 4, wherein R is an alkyl group having 1 to 5 carbon atoms and Ph is a phenyl group.
合物１種以上を光重合開始剤として含有することを特徴
とする光硬化性重合体組成物。7. A photocurable polymer composition comprising one or more compounds according to any one of claims 1 to 6 as a photopolymerization initiator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR150/1994 | 1994-01-06 | ||
| KR1019940000150A KR0124966B1 (en) | 1994-01-06 | 1994-01-06 | Novel photoinitiators and photosensitive polymer composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07206775A true JPH07206775A (en) | 1995-08-08 |
| JP2726803B2 JP2726803B2 (en) | 1998-03-11 |
Family
ID=19375325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6173835A Expired - Fee Related JP2726803B2 (en) | 1994-01-06 | 1994-07-26 | Novel photopolymerization initiator compound and photocurable polymer composition containing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2726803B2 (en) |
| KR (1) | KR0124966B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100871397B1 (en) * | 2006-12-29 | 2008-12-02 | 주식회사 잉크테크 | Water-Soluble Photoinitiators |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6480946A (en) * | 1987-08-05 | 1989-03-27 | Ciba Geigy Ag | Image formation |
-
1994
- 1994-01-06 KR KR1019940000150A patent/KR0124966B1/en not_active IP Right Cessation
- 1994-07-26 JP JP6173835A patent/JP2726803B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6480946A (en) * | 1987-08-05 | 1989-03-27 | Ciba Geigy Ag | Image formation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2726803B2 (en) | 1998-03-11 |
| KR950024015A (en) | 1995-08-21 |
| KR0124966B1 (en) | 1997-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0007508B1 (en) | Acylphosphinoxide compounds, their preparation and their use | |
| JP2855429B2 (en) | Photoreactive photopolymerization initiator | |
| Temel et al. | Polymeric side chain thioxanthone photoinitiator for free radical polymerization | |
| JP3914363B2 (en) | Re-dissolvable acid-crosslinking polymer and photosensitive resin composition combining the polymer and a photoacid generator | |
| JP2007008875A (en) | Calixarene-based derivative and composition containing the same | |
| CN102770465A (en) | Macro-photoinitiators and curable compositions thereof | |
| JP6966764B2 (en) | Resin compositions, compounds and photopolymerization initiators | |
| JP3736817B2 (en) | Polyfunctional vinyl ether, polymerizable composition and cured product thereof | |
| CN113248636B (en) | Thioxanthone visible light initiator, preparation method and application | |
| JP3892926B2 (en) | Calixarene derivative and curable resin composition containing the same | |
| JP2726803B2 (en) | Novel photopolymerization initiator compound and photocurable polymer composition containing the same | |
| US5624788A (en) | Organic silicon compound, resist thermal polymerization composition and photopolymerization composition | |
| JP3021152B2 (en) | Radical polymerizable bifunctional (meth) acrylate | |
| JPS5854337A (en) | Photosensitive resin composition | |
| JP2007131707A (en) | Azo functional group-containing copolymer | |
| JPH0645697B2 (en) | Curable resin composition | |
| JP6961189B2 (en) | Acidic group-containing polymerizable monomer having a functional group with a high dielectric constant | |
| JP2009263441A (en) | Decomposable curing resin | |
| JPH04145055A (en) | Acrylamide derivative | |
| US4458063A (en) | 2-Methyl-1,3-propylene glycol mono- or di-alkylene oxide ether | |
| WO2021049564A1 (en) | Photobase generator, compound, photoreactive composition, and reaction product | |
| JP7344001B2 (en) | polymer | |
| JPS6318935B2 (en) | ||
| JPS61145268A (en) | Moisture-curing self-adhesive composition | |
| JP3021151B2 (en) | (Meth) acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |