KR0124966B1 - Novel photoinitiators and photosensitive polymer composition containing the same - Google Patents
Novel photoinitiators and photosensitive polymer composition containing the sameInfo
- Publication number
- KR0124966B1 KR0124966B1 KR1019940000150A KR19940000150A KR0124966B1 KR 0124966 B1 KR0124966 B1 KR 0124966B1 KR 1019940000150 A KR1019940000150 A KR 1019940000150A KR 19940000150 A KR19940000150 A KR 19940000150A KR 0124966 B1 KR0124966 B1 KR 0124966B1
- Authority
- KR
- South Korea
- Prior art keywords
- photoinitiator
- group
- initiator compound
- photo
- present
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- -1 benzoin alkyl ether Chemical class 0.000 abstract description 9
- 239000004593 Epoxy Substances 0.000 abstract description 7
- 244000028419 Styrax benzoin Species 0.000 abstract description 2
- 235000000126 Styrax benzoin Nutrition 0.000 abstract description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 abstract description 2
- 229960002130 benzoin Drugs 0.000 abstract description 2
- 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 2
- 235000019382 gum benzoic Nutrition 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract 6
- 239000002253 acid Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 230000007096 poisonous effect Effects 0.000 abstract 1
- 238000000016 photochemical curing Methods 0.000 description 18
- 125000003700 epoxy group Chemical group 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000001588 bifunctional effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000000243 solution Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000002845 discoloration Methods 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
- 239000000463 material Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 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
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 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
- 239000005711 Benzoic acid Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 125000004386 diacrylate group Chemical group 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 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
- 125000000524 functional group Chemical group 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 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
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance 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
본 발명은 신규한 광개시제 화합물 및 이를 함유하는 감광성 중합체 조성물에 관한 것이다. 더욱 상세히 설명하자면, 본 발명은 벤조인알킬에테르(benzoin alkyl ether : 이하, 「BAE」로 표기함) 광개시제를 에폭시 프레폴리머 또는 아크릴산 에스테르 프레폴리머에 화학적으로 결합시켜 얻은 신규의 광개시제 화합물 및 이를 함유하는 광경화 조성물에 관한 것이다.The present invention relates to novel photoinitiator compounds and photosensitive polymer compositions containing them. More specifically, the present invention provides a novel photoinitiator compound obtained by chemically bonding a benzoin alkyl ether (hereinafter referred to as "BAE") photoinitiator to an epoxy prepolymer or an acrylic acid ester prepolymer, and a composition containing the same. It relates to a photocurable composition.
일반적으로, 광개시제 화합물에 저분자량의 광개시제를 사용할 경우, 이 저분자 화합물은 조성물중에 함유되어 있는 다른 성분들, 예를 들면 감광성 프레폴리머, 단량체 희석제, 첨가제, 색소 등과 같은 성분들과의 상용성이 부족하고, 광경화 효율도 낮기 때문에 많은 문제점들이 발생한다. 특히, 다른 성분들과의 상용성 부족은 광경화 반응을 저해하여 반응 물질등을 미반응된 상태로 남게할 뿐만 아니라, 광개시제 자체도 저분자 물질인 채로 그대로 남게 되어 광경화된 조성물의 물리적 성질에 나쁜 영향을 미치게 된다. 또한, 저분자 광개시제는 광경화 반응을 전후하여 조성물로부터 이탈되어 나오기 쉬우므로 독성, 악취, 탈색 등의 문제도 일으키게 된다.Generally, when a low molecular weight photoinitiator is used in the photoinitiator compound, the low molecular weight compound lacks compatibility with other components contained in the composition, such as components such as photosensitive prepolymers, monomer diluents, additives, and pigments. In addition, many problems arise because of the low photocuring efficiency. In particular, the lack of compatibility with other components inhibits the photocuring reaction to leave the reactants and the like unreacted, and the photoinitiator itself remains as a low molecular material, which is bad for the physical properties of the photocured composition. Will be affected. In addition, since the low molecular weight photoinitiator is easily released from the composition before and after the photocuring reaction, problems such as toxicity, odor, and discoloration also occur.
