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CN103073658A - Photoinitiator mixture of novel aromatic hydroxyl ketone and acylphosphine oxide, and composite system of photoinitiator mixture and photoabsorber - Google Patents

Photoinitiator mixture of novel aromatic hydroxyl ketone and acylphosphine oxide, and composite system of photoinitiator mixture and photoabsorber Download PDF

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CN103073658A
CN103073658A CN2011103304344A CN201110330434A CN103073658A CN 103073658 A CN103073658 A CN 103073658A CN 2011103304344 A CN2011103304344 A CN 2011103304344A CN 201110330434 A CN201110330434 A CN 201110330434A CN 103073658 A CN103073658 A CN 103073658A
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phenyl
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王智刚
张永波
王衍超
宋怀海
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SHENZHEN YOUWEI CHEMICAL TECHNOLOGY Co Ltd
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SHENZHEN YOUWEI CHEMICAL TECHNOLOGY Co Ltd
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Priority to PCT/CN2012/083322 priority patent/WO2013060254A1/en
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    • 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

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Abstract

The invention discloses a novel photoinitiator system compounded by using aromatic hydroxyl ketone and acylphosphine oxide compounds, and an alkene-containing unsaturated system which can be cured through light (ultraviolet light or visible light or equivalent light sources) irradiation. The alkene-containing unsaturated system is obtained by compounding the photoinitiator system and an appropriate hydroxybenzotriazole photoabsorber with a red-shift light absorption characteristic.

Description

The photoinitiator mixtures of novel aromatic hydroxyketone and phosphono oxide compound and with the compound system of light absorber
[technical field]
The present invention relates to optical radiation curing technology field; be particularly related to the novel photoinitiator system of some aromatic hydroxy group ketone and the composite composition of acylphosphine oxide, and such photoinitiator system and the suitable composite formation of hydroxybenzotriazole class light absorber with red shift light absorption characteristics can be via light (UV-light or visible light or equal lamp-house) hardening with radiation contain the unsaturated system of alkene.
[background technology]
The phosphono compounds is important light trigger, in patent documentation by quite abundant disclosure, EP1106627A1 for example, EP0615980A2, WO2006056541A1, WO2011003772A1, CN1823077A, CN1659175A etc.Its atmospheric oxygen inhibition effect was remarkable when the characteristic shortcoming that the phosphono compounds embodies in practical application was initiated polymerization, so that it is not good enough to contain its solidified coating surface drying (Surface Curing) effect.In view of this, the phosphono compounds usually with the composite use of the light-initiated machine of hydroxyl ketone, solidify (Through Curing) solidification effect with the surface drying that averages out and deep layer.
We have disclosed novel " a position substituted type " alcohol ketone photoinitiator of a class in the recent period in patent CN102060684, such hydroxyketone can directly for example Darocure 1173 or Irgacure 184 possess excellent light-initiated activity and economic competitiveness as the derivative preparation of raw material take traditional commercially available prod.
Having now found that, is the novel mixed light initiator system of excellent performance after the phosphono compounds that this class hydroxyacetone compounds and document are known is composite; Further find simultaneously, the novel photoinitiator system that forms like this and ultraviolet absorbers (for example US5977219, US6187845) thus--the hydroxybenzotriazole class ultraviolet absorbers that particularly has the red shift light absorption characteristics--can effectively overcome the strong photoabsorption of light absorber after further composite to be disturbed and has obtained unexpectedly the mixture that has satisfied solidification effect to containing the unsaturated system of alkene.
[summary of the invention]
Define following acylphosphine oxide, aromatic hydroxy group ketone compound, and three kinds of compound systems of benzotriazole compound:
Described acylphosphine oxide can contain the light-initiated active function groups of single or a plurality of acylphosphanes oxygen [namely-P (O)-C (O)-unit], and its formula (I) is:
Figure BSA00000599589000021
In this general formula (I), X is oxygen or sulphur, and n and m can value be 1 or 2 independently of one another.
