WO2013060254A1 - Nouveau mélange photoinitiateur composé d'une hydroxyle cétone aromatique et d'un oxyde de phosphoryle et système composite doté de celui-ci et d'un photoabsorbeur - Google Patents

Nouveau mélange photoinitiateur composé d'une hydroxyle cétone aromatique et d'un oxyde de phosphoryle et système composite doté de celui-ci et d'un photoabsorbeur Download PDF

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Publication number
WO2013060254A1
WO2013060254A1 PCT/CN2012/083322 CN2012083322W WO2013060254A1 WO 2013060254 A1 WO2013060254 A1 WO 2013060254A1 CN 2012083322 W CN2012083322 W CN 2012083322W WO 2013060254 A1 WO2013060254 A1 WO 2013060254A1
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group
alkyl
phenyl
parts
compound
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PCT/CN2012/083322
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English (en)
Chinese (zh)
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王智刚
张永波
王衍超
宋怀海
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深圳市有为化学技术有限公司
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Publication of WO2013060254A1 publication Critical patent/WO2013060254A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
    • C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • 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

Definitions

  • the invention relates to the technical field of light radiation curing, in particular to a novel photoinitiator system composed of a combination of an aromatic hydroxy ketone and an acylphosphine oxide compound, and a photoinitiator system and a suitable hydroxybenzoic acid having red light absorbing characteristics.
  • the triazole-based light absorbing agent is compounded to form an ethylenically unsaturated system which can be cured by irradiation of light (ultraviolet light or visible light or an equivalent source).
  • Phosphonoyl compounds are important photoinitiators and have been extensively disclosed in the patent literature, for example EP 1106627 A1, EP0615980A2, WO2006056541A1, WO2011003772A1, CN1823077A, CN1659175A and the like.
  • a characteristic disadvantage of the phosphono compounds in practical applications is that the air oxygen barrier effect is remarkable when the polymerization is initiated, so that the cured coating containing the surface is dry. ) The effect is not good.
  • phosphono compounds are often used in combination with hydroxyketone photoinitiators to achieve balanced surface and through Curing curing.
  • the acylphosphine oxide compound may contain a single or a plurality of acylphosphine oxide [ie, -P(O)-C(O)- units] photoinitiating reactive functional groups, and the general structure ( I ) thereof is:
  • X is oxygen or sulfur
  • n and m each independently may have a value of 1 or 2.
  • R 1 is an unsubstituted straight or branched alkyl group having 1 to 18 carbon atoms (labeled C 1 -C 18 ) or containing 2 to 18 carbon atoms (labeled C 2 ) -C 18 , the same alkenyl group; or a linear or branched alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, which has one or more substituents.
  • R 1 is -OR 10 base
  • R 1 is -CO 2 H , -CO 2 R 10 , -CONR 10 R 11 , -CO-ethylene-, -CO-phenyl- (wherein the phenyl group may contain one or more C 1 -C 8 alkanes Or a C 1 -C 8 alkoxy group or a C 1 -C 8 alkylthio group or a chlorine atom), or -CO-CR 10 R 11 R 12 ;
  • R 1 is phenyl-C 1 -C 4 -alkyl, phenyl, naphthyl, biphenyl, C 5 -C 12 cycloalkyl, or a five or six membered heterocyclic ring containing an oxygen or sulfur or nitrogen atom
  • substituents may each contain one or more C 1 -C 8 alkyl or C 1 -C 8 alkoxy or C 1 -C 8 alkylthio or chlorine atom or -NR 10 R 11 substituent;
  • R 3 has the same definition as R 1 ;
  • acylphosphine oxides conforming to the general structure ( I ) include, but are not limited to, the following structures:
  • the aromatic hydroxy ketone compound may contain one or more photoinitiating hydroxy ketone functional groups, characterized in that the hydroxy ketone structure and other substituents exhibit an unusual meta relationship on the aromatic ring, and the general structure thereof ( II ) is:
  • p is an integer between 1 and 2000, preferably, p is an integer between 1 and 20; more preferably, p is an integer between 1 and 6; When the value is much larger than 20, it represents a p-repolymerized structure ( II );
  • R 6 and R 7 are each independently a phenyl group, a linear or branched C 1 -C 12 alkyl group, and the alkyl group may contain a phenyl or naphthyl or biphenyl substituted by one to five R 10 or OR 10 or halogen, or the alkyl group may be interrupted by one or more non-continuous oxygen or sulfur or nitrogen atoms;
  • R 6 and R 7 It is also possible to form a ring structure of 5 to 10 yuan.
  • R 8 is hydrogen or a group conforming to the definition of R 10 , preferably R 8 is hydrogen, C 1 -C 6 alkyl, or a silane group having a total number of carbon atoms of C 3 -C 12 , the silane-based carbon chain may be One to four discontinuous oxygen or sulfur or nitrogen atoms are interrupted;
  • R 9 is a p-valent linking unit corresponding to the definition of R 1 above; preferably, when p is 1 , R 9 is OH , Cl , SH , NH 2 , OR 10 , SR 10 , NHR 10 , NR 10 R 11 , or a quaternary ammonium salt cation form ( R 10 R 11 R 12 N + ); when p is greater than or equal to 2, R 9 is N , NR 10 , SO 2 , P(O)O 3 , PO 3 , or R 9 (H) p is correspondingly a p-alcohol, a p-mercaptan, a p-phenol, a p-carboxylic acid, a p-acid chloride, a p-amine, a p-ary amide, or a p-membered isocyanate. When p is 2, R 9 can also be a single key;
  • An example of a preferred p-acid chloride is an acid chloride structure corresponding to the above p-carboxylic acid example