본 발명자들은 상기한 저분자 광개시제 화합물의 단점을 해결하기 위하여 예의 연구를 거듭한 결과, 기존의 광개시제 화합물을 프레폴리머 분자에 결합시켜 제조한 새로운 광개시제 화합물이 광경화 조성물 중의 다른 성분들과의 상용성이 좋으며, 광경화 효율도 높다는 사실을 발견하여 본 발명을 완성하기에 이르렀다.The present inventors have intensively researched to solve the above-mentioned disadvantages of the low molecular weight photoinitiator compound. As a result, the new photoinitiator compound prepared by binding the existing photoinitiator compound to the prepolymer molecule is compatible with other components in the photocuring composition. It was found to be good and the photocuring efficiency was also high to complete the present invention.
따라서, 본 발명의 목적은 광경화 조성물 중의 다른 성분들과의 상용성이 우수하여 종래의 저분자 광개시제 화합물을 사용하는데서 연유하는 문제점들을 해결할 수 있을 뿐만 아니라, 광경화 효율도 높은 신규의 광개시제 화합물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a novel photoinitiator compound which is excellent in compatibility with other components in the photocurable composition to solve the problems inherent in using the conventional low molecular weight photoinitiator compound, and also has high photocuring efficiency. It is.
본 발명의 다른 목적은 상기한 신규의 광개시제 화합물을 함유하는 광경화성 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a photocurable composition containing the novel photoinitiator compound described above.
이러한 본 발명의 목적은, 저분자 광개시제인 BAE가 에폭시 프레폴리머 또는 에폭시 수지를 변형시킨 아크릴산 에스테르 프레폴리머에 화학 결합된 신규한 광개시제 화합물에 의해 달성될 수 있다.This object of the present invention can be achieved by a novel photoinitiator compound in which BAE, a low molecular photoinitiator, is chemically bonded to an epoxy prepolymer or an acrylic ester prepolymer modified with an epoxy resin.
본 발명의 광개시제 화합물은 프레폴리머에 화학 결합시켜 제조했기 때문에 프레폴리머를 주성분으로 하는 광경화 조성물의 다른 성분들과의 상용성이 뛰어나고, 광개시제 화합물 한 분자가 광개시제로서 및 중합성 단량체로서의 기능을 함께 갖고 있으므로 광개시제의 저장 안정성 및 광경화 효율을 향상시킬 수 있다. 또한, 광 조사에 의해 프레폴리머의 중합이 완료되어 경화된 최종 물질에서 광개시제는 고분자의 측쇄에 결합되어 있으므로, 독성, 악취, 탈색 등의 문제를 해결할 수 있다.Since the photoinitiator compound of the present invention is prepared by chemical bonding to a prepolymer, the photoinitiator compound has excellent compatibility with other components of the photocuring composition containing the prepolymer as a main component, and one molecule of the photoinitiator compound functions as both a photoinitiator and a polymerizable monomer. Since it has, the storage stability and photocuring efficiency of a photoinitiator can be improved. In addition, since the photoinitiator is bonded to the side chain of the polymer in the final material cured after completion of polymerization of the prepolymer by light irradiation, problems such as toxicity, odor, and discoloration can be solved.
본 발명의 광개시제 화합물은 하기 식으로 표시되는 것들을 포함한다 :Photoinitiator compounds of the present invention include those represented by the following formula:
그 대표적인 예로서 다음과 같은 화합물이 있다.Representative examples thereof include the following compounds.
상기 식들중, R은 알킬기[CnH2n+1(여기서, n은 1 내지 5임)]이고, Y는, 원래의 에폭시 수지에 있어서 글리시딜기가 결합되어 있던, 산소 또는 질소 원자에 의해 연결되는 다관능성 방향족 또는 지방족 탄화수소기이고, Ph는 페닐기이고, x는 1 내지 5이다.In the above formula , R is an alkyl group [C n H 2n + 1 , wherein n is 1 to 5], and Y is an oxygen or nitrogen atom to which a glycidyl group is bonded in the original epoxy resin. To which a polyfunctional aromatic or aliphatic hydrocarbon group is linked, Ph is a phenyl group, x is 1 to 5.