When n=1, R 11-18 the carbon atom that contain that is unsubstituted straight or branched (is labeled as C 1-C 18) alkyl or contain 2-18 carbon atom and (be labeled as C 2-C 18, lower with) thiazolinyl; Or contain the alkyl that contains 1-18 carbon atom of one or more substituent straight or branched or contain the thiazolinyl of 2-18 carbon atom, these one or more substituting groups can be halogen atoms ,-NCO base ,-CN base, Oxyranyle, N-alkyl (C 1-C 8Alkyl) imide that replaces ,-OR 10Base ,-CO-R 10Base ,-CONR 10R 11Base ,-NR 10R 11Base ,-SiR 10R 11R 12Base ,-OSiR 10R 11R 12Base ,-NR-CO-R 10Base ,-NR-CO-OR 10Base ,-NR-COR 10R 11Base ,-SR 10Base ,-SO 2R 10Base ,-SO 2-OR 10Base ,-SO 2-NR 10R 11Base ,-PO-OR 10R 11Base ,-PO-R 10R 11Base ,-COOR 10Base ,-OC (O) R 10Base ,-CH=CH-CO-OR 10Base, or-C (C 1-C 4Alkyl)=C (C 1-C 4Alkyl)-CO-OR 10Here R 10, R 11, R 12Hydrogen independently of one another, C 1-C 18Alkyl, the C that is interrupted for one or more discontinuity oxygen or sulphur or nitrogen-atoms 2-C 18Base contains the substituting group of one or more vinyl alcohol units, C 3-C 12Cyclic alkyl, 2-furyl, tetrahydrofuran base, phenyl-C 1-C 4-alkylidene group, phenyl-C 1-C 4-thiazolinyl contains the C of halogen or cyclohexyl or cyclopentyl or tetrahydrofuran base or furyl 1-C 6Alkyl, C 2-C 18Thiazolinyl, phenyl, unsubstituted naphthyl or xenyl contain one to five C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8The phenyl or naphthyl of alkylthio or halogenic substituent or xenyl; R 10, R 11, or R 12One or more hydrogen atoms can also be replaced by fluorine atom;
Or R 1Be-OR 10Base;
Or R 1By-CO-,-COO-,-OCO-,-OCOO-,-CO-NR 10-,-NR 10-CO-,-NR 10-CO-NR 10-,-NR 10-COO-,-COO-C 1-C 18-alkylidene group ,-COS-C 1-C 18-alkylidene group ,-SO 2-,-SO 2-O-,-SO 2-NR10-,-(CH 3) 2Si-[OSi (CH 3) 2] m-(m=1-6 here), phenyl-C 1-C 4-alkylidene group-,-C 6H 4-, naphthalene nucleus, cyclohexyl biphenyl, C 5-C 12Encircle, or contain the C of five or the hexa-member heterocycle interruption of oxygen or sulphur or nitrogen-atoms 1-C 18Alkyl or C 2-C 18Thiazolinyl;
Or R 1Trimethyl silicon based, Cl-(CH 3) 2Si-[OSi (CH 3) 2] s-, or-(CH 3) 3Si-[OSi (CH 3) 2] s-(s=1-6 here);
Or R 1Be-CO 2H ,-CO 2R 10,-CONR 10R 11,-CO-ethene-,-CO-phenyl-(the phenyl here can contain one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8Alkylthio or chlorine atom), or-CO-CR 10R 11R 12
Or R 1Phenyl-C 1-C 4-alkyl, phenyl, naphthyl, xenyl, C 5-C 12Cycloalkyl, or contain five or hexa-member heterocycle of oxygen or sulphur or nitrogen-atoms; Here these substituting groups all can contain one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8Alkylthio or chlorine atom or-NR 10R 11Substituting group;
When n=2, R 1One and above-mentioned R 1The divalent group that (when n=1) definition conforms to, or R 1Be-CH 2CH=CHCH 2-,-CH 2-C-acetylene bond-C-CH 2-,-CH 2CH 2-C 6H 4-CH 2CH 2-,-CH 2CH 2O-C 6H 4-OCH 2CH 2-,-CH 2-CO 2-Y-OCO-CH 2-, or-C 6H 3R 4-T-C 6H 3R 5-; Here T is a singly-bound, CH 2, C (CH 3) 2, CH 2CH 2, O, or S; R 4And R 5Hydrogen independently of one another, C 1-C 8Alkyl, or C 1-C 8Alkoxyl group; Y is C 1-C 18Alkylidene group or the divalence connected body that is formed by one or more vinyl alcohol repeating units;
R 2The C of straight or branched 1-C 18Alkyl or C 2-C 18Thiazolinyl, or contain the C of one or more halogenic substituent 1-C 18Alkyl or C 2-C 18Thiazolinyl, or-OR 10,-COR 10,-CO 2R 10,-CH=CH-CO 2R 10,-C (C 1-C 4Alkyl)=C (C 1-C 4Alkyl)-CO-OR 10,-NR 10-CO-R 11,-CO-NR 10R 11,-CH=CH-Ph-,-C (C 1-C 4Alkyl)=C (C 1-C 4Alkyl)-and Ph-, C 3-C 12Cycloalkyl, phenyl-C 1-C 4Alkyl, phenyl, naphthyl, anthryl, xenyl contains five or hexa-member heterocycle of oxygen or sulphur or nitrogen-atoms, or contains one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8The phenyl of alkylthio or chlorine replacing group, naphthyl, anthryl, xenyl contains five or hexa-member heterocycle of oxygen or sulphur or nitrogen-atoms;
