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WO2013091521A1 - Oxyde d'acylphosphine à groupes multifonctionnels ou polymérisé dérivé d'un système cyclique aroylique - Google Patents

Oxyde d'acylphosphine à groupes multifonctionnels ou polymérisé dérivé d'un système cyclique aroylique Download PDF

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Publication number
WO2013091521A1
WO2013091521A1 PCT/CN2012/086789 CN2012086789W WO2013091521A1 WO 2013091521 A1 WO2013091521 A1 WO 2013091521A1 CN 2012086789 W CN2012086789 W CN 2012086789W WO 2013091521 A1 WO2013091521 A1 WO 2013091521A1
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Prior art keywords
group
acid
atoms
alkyl
compound
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PCT/CN2012/086789
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English (en)
Chinese (zh)
Inventor
王智刚
张永波
宋怀海
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SHENZHEN UV-CHEMTECH Co Ltd
Shenzhen Uv Chemtech Co Ltd
Original Assignee
SHENZHEN UV-CHEMTECH Co Ltd
Shenzhen Uv Chemtech Co Ltd
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Priority claimed from CN201110432953.1A external-priority patent/CN103172770B/zh
Application filed by SHENZHEN UV-CHEMTECH Co Ltd, Shenzhen Uv Chemtech Co Ltd filed Critical SHENZHEN UV-CHEMTECH Co Ltd
Publication of WO2013091521A1 publication Critical patent/WO2013091521A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C07F9/28—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)
    • 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
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters

Definitions

  • the invention relates to the technical field of radiation polymerization curing new materials, in particular to a novel aromatic aryl ring-based polyfunctional or polymeric acylphosphine oxide represented by the general formula (I-III), and a chemical preparation method thereof.
  • a photoinitiator for radiation polymerization curing of an ethylenically unsaturated compound system and a radiation polymerization cured composite system containing such a compound.
  • Photoinitiators are one of the key composite components in the field of radiation (ultraviolet or visible or electron beam or ray) curing.
  • the research literature on photoinitiator structures and manufacturing processes has been extensively disclosed, with particularly important industries.
  • Application values are, for example, the hydroxyketone type photoinitiator 1173 and the acylphosphine oxide type photoinitiators TPO, TPO-L, and BAPO.
  • the aroyl precursor of the group is coupled with a suitable phosphorus-containing precursor to prepare the acylphosphine oxide type compound; and there is no direct aroyl ring in the presence of the acylphosphine oxide ⁇ )- ⁇ ( ⁇ ) core photoactive functional group Report on structural transformation
  • ⁇ takes a value of 1 or 2 or 3, preferably, ⁇ takes a value of 1 or 2;
  • X oxygen or sulfur.
  • p, r, and s are integers describing the functionality, where p is an integer greater than or equal to 1, and r and s are integers greater than or equal to 2.
  • Ri , R 2 , and R 3 are each independently hydrogen, halogen, a branched or straight chain containing one or more substituents having 1 to 24 carbon atoms (labeled as C r c 24 , the same below), containing Or an alkyl group not containing a c 3 -c 12 ring structure, or a c 2 -c 24 branched or straight chain containing one or more substituents, with or without a C 3 -C 12 ring structure
  • the alkenyl group is either an unsubstituted or substituted 1-4 ring aryl (phenyl, naphthyl, anthracenyl, or biphenylyl) or heteroaryl group having a C 6 -C 24 carbon number. !
  • the segments of ⁇ , R 2 , and , independently of each other, may be interrupted by 1-6 non-contiguous oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms.
  • a ring structure can also be formed between R 2 and any two.
  • the segments of ⁇ , R 2 , and their independently bonded benzene rings may also be inserted independently of one another by oxygen, sulfur, or a nitrogen, silicon, or phosphorus containing a C r C 4 alkyl or a house oxygen substituent.
  • R 4 is a branched or straight chain having one or more substituents having a carbon number of C r C 24 , an alkyl or alkoxy group having or not containing a C 3 -C 12 ring structure, or a C 2 -C 24 containing one or more substituents Branched or linear, alkenyl group with or without a C 3 -C 12 ring structure.
  • the segment can be interrupted by 1-6 non-contiguous oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms.
  • R 5 is hydrogen, OH, C r is the number of carbon atoms with one or more substituents containing a linear or branched chain of C 24, alkyl group with or without structure-based c 3 -c 12 cycloalkyl or satisfy such conditions An alkoxy or alkylindenyl or silane group, an unsubstituted or substituted 1-4 aryl group (phenyl, naphthyl, anthryl, or biphenyl) or heteroaryl having a C 6 -C 24 carbon number A phenolic or thiophenol group that satisfies such conditions.
  • the segment of R 5 may be interrupted by 1-6 non-contiguous oxygen atoms, halogen atoms, nitrogen atoms, silicon atoms, sulfur atoms, double bonds, or triple bonds.