이하, 본 발명의 광개시제 화합물의 제조 방법을 설명한다.Hereinafter, the manufacturing method of the photoinitiator compound of this invention is demonstrated.
먼저, 저분자 광개시제인 BAE에 반응성기를 도입시켜 하기 일반식의 화합물을 제조한다(J.Photopolym. Sci. Technol, 제3호, 137 페이지, 1990년 참조).First, a reactive group is introduced into BAE, a low molecular photoinitiator, to prepare a compound of the following general formula (see J. Photopolym. Sci. Technol, No. 3, page 137, 1990).
상기 식중, R은 알킬기[CnH2n+1(여기서, n은 1 내지 5임)]이고, Ph는 페닐기이며, X는 COOH 또는 NCO이다.Wherein R is an alkyl group [C n H 2n + 1 wherein n is 1 to 5], Ph is a phenyl group and X is COOH or NCO.
도입되는 반응성기로서는 카르복시 또는 이소시아네이트 관능기가 사용된다. 카르복시 관능기를 도입시킬 경우에는 상기 식에서 X가 COOH인 α-(2-카르복시에틸)벤조인알킬에테르(이하, 「CEBAE」로 표기함)가 생성되며, 이소시아네이트 관능기를 도입시키면 X가 NCO인 α-(2-이소시아네이토에틸)벤조인알킬에테르(이하, 「IEBAE」로 표기함)가 생성된다.As the reactive group to be introduced, a carboxy or isocyanate functional group is used. In the case of introducing a carboxyl functional group, α- (2-carboxyethyl) benzoinalkyl ether (hereinafter referred to as "CEBAE") in which X is COOH is formed, and when an isocyanate functional group is introduced, α- in which X is NCO is introduced. (2-isocyanatoethyl) benzoin alkyl ether (hereinafter referred to as "IEBAE") is produced.
이어서, 상기 일반식의 화합물을 에폭시 프레폴리머 또는 에폭시 수지를 변형시킨 아크릴산 에스테르 프레폴리머에 화학 결합시켜 신규의 광개시제 화합물을 합성한다.Subsequently, the compound of the general formula is chemically bonded to an epoxy prepolymer or an acrylic ester prepolymer modified with an epoxy resin to synthesize a novel photoinitiator compound.
에폭시 프레폴리머에 결합시키는 방법의 구체적인 예가 하기 반응식(1)에 도시되어 있다. 이 방법에서는 에폭시 수지(이하, 「EpY」로 표기함)에 CEBAE를 반응시켜 본 발명에 따른 올리고머형 광개시제 EpY-BAE를 합성한다.Specific examples of the method of bonding to the epoxy prepolymer are shown in Scheme (1) below. In this method, CEBAE is reacted with an epoxy resin (hereinafter referred to as "EpY") to synthesize an oligomer-type photoinitiator EpY-BAE according to the present invention.
에폭시 수지를 변형시킨 아크릴산 에스테르 프레폴리머에 화학 결합시키는 방법의 한가지 예가 하기 반응식(2)에 도시되어 있다.One example of a method of chemically bonding an epoxy resin to a modified acrylic ester prepolymer is shown in Scheme (2) below.
이 방법에 따르면, 우선 EpY에 아크릴산을 반응시켜 아크릴산 에스테르(EpY-A) 프레폴리머를 제조한 다음, 여기에 IEBAE를 반응시키면, EpY-A의 수산기(OH)와 IEBAE의 이소시아네이트기가 반응하여 우레탄 구조를 형성하면서 본 발명의 광개시제 화합물인 EpY-A-BAE가 합성된다.According to this method, first, an acrylic acid is reacted with EpY to prepare an acrylic ester (EpY-A) prepolymer, and then an IEBAE is reacted thereto, whereby a hydroxyl group (OH) of EpY-A and an isocyanate group of IEBAE react to form a urethane structure. EpY-A-BAE, which is a photoinitiator compound of the present invention, is synthesized.