R 3Definition and R 1Identical;
The acylphosphine oxide example that preferably meets formula (I) is including, but not limited to following structure:
Figure BSA00000599589000041
Described aromatic hydroxy group ketone compound can contain the hydroxyketone functional group of one or more light-initiated activity, it is characterized in that hydroxyketone structure on the aromatic ring and other substituting group present unusual between position (meta) relation, its formula (II) is:
Figure BSA00000599589000042
In this general formula (II), the p value is 1 to 2000 integer, and preferred, the p value is 1 to 20 integer; Preferred, the p value is 1 to 6 integer; When the p value much larger than 20 the time, it represents the structure (II) of a p reunion mould assembly; R 6And R 7Phenyl independently of one another, the C of straight or branched 1-C 12Alkyl, this alkyl can contain by one to five R 10Or OR 10Or the halogen phenyl or naphthyl or the xenyl that replace, or this alkyl can be interrupted by one or more discontinuity oxygen or sulphur or nitrogen-atoms; R 6And R 7Also can form one 5 to 10 yuan ring texture.Preferred example is R 6=R 7=CH 3, or R 6And R 7Form one 6 yuan rings (being cyclohexyl);
R 8Be hydrogen or meet R 10The group of definition, preferably R 8Hydrogen, C 1-C 6Alkyl, or carbon atoms adds up to C 3-C 12Silylation, this silylation carbochain can be interrupted by one to four discontinuity oxygen or sulphur or nitrogen-atoms;
R 9One and above-mentioned R 1The p valency connective element that definition conforms to; Preferably, when the p value is 1, R 9OH, Cl, SH, NH 2, OR 10, SR 10, NHR 10, NR 10R 11, or quaternary ammonium salt cationic form (R 10R 11R 12N +); When the p value more than or equal to 2 the time, R 9N, NR 10, SO 2, P (O) O 3, PO 3, or R 9(H) pCorrespondingly be a p unit alcohol, p unit mercaptan, p unit phenol, p unit carboxylic acid, p unit acyl chlorides, p unit amine, p unit acid amides, or p unit isocyanic ester.When the p value is 2, R 9It also can be a singly-bound;
Preferred p unit's alcohol or p unit's mercaptan or p unit phenol example are:
Figure BSA00000599589000051
The first carboxylic acid example of preferred p is:
Figure BSA00000599589000061
The example of the first acyl chlorides of preferred p is the corresponding acyl chlorides structure of above-mentioned p unit's carboxylic acid example;
The example of preferred p unit's amine or p unit acid amides is:
Figure BSA00000599589000062
The example of the first isocyanic ester of preferred p is:
Figure BSA00000599589000071
Preferably, R 9(H) pCan be p unit 1,2-glycol, p unit 1,2-mercaptan, p unit 1,2-amido alcohol, or p unit 1,2-N-substituted amido alcohol; Work as R 9(H) pWhen getting these structures, have that a position substituted type aromatic hydroxy group ketone compound [is that the p value is 1, R via corresponding monomeric compound preferably between the p unit of formula (II) 9OH, SH, NH 2, or NHR 10The time compound (II)] and the structure that obtains via the epoxy addition reaction of classics of suitable p unit epoxy compounds.The example of the first epoxy compounds of preferred p is:
Figure BSA00000599589000081
Z is hydrogen or CH 2R 9
Preferably meet formula (II) between the example of position substituted type aromatic hydroxy group ketone compound including, but not limited to following structure:
Figure BSA00000599589000091
Described formula (III) with hydroxybenzotriazole class ultraviolet absorbers (Hydroxyphenylbenzotriazole UV absorber) of red shift (Red-shifted) light absorption characteristics is:
Figure BSA00000599589000101
In (a-b-c) of this general formula (III) three structures, R 13And R ' 13Hydrogen or halogen independently of one another; , R 14And R ' 14Independent of each other is halogen ,-CF 3,-NO 2,-CN ,-COR 20,-CO 2R 20,-CONHR 20,-CONR 20R 21,-POR 20R 21,-NR 20-COR 21,-OSR 20,-O 2SR 20, or C 1-C 12The polyfluoro substituted alkyl;