  • R 9 (H) p may be p-member 1,2-diol, p-member 1,2-thiol, p-member 1,2-amino alcohol, or p-member 1,2-N-substituted amine a base alcohol; when R 9 (H) p takes these structures, the p-membered meta-substituted aromatic hydroxy ketone compound having the general structure ( II ) is preferably via a corresponding monomer compound [i.e., p has a value of 1, R 9 is a structure obtained by a classical epoxy ring-opening reaction of OH, SH, NH 2 , or NHR 10 compound ( II )] and a suitable p-epoxy compound. Examples of preferred p-epoxy compounds are:
  • Z is hydrogen or CH 2 R 9 ;
  • meta-substituted aromatic hydroxy ketone compounds conforming to the general structure ( II ) include, but are not limited to, the following structures:
  • the general structure ( III ) of the Hydroxyphenylbenzotriazole UV absorber having red-shifted light absorption characteristics is:
  • R 13 and R ' 13 are each independently hydrogen or halogen; and R 14 and R ' 14 are independently of each other, halogen, -CF 3 , -NO 2 , -CN , -COR 20 , -CO 2 R 20 , -CONHR 20 , -CONR 20 R 21 , -POR 20 R 21 , -NR 20 -COR 21 , -OSR 20 , -O 2 SR 20 , or C 1 -C 12 polyfluoro substituted alkyl;
  • R 20 and R 21 are each independently hydrogen, a linear or branched C 1 -C 24 alkyl group, a linear or branched C 2 -C 24 alkenyl group, a C 5 -C 24 -containing cycloalkyl group, a C 7 -C 15 -containing phenylalkyl group, or a phenyl group, which may have from 1 to 4 C 1 -C 4 alkyl or alkoxy substituents on the phenyl ring;
  • R 20 And the chain of R 21 may be interrupted by not more than 6 discontinuous oxygen or sulfur or nitrogen atoms, or may contain no more than 4 OH, NH 2 , substituted NH 2 , SH , NCO , or ester groups;
  • R 15 is the same as R 20 or R 21 ; when R 15 is a C 7 -C 15 -containing phenylalkyl group, or a phenyl group, the phenylalkyl group or the phenyl group may have 1 to 4 benzene rings a C 1 -C 4 alkyl or alkoxy substituent, in which case R 14 can be hydrogen;
  • R 16 and R ' 16 are independent of each other and are the same as R 20 or R 21 ;
  • r takes a value of 1 or 2
  • q takes a value of 0 , 1 or 2 ;
  • R 17 is R 20 , -OR 20 , -NR 20 R 21 , -PO(OR 20 ) 2 , -OSi(R 20 ) 3 , or -OCO-R 20 ;
  • Q is a divalent linking unit which is a C 1 -C 24 alkyl group or a C 6 -C 24 substituted aryl group; the chain may be no more than 6 non-continuous oxygen or sulfur or nitrogen atoms Intermittent
  • Examples of preferred hydroxybenzotriazole-like compounds conforming to the general structure ( III ) include, but are not limited to, the following structures:
  • the present invention discloses a novel photoinitiator compounding mixture system characterized by comprising at least one acylphosphine oxide compound represented by the general structure ( I ) and at least one aromatic compound represented by the general structure ( II ) Hydroxyketone compound.
  • the weight percentage of the acylphosphine oxide represented by the general formula ( I ) may be from 0.5% to 99.5, based on 100% by weight of the unit parts.
  • the change between %, correspondingly, the weight percentage of the aromatic hydroxyketone compound represented by the general structure ( II ) may vary from 99.5% to 0.5%.
  • the invention also discloses a mixture curable by radiation (ultraviolet or visible light or equivalent light source), the mixture being characterized by containing at least one polymerizable ethylenically unsaturated compound and a novel definition of claim ( 1 ) Acylphosphine oxide / aromatic hydroxy ketone complex photoinitiator system.
  • the acylphosphine oxide/aromatic hydroxyketone compound photoinitiator as defined in claim ( 1 ) may be used in an amount of from 0.01 to 20 parts per 100 parts by weight based on the total weight of such an ethylenically unsaturated compound. 0.5 to 10 servings.
  • the invention also discloses a novel mixture system curable by radiation (ultraviolet or visible light or equivalent light source), the system characterized by comprising at least one photoinitiator mixture as defined in claim ( 1 ), at least one A hydroxybenzotriazole-based light absorbing agent compound of the general structure ( III ), and at least one polymerizable ethylenically unsaturated compound.
  • the photocured mixture system was prepared in the following percentage by weight (100 parts in total), and the mixture was stirred or dissolved and sprayed on an aluminum plate (about 20 Micron) with high pressure mercury lamp (400 W/cm) ) initiate polymerization for radiation from the source.
  • the acylphosphine oxide photoinitiator and meta-substituted hydroxyketone initiator used in the examples are characterized by a structure after each case.
  • the curing efficiency was judged by the finger pressing method (that is, the thumb nail pressing film repeatedly wiped the coating without breaking) to confirm the completion of photocuring.
  • Embodiment 6 UV disc ink
  • Example 7 Light absorber containing UV ink
  • the photoinitiator mixture of the above examples all achieved sufficient curing of the system, exhibiting excellent photopolymerization initiating activity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention a trait à un nouveau système photoinitiateur constitué d'une combinaison d'hydroxyle cétones aromatiques et d'oxydes de phosphoryle et à un système contenant une insaturation oléfinique qui est durcissable par rayonnement lumineux (rayonnement ultraviolet ou lumière visible ou source lumineuse équivalente) et formulé à partir d'un tel système photoinitiateur et d'un photoabsorbeur approprié doté de la caractéristique d'absorption de la lumière à décalage vers le rouge, tel qu'un hydroxyle benzotriazole.
PCT/CN2012/083322 2011-10-26 2012-10-22 Nouveau mélange photoinitiateur composé d'une hydroxyle cétone aromatique et d'un oxyde de phosphoryle et système composite doté de celui-ci et d'un photoabsorbeur WO2013060254A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110330434.4 2011-10-26
CN2011103304344A CN103073658A (zh) 2011-10-26 2011-10-26 新型芳香羟基酮和膦酰氧化物的光引发剂混合物及其与光吸收剂的复合体系