위 방법에 사용되는 EpY로서는 시판되는 임의의 다관능성 에폭시 수지가 사용될 수 있다. 이러한 EpY의 예로서는, 2관능성 에폭시기를 갖는 비스페놀 A, 2관능성 에폭시기를 갖는 비스페놀 F, 2관능성 에폭시기를 갖는 테트라브로모비스페놀 A, 4관능성 에폭시기를 갖는 테트라페닐올에탄, 3관능성 에폭시기를 갖는 페놀노볼락, 3관능성 에폭시기를 갖는 o-크레졸노볼락, 2관능성 에폭시기를 갖는 폴리프로필렌글리콜, 2관능성 에폭시기를 갖는 수첨 비스페놀 A, 2관능성 에폭시기를 갖는 헥사히드로무수프탈산, 4관능성 에폭시기를 갖는 디아미노디페닐메탄, 3관능성 에폭시기를 갖는 이소시아눌산, 2관능성 에폭시기를 갖는 히단토인, 3관능성 에폭시기를 갖는 p-아미노페놀, 2관능성 에폭시기를 갖는 p-옥시안식향산 등을 들 수 있다.As the EpY used in the above method, any commercially available polyfunctional epoxy resin can be used. Examples of such EpY include bisphenol A having a bifunctional epoxy group, bisphenol F having a bifunctional epoxy group, tetrabromobisphenol A having a bifunctional epoxy group, tetraphenylolethane having a tetrafunctional epoxy group, and a trifunctional epoxy group. Phenol novolac having a, o-cresol novolac having a trifunctional epoxy group, polypropylene glycol having a bifunctional epoxy group, hydrogenated bisphenol A having a bifunctional epoxy group, hexahydrophthalic anhydride having a bifunctional epoxy group, 4 Diaminodiphenylmethane having a functional epoxy group, isocyanuric acid having a trifunctional epoxy group, hydantoin having a bifunctional epoxy group, p-aminophenol having a trifunctional epoxy group, p-oxy having a bifunctional epoxy group Benzoic acid; and the like.
하기 반응식(3)에는 본 발명의 대표적인 광개시제 화합물의 제조 방법이 도시되어 있다. 이 방법에 따르면 화학 반응성 광개시제 CEBAE를 에폭시 프레폴리머(이하, 「Ep」라 표기함)에 반응시켜 본 발명의 광개시제인 Ep-BAE를 제조할 수 있다.Scheme (3) below shows a method for preparing a representative photoinitiator compound of the present invention. According to this method, the chemically reactive photoinitiator CEBAE can be reacted with an epoxy prepolymer (hereinafter referred to as "Ep") to produce Ep-BAE, which is the photoinitiator of the present invention.
하기 반응식(4)에 도시한 바와 같이, 광경화성 프레폴리머로 널리 사용되는 시판되는 에폭시디아크릴레이트 프레폴리머(이하, 「EpA」로 표기함)에 IEBAE를 화학 반응시켜 본 발명에 따른 광개시제 화합물인 EpA-BAE를 제조할 수 있다.As shown in the following Reaction Scheme (4), IEBAE is chemically reacted with a commercially available epoxy diacrylate prepolymer (hereinafter referred to as "EpA") widely used as a photocurable prepolymer, which is a photoinitiator compound according to the present invention. EpA-BAE can be prepared.
본 발명의 또 다른 실시태양이 하기 반응식(5)에 도시되어 있다. 이 방법에 따르면, 시판되는 테트라글리시딜디아미노디페닐메탄(이하, 「TGAM」으로 표기함)을 아크릴산과 반응시켜 아크릴산 에스테르 TGAM-A를 제조한 다음, 이를 IEBAE와 반응시켜 TGAM-A의 수산기와 IEBAE를 반응시킴으로써 본 발명의 광개시제 TGAM-A-BAE를 합성할 수 있다.Another embodiment of the invention is shown in Scheme 5 below. According to this method, commercially available tetraglycidyldiaminodiphenylmethane (hereinafter referred to as "TGAM") is reacted with acrylic acid to prepare acrylic ester TGAM-A, which is then reacted with IEBAE to produce TGAM-A. The photoinitiator TGAM-A-BAE of the present invention can be synthesized by reacting a hydroxyl group with IEBAE.