R 20And R 21Hydrogen independently of one another, the C of straight or branched 1-C 24Alkyl, the C of straight or branched 2-C 24Thiazolinyl contains C 5-C 24Cycloalkyl, contain C 7-C 15Phenylalkyl, or phenyl can contain 1-4 C on the phenyl ring of this phenylalkyl or phenyl 1-C 4Alkyl or alkoxy substituted; R 20And R 21Chain can be interrupted by being no more than 6 discontinuity oxygen or sulphur or nitrogen-atoms, also can contain and be no more than 4 OH, NH 2, replace NH 2, SH, NCO, or ester group;
R 15Definition and R 20Or R 21Identical; Work as R 15To contain C 7-C 15Phenylalkyl, or phenyl can contain 1-4 C on the phenyl ring of this phenylalkyl or phenyl 1-C 4Alkyl or alkoxy substituted, this moment R 14Can be hydrogen;
R 16And R ' 16The independent of each other and R of definition 20Or R 21Identical;
R value 1 or 2; The q value is 0,1 or 2;
R 17R 20,-OR 20,-NR 20R 21,-PO (OR 20) 2,-OSi (R 20) 3, or-OCO-R 20
Q is a divalence connective element, and it is for containing C 1-C 24Alkyl or C 6-C 24The aryl of replacement; Its chain can be interrupted by being no more than 6 discontinuity oxygen or sulphur or nitrogen-atoms;
Preferably meet the example of hydroxybenzotriazole class compounds of formula (III) including, but not limited to following structure:
Figure BSA00000599589000111
The application's core summary of the invention and claim are as follows:
1。The present invention discloses the composite mixture system of a kind of novel photoinitiator, and the feature of this system is to comprise the aromatic hydroxy group ketone compound shown in the acylphosphine oxide shown at least a formula (I) and at least a formula (II).
2。In the composite photoinitiator mixtures system of claim (1) definition; take every unit part weight as 100%; wherein the weight percent of the acylphosphine oxide shown in the formula (I) can change between 0.5% to 99.5%; accordingly, the weight percent of the aromatic hydroxy group ketone compound shown in the formula (II) can change between 99.5% to 0.5%.
3。The present invention disclose simultaneously a kind of can be via the mixture of light (ultraviolet or visible light or equal lamp-house) radiation curing, the feature of this mixture is to contain at least a polymerisable novel acylphosphanes oxygen that contains the definition of unsaturated allyl compound and claim (1)/composite photoinitiator system of aromatic hydroxy group ketone.With so total restatement of unsaturated allyl compound that contains of per 100 parts of weight, the usage quantity of the acylphosphanes oxygen of claim (1) definition/composite light trigger of aromatic hydroxy group ketone can change preferred 0.5 to 10 part between 0.01 to 20 part.
4。The present invention disclose simultaneously a kind of novel can be via the mixture system of light (ultraviolet or visible light or equal lamp-house) radiation curing, the feature of this system is the photoinitiator mixtures that comprises at least a claim (1) definition, the hydroxybenzotriazole class light absorber compound that at least a formula (III) is described, and at least a polymerisable unsaturated allyl compound that contains.
5。In claim (4) but the definition light (ultraviolet or visible light or equal lamp-house) radiation curing mixture system in, with its per 100 parts of weighing scales, the content of the hydroxybenzotriazole compounds light absorber that formula (III) is described can change between 0.1 to 10 part, preferably, can between 0.5 to 5 part, change; And the photoinitiator levels of claim (1) definition can change between 0.1 to 20 part, and is preferred, can change between 1 to 10 part.
[embodiment]
The below illustrate above-mentioned mixed light initiator system and with the practical application of light absorber compound system in containing the unsaturated system Light Curing of alkene.