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2508454A (en) * 2012-07-24 2014-06-04 Lambson Ltd Photopolymerisation processes and novel compounds therefor
WO2018059561A1 (fr) * 2016-09-30 2018-04-05 Allnex Belgium S.A. Compositions durcissables par rayonnement présentant des propriétés anti-taches
US10919867B2 (en) 2015-07-07 2021-02-16 3M Innovative Properties Company Substituted benzotriazole phenols

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EP3019508B1 (fr) * 2013-07-08 2019-01-30 IGM Group B.V. Photo-initiateur d'oxyde bisacylphosphine liquide
CN107400144B (zh) * 2017-08-03 2020-04-14 深圳有为技术控股集团有限公司 酰基膦(氧)化合物及其制备方法和应用
CN109517432A (zh) * 2018-11-13 2019-03-26 长沙新宇高分子科技有限公司 一种含液态酰基膦氧化物的组合物及其应用
JP7432616B2 (ja) * 2018-12-07 2024-02-16 アンチン ライティング オプトエレクトロニクス テクノロジー カンパニー リミテッド アシルホスフィンオキシド化合物及びその調製方法
JP7455858B2 (ja) * 2019-11-11 2024-03-26 富士フイルム株式会社 活性エネルギー線硬化型インク及び画像記録方法
CN112485963A (zh) * 2020-11-27 2021-03-12 上海新阳半导体材料股份有限公司 一种KrF厚膜光刻胶添加剂及含其的光刻胶组合物
CN115612112B (zh) * 2021-07-16 2023-11-10 常州强力先端电子材料有限公司 有机磷类大分子类引发剂及其制备方法、光固化组合物

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CN102076426A (zh) * 2008-07-31 2011-05-25 世联株式会社 合成树脂成型品的装饰面结构体、其制造方法和汽车内装部件

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CN103601629B (zh) * 2010-11-12 2015-08-26 深圳市有为化学技术有限公司 对位或间位官能团化芳香酮类化合物、其制备方法及其光聚合引发剂

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CN1175583A (zh) * 1996-08-28 1998-03-11 希巴特殊化学控股公司 作为光引发剂的分子复合体化合物
CN101484515A (zh) * 2006-07-04 2009-07-15 西巴控股有限公司 用多相聚合技术制造的光引发剂的水基浓缩产品形式
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2508454A (en) * 2012-07-24 2014-06-04 Lambson Ltd Photopolymerisation processes and novel compounds therefor
US10919867B2 (en) 2015-07-07 2021-02-16 3M Innovative Properties Company Substituted benzotriazole phenols
WO2018059561A1 (fr) * 2016-09-30 2018-04-05 Allnex Belgium S.A. Compositions durcissables par rayonnement présentant des propriétés anti-taches
US11359110B2 (en) 2016-09-30 2022-06-14 Allnex Belgium S.A. Radiation curable compositions with anti-stain properties

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