본 발명에 따라 제조한, 프레폴리머에 결합되어 있는 광개시제 화합물의 광경화 성능을 평가하기 위하여, 본 발명의 광개시제 화합물에 아크릴레이트 프레폴리머 및 아크릴레이트 단량체를 희석제로 첨가하여 광경화성 조성물을 제조한다. 이때, 광개시제 화합물은 조성물 내의 모든 반응성 아크릴레이트기에 대하여 0.1내지 15몰%의 양으로 광경화 조성물 중에 함유될 수 있다.In order to evaluate the photocuring performance of the photoinitiator compound bound to the prepolymer prepared according to the present invention, a photocurable composition is prepared by adding an acrylate prepolymer and an acrylate monomer to the photoinitiator compound of the present invention as a diluent. In this case, the photoinitiator compound may be contained in the photocurable composition in an amount of 0.1 to 15 mole% with respect to all reactive acrylate groups in the composition.
본 발명에 따른 광경화성 조성물은 저분자 벤조인이소부틸에테르를 광개시제로 사용하여 제조한 광경화성 조성물에 비하여 훨씬 더 높은 광반응성을 나타낸다.The photocurable compositions according to the invention exhibit much higher photoreactivity compared to photocurable compositions prepared using low molecular weight benzoin isobutylether as photoinitiator.
이와 같이, 본 발명의 광경화성 조성물이 높은 광경화 효율을 나타내는 이유는, 광경화시의 광반응에 의해 생성된 본 발명의 광개시제 화합물의 라디칼이 근접한 아크릴기와 반응하기 쉽고, 라디칼간의 상호 결합 정도가 낮아 중합개시 효율이 높은 점과 본 발명 화합물의 다른 조성물 성분들과의 높은 상용성으로 설명될 수 있다.As described above, the photocurable composition of the present invention exhibits high photocuring efficiency because radicals of the photoinitiator compound of the present invention generated by photoreaction at the time of photocuring are likely to react with adjacent acrylic groups, and the degree of mutual bonding between radicals is high. It can be explained by the low polymerization initiation efficiency and the high compatibility with other composition components of the compound of the present invention.
이하, 본 발명을 실시예에 의하여 구체적으로 설명한다. 그러나, 이들 실시예는 예시의 목적으로 제공된 것으로, 본 발명의 범위를 제한하고자 하는 것은 아니다.Hereinafter, an Example demonstrates this invention concretely. However, these examples are provided for the purpose of illustration and are not intended to limit the scope of the invention.
[실시예 1]Example 1
EpA-BAE의 합성Synthesis of EpA-BAE
α-(2-이소시아네이토에틸)벤조인이소부틸에테르(이하, 「IEBIBE」로 표기함)16.7g(50mmol)을 클로로포름 100mL중에 용해시킨 다음, 이 용액에 EpA 12.1g(25mmol)을 가하여 60℃에서 10시간 동안 반응시켰다. 반응 종료 후 용액을 여과하고, 여과액의 용매를 증발시켜 점성의 EpA-BAE를 얻었다.16.7 g (50 mmol) of α- (2-isocyanatoethyl) benzoin isobutyl ether (hereinafter referred to as "IEBIBE") were dissolved in 100 mL of chloroform, and then 12.1 g (25 mmol) of EpA was added to the solution. The reaction was carried out at 60 ° C. for 10 hours. The solution was filtered after completion | finish of reaction, and the solvent of the filtrate was evaporated and viscous EpA-BAE was obtained.