By following weight percent (amounting to 100 parts) preparation photocuring mixture system, with being sprayed on (approximately 20 microns) on the aluminium sheet after this mixture dispersed with stirring or the dissolving, take high voltage mercury lamp (400W/cm) as the radiation of light source initiated polymerization.Acylphosphine oxide light trigger and a position substituted type hydroxyketone initiator that embodiment uses have all been indicated structure after each example.Curing efficiency is finished with finger-press method (being that repeatedly wiping coating of thumb nail press mold is not damaged) judgement photocuring.
Embodiment one: UV white woodwork coating
77.2 part PEA, 5.9 parts of HDDA, 2.9 parts of TMPTA, 2.5 parts of acylphosphanes oxygen light triggers, 1.5 parts of alcohol ketone photoinitiators, 10 parts of TiO 2
Figure BSA00000599589000131
Embodiment two: UV floor dull surface lacquer
14.78 part high gloss UP (VP LS2100); 14.78 part Tromox R KB6; 7.39 part Banc-Fixe N, 1666,2.95 parts of TPGDA of 1.18 parts of Lancowax HM; add again 14.78 parts of high gloss UP (VP LS2100) after below the mixed grinding to 10 micron; 5.91 part Gasil EBN, 35.47 parts of TPGDA, 0.06 part of BYK 300; 1 part of acylphosphanes oxygen light trigger, 1.7 parts of alcohol ketone photoinitiators.
Embodiment three: the UV vehicle paint base
55.17 part aliphatics PUA (VP LS 2258), 1.65 parts of EB168,10.98 parts of POEA, 10.98 parts of talcum powder, 10.98 parts of clays, 5.49 parts of Heucophos ZPA, 1.38 parts of TiO 2, 0.08 part of auxiliary agent B ayferrox 303T, 2.46 parts of alcohol ketone photoinitiators, 0.83 part of acylphosphanes oxygen light trigger.
Figure BSA00000599589000133
Embodiment four: the UV powder coating
62.7 part UPE, 12.8 parts of vinyl ether resins, 20.0 parts of TiO 2, 1.5 parts of flow agents, 2.0 parts of acylphosphanes oxygen light triggers, 1.0 parts of alcohol ketone photoinitiators.
Embodiment five: the UV ater Paint for Wood
75.2 part water-based PUA dispersion, 16.2 parts of 75%TiO 2Pigment, 3.3 parts of auxiliary agents, 1.3 parts of deionized waters, 2.0 parts of acylphosphanes oxygen photoinitiator b APO (50% water dispersion), 2.0 parts of alcohol ketone photoinitiators.
Figure BSA00000599589000142
Embodiment six: UV CD printing ink
20 parts of PEA (EB525), 20 parts of EB1710,15 parts of EO-TMPTA, 10 parts of TPGDA, 25 parts of TiO 2, 2.5 parts of acylphosphanes oxygen light triggers, 2.5 parts of alcohol ketone photoinitiators, 3.0 parts of SiO 2, 2.0 parts of defoamer Airex 900.
Figure BSA00000599589000143
Embodiment seven: contain light absorber UV printing ink
19.4 part urethane acrylate (Sartomer CN999); 19.4 part ethoxylated bisphenol A diacrylate (Sartomer SR601); 31 parts of Sartomer SR492; 24 parts of Sartomer SR355; 0.32 part acylphosphanes oxygen light trigger; 2.60 part alcohol ketone photoinitiator, 3.28 parts of hydroxybenzotriazole light absorbers (note: the irradiation of this sample carries out under nitrogen protection atmosphere).
Figure BSA00000599589000151
Above-described embodiment photoinitiator mixtures has all been finished system and has fully been solidified, and has represented good photopolymerization initiating activity.

Claims (5)

1. composite mixture system of novel photoinitiator, the feature of this system is to comprise the aromatic hydroxy group ketone compound shown in the acylphosphine oxide shown at least a formula (I) and at least a formula (II).
Described acylphosphine oxide can contain the light-initiated active function groups of single or a plurality of acylphosphanes oxygen [namely-P (O)-C (O)-unit], and its formula (I) is:
Figure FSA00000599588900011
In this general formula (I), X is oxygen or sulphur, and n and m can value be 1 or 2 independently of one another.
When n=1, R 11-18 the carbon atom that contain that is unsubstituted straight or branched (is labeled as C 1-C 18) alkyl or contain 2-18 carbon atom and (be labeled as C 2-C 18, lower with) thiazolinyl; Or contain the alkyl that contains 1-18 carbon atom of one or more substituent straight or branched or contain the thiazolinyl of 2-18 carbon atom, these one or more substituting groups can be halogen atoms ,-NCO base ,-CN base, Oxyranyle, N-alkyl (C 1-C 8Alkyl) imide that replaces ,-OR 10Base ,-CO-R 10Base ,-CONR 10R 11Base ,-NR 10R 11Base ,-SiR 10R 11R 12Base ,-OSiR 10R 11R 12Base ,-NR-CO-R 10Base ,-NR-CO-OR 10Base ,-NR-COR 10R 11Base ,-SR 10Base ,-SO 2R 10Base ,-SO 2-OR 10Base ,-SO 2-NR 10R 11Base ,-PO-OR 10R 11Base ,-PO-R 10R 11Base ,-COOR 10Base ,-OC (O) R 10Base ,-CH=CH-CO-OR 10Base, or-C (C 1-C 4Alkyl)=C (C 1-C 4Alkyl)-CO-OR 10Here R 10, R 11, R 12Hydrogen independently of one another, C 1-C 18Alkyl, the C that is interrupted for one or more discontinuity oxygen or sulphur or nitrogen-atoms 2-C 18Base contains the substituting group of one or more vinyl alcohol units, C 3-C 12Cyclic alkyl, 2-furyl, tetrahydrofuran base, phenyl-C 1-C 4-alkylidene group, phenyl-C 1-C 4-thiazolinyl contains the C of halogen or cyclohexyl or cyclopentyl or tetrahydrofuran base or furyl 1-C 6Alkyl, C 2-C 18Thiazolinyl, phenyl, unsubstituted naphthyl or xenyl contain one to five C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8The phenyl or naphthyl of alkylthio or halogenic substituent or xenyl; R 10, R 11, or R 12One or more hydrogen atoms can also be replaced by fluorine atom;
Or R 1Be-OR 10Base;
Or R 1By-CO-,-COO-,-OCO-,-OCOO-,-CO-NR 10-,-NR 10-CO-,-NR 10-CO-NR 10-,-NR 10-COO-,-COO-C 1-C 18-alkylidene group ,-COS-C 1-C 18-alkylidene group ,-SO 2-,-SO 2-O-,-SO 2-NR10-,-(CH 3) 2Si-[OSi (CH 3) 2] m-(m=1-6 here), phenyl-C 1-C 4-alkylidene group-,-C 6H 4-, naphthalene nucleus, cyclohexyl biphenyl, C 5-C 12Encircle, or contain the C of five or the hexa-member heterocycle interruption of oxygen or sulphur or nitrogen-atoms 1-C 18Alkyl or C 2-C 18Thiazolinyl;
Or R 1Trimethyl silicon based, Cl-(CH 3) 2Si-[OSi (CH 3) 2] s-, or-(CH 3) 3Si-[OSi (CH 3) 2] s-(s=1-6 here);
Or R 1Be-CO 2H ,-CO 2R 10,-CONR 10R 11,-CO-ethene-,-CO-phenyl-(the phenyl here can contain one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8Alkylthio or chlorine atom), or-CO-CR 10R 11R 12
Or R 1Phenyl-C 1-C 4-alkyl, phenyl, naphthyl, xenyl, C 5-C 12Cycloalkyl, or contain five or hexa-member heterocycle of oxygen or sulphur or nitrogen-atoms; Here these substituting groups all can contain one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8Alkylthio or chlorine atom or-NR 10R 11Substituting group;
When n=2, R 1One and above-mentioned R 1The divalent group that (when n=1) definition conforms to, or R 1Be-CH 2CH=CHCH 2-,-CH 2-C-acetylene bond-C-CH 2-,-CH 2CH 2-C 6H 4-CH 2CH 2-,-CH 2CH 2O-C 6H 4-OCH 2CH 2-,-CH 2-CO 2-Y-OCO-CH 2-, or-C 6H 3R 4-T-C 6H 3R 5-; Here T is a singly-bound, CH 2, C (CH 3) 2, CH 2CH 2, O, or S; R 4And R 5Hydrogen independently of one another, C 1-C 8Alkyl, or C 1-C 8Alkoxyl group; Y is C 1-C 18Alkylidene group or the divalence connected body that is formed by one or more vinyl alcohol repeating units;
R 2The C of straight or branched 1-C 18Alkyl or C 2-C 18Thiazolinyl, or contain the C of one or more halogenic substituent 1-C 18Alkyl or C 2-C 18Thiazolinyl, or-OR 10,-COR 10,-CO 2R 10,-CH=CH-CO 2R 10,-C (C 1-C 4Alkyl)=C (C 1-C 4Alkyl)-CO-OR 10,-NR 10-CO-R 11,-CO-NR 10R 11,-CH=CH-Ph-,-C (C 1-C 4Alkyl)=C (C 1-C 4Alkyl)-and Ph-, C 3-C 12Cycloalkyl, phenyl-C 1-C 4Alkyl, phenyl, naphthyl, anthryl, xenyl contains five or hexa-member heterocycle of oxygen or sulphur or nitrogen-atoms, or contains one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group or C 1-C 8The phenyl of alkylthio or chlorine replacing group, naphthyl, anthryl, xenyl contains five or hexa-member heterocycle of oxygen or sulphur or nitrogen-atoms;