[실시예 2]Example 2
TGAM-A-BAE의 합성Synthesis of TGAM-A-BAE
TGAM 5.0g(12mmol) 및 트리에틸벤질암모늄클로라이드 0.5g을 실온에서 클로로포름 50mL에 용해시켰다. 이어서, 아크릴산 3.6g(50mmol)을 클로로포름 50mL에 용해시킨 용액을 적가하여 4시간 동안 환류시켰다. 용매를 제거한 후 잔류물을 에틸아세테이트 및 포화 소금물로 4회 추출시켰다. 에틸아세테이트 추출액을 무수 황산 마그네슘으로 건조시킨 다음, 용매를 증발시켜 점성의 TGAM-A를 얻었다. TGAM-A 5.0g(7mmol) 및 IEBIBE 9.4g(28mmol)을 클로로포름 50mL에 용해시켜 60℃에서 반응시켰다. 반응 후 용매를 증발시켜 점성의 TGAM-A-BAE를 얻었다.5.0 g (12 mmol) of TGAM and 0.5 g of triethylbenzylammonium chloride were dissolved in 50 mL of chloroform at room temperature. Then, a solution of 3.6 g (50 mmol) of acrylic acid dissolved in 50 mL of chloroform was added dropwise to reflux for 4 hours. After removing the solvent, the residue was extracted four times with ethyl acetate and saturated brine. The ethyl acetate extract was dried over anhydrous magnesium sulfate, and then the solvent was evaporated to give viscous TGAM-A. 5.0 g (7 mmol) of TGAM-A and 9.4 g (28 mmol) of IEBIBE were dissolved in 50 mL of chloroform and reacted at 60 ° C. After the reaction, the solvent was evaporated to give viscous TGAM-A-BAE.
[실시예 3]Example 3
광경화 조성물의 광경화 효율 평가Evaluation of Photocuring Efficiency of Photocuring Composition
상기 실시예 1 및 2에서 제조한 본 발명의 프레폴리머에 결합된 광개시제 화합물에 아크릴레이트 프레폴리머 및 경우에 따라, 다관능성 아크릴레이트 단량체를 첨가하여 본 발명에 따른 광경화 조성물을 제조하였다. 이때, 광개시제 화합물은 조성물 내의 모든 반응성 아크릴레이트기에 대하여 3몰%의 양으로 함유되었다.The photocuring composition according to the present invention was prepared by adding an acrylate prepolymer and optionally a multifunctional acrylate monomer to the photoinitiator compound bound to the prepolymers of the present invention prepared in Examples 1 and 2. At this time, the photoinitiator compound was contained in an amount of 3 mol% relative to all the reactive acrylate groups in the composition.
광개시제 화합물로서 종래의 저분자 광개시제 화합물인 벤조인이소부틸에테르를 사용하여 상기한 바와 같이 대조용 광경화 조성물을 제조하였다.As the photoinitiator compound, a control photocurable composition was prepared as described above using benzoin isobutyl ether, which is a conventional low molecular photoinitiator compound.
이들 광경화 조성물을 스핀 코터를 사용하여 암염판에 두께 약 5미크론으로 도포하여 필름을 형성시킨 다음 고압 수은등(500W, 파장 365㎚에서의 광세기 45.0mW/㎠)으로 광조사하였다. 이어서, 노광량에 따른 광경화 반응 정도를 적외선 흡수 스펙트럼에서 탄소-탄소 이중결합에 기인하는 1405㎝-1흡수 밴드의 세기 감소를 측정하여 평가하였다.These photocurable compositions were applied to a rock salt plate using a spin coater with a thickness of about 5 microns to form a film, and then irradiated with a high pressure mercury lamp (500 W, light intensity 45.0 mW / cm 2 at a wavelength of 365 nm). Subsequently, the degree of photocuring reaction according to the exposure dose was evaluated by measuring the intensity reduction of the 1405 cm -1 absorption band due to the carbon-carbon double bond in the infrared absorption spectrum.
그 결과, 실시예 1 및 2에서 제조한 본 발명의 광개시제 화합물을 함유하는 광경화 조성물은 광개시제로서 벤조인이소부틸에테르를 사용한 대조용 광경화 조성물에 비하여 2배 이상 높은 광경화 속도를 나타내었다.As a result, the photocuring composition containing the photoinitiator compound of the present invention prepared in Examples 1 and 2 exhibited a photocuring rate at least two times higher than the control photocuring composition using benzoin isobutyl ether as the photoinitiator.
Claims (6)
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