R 3Definition and R 1Identical;
The acylphosphine oxide example that preferably meets formula (I) is including, but not limited to following structure:
Figure FSA00000599588900031
Described aromatic hydroxy group ketone compound can contain the hydroxyketone functional group of one or more light-initiated activity, it is characterized in that hydroxyketone structure on the aromatic ring and other substituting group present unusual between position (meta) relation, its formula (II) is:
Figure FSA00000599588900032
In this general formula (II), the p value is 1 to 2000 integer, and preferred, the p value is 1 to 20 integer; Preferred, the p value is 1 to 6 integer; When the p value much larger than 20 the time, it represents the structure (II) of a p reunion mould assembly; R 6And R 7Phenyl independently of one another, the C of straight or branched 1-C 12Alkyl, this alkyl can contain by one to five R 10Or OR 10Or the halogen phenyl or naphthyl or the xenyl that replace, or this alkyl can be interrupted by one or more discontinuity oxygen or sulphur or nitrogen-atoms; R 6And R 7Also can form one 5 to 10 yuan ring texture.Preferred example is R 6=R 7=CH 3, or R 6And R 7Form one 6 yuan rings (being cyclohexyl);
R 8Be hydrogen or meet R 10The group of definition, preferably R 8Hydrogen, C 1-C 6Alkyl, or carbon atoms adds up to C 3-C 12Silylation, this silylation carbochain can be interrupted by one to four discontinuity oxygen or sulphur or nitrogen-atoms;
R 9One and above-mentioned R 1The p valency connective element that definition conforms to; Preferably, when the p value is 1, R 9OH, Cl, SH, NH 2, OR 10, SR 10, NHR 10, NR 10R 11, or quaternary ammonium salt cationic form (R 10R 11R 12N +); When the p value more than or equal to 2 the time, R 9N, NR 10, SO 2, P (O) O 3, PO 3, or R 9(H) pCorrespondingly be a p unit alcohol, p unit mercaptan, p unit phenol, p unit carboxylic acid, p unit acyl chlorides, p unit amine, p unit acid amides, or p unit isocyanic ester.When the p value is 2, R 9It also can be a singly-bound;
Preferred p unit's alcohol or p unit's mercaptan or p unit phenol example are:
The first carboxylic acid example of preferred p is:
Figure FSA00000599588900051
The example of the first acyl chlorides of preferred p is the corresponding acyl chlorides structure of above-mentioned p unit's carboxylic acid example;
The example of preferred p unit's amine or p unit acid amides is:
Figure FSA00000599588900052
The example of the first isocyanic ester of preferred p is:
Preferably, R 9(H) pCan be p unit 1,2-glycol, p unit 1,2-mercaptan, p unit 1,2-amido alcohol, or p unit 1,2-N-substituted amido alcohol; Work as R 9(H) pWhen getting these structures, have that a position substituted type aromatic hydroxy group ketone compound [is that the p value is 1, R via corresponding monomeric compound preferably between the p unit of formula (II) 9OH, SH, NH 2, or NHR 10The time compound (II)] and the structure that obtains via the epoxy addition reaction of classics of suitable p unit epoxy compounds.The example of the first epoxy compounds of preferred p is:
Figure FSA00000599588900071
Z is hydrogen or CH 2R 9
Preferably meet formula (II) between the example of position substituted type aromatic hydroxy group ketone compound including, but not limited to following structure:
Figure FSA00000599588900081
2. in the composite photoinitiator mixtures system of claim (1) definition; take every unit part weight as 100%; wherein the weight percent of the acylphosphine oxide shown in the formula (I) can change between 0.5% to 99.5%; accordingly, the weight percent of the aromatic hydroxy group ketone compound shown in the formula (II) can change between 99.5% to 0.5%.
The present invention disclose simultaneously a kind of can be via the mixture of light (ultraviolet or visible light or equal lamp-house) radiation curing, the feature of this mixture is to contain at least a polymerisable novel acylphosphanes oxygen that contains the definition of unsaturated allyl compound and claim (1)/composite photoinitiator system of aromatic hydroxy group ketone.With so total restatement of alkene unsaturated materials that contains of per 100 parts of weight, the usage quantity of the acylphosphanes oxygen of claim (1) definition/composite light trigger of aromatic hydroxy group ketone can change preferred 0.5 to 10 part between 0.01 to 20 part.
The present invention disclose simultaneously a kind of novel can be via the mixture system of light (ultraviolet or visible light or equal lamp-house) radiation curing, the feature of this system is the photoinitiator mixtures that comprises at least a claim (1) definition, the hydroxybenzotriazole class light absorber compound that at least a formula (III) is described, and at least a polymerisable unsaturated allyl compound that contains.
The formula (III) of described hydroxybenzotriazole class light absorber is:
Figure FSA00000599588900091
In (a-b-c) of this general formula (III) three structures, R 13And R ' 13Hydrogen or halogen independently of one another; , R 14And R ' 14Independent of each other is halogen ,-CF 3,-NO 2,-CN ,-COR 20,-CO 2R 20,-CONHR 20,-CONR 20R 21,-POR 20R 21,-NR 20-COR 21,-OSR 20,-O 2SR 20, or C 1-C 12The polyfluoro substituted alkyl;
R 20And R 21Hydrogen independently of one another, the C of straight or branched 1-C 24Alkyl, the C of straight or branched 2-C 24Thiazolinyl contains C 5-C 24Cycloalkyl, contain C 7-C 15Phenylalkyl, or phenyl can contain 1-4 C on the phenyl ring of this phenylalkyl or phenyl 1-C 4Alkyl or alkoxy substituted; R 20And R 21Chain can be interrupted by being no more than 6 discontinuity oxygen or sulphur or nitrogen-atoms, also can contain and be no more than 4 OH, NH 2, replace NH 2, SH, NCO, or ester group;
R 15Definition and R 20Or R 21Identical; Work as R 15To contain C 7-C 15Phenylalkyl, or phenyl can contain 1-4 C on the phenyl ring of this phenylalkyl or phenyl 1-C 4Alkyl or alkoxy substituted, this moment R 14Can be hydrogen;
R 16And R ' 16The independent of each other and R of definition 20Or R 21Identical;
R value 1 or 2; The q value is 0,1 or 2;
R 17R 20,-OR 20,-NR 20R 21,-PO (OR 20) 2,-OSi (R 20) 3, or-OCO-R 20
Q is a divalence connective element, and it is for containing C 1-C 24Alkyl or C 6-C 24The aryl of replacement; Its chain can be interrupted by being no more than 6 discontinuity oxygen or sulphur or nitrogen-atoms;
Preferably meet the example of hydroxybenzotriazole class compounds of formula (III) including, but not limited to following structure:
Figure FSA00000599588900111
Claim (4) definition can the mixture system via light (ultraviolet or visible light or equal lamp-house) radiation curing in, with its per 100 parts of weighing scales, the content of the hydroxybenzotriazole compounds light absorber that formula (III) is described can change between 0.1 to 10 part, preferably, can between 0.5 to 5 part, change; And the photoinitiator levels of claim (1) definition can change between 0.1 to 20 part, and is preferred, can change between 1 to 10 part.
CN2011103304344A 2011-10-26 2011-10-26 Photoinitiator mixture of novel aromatic hydroxyl ketone and acylphosphine oxide, and composite system of photoinitiator mixture and photoabsorber Pending CN103073658A (en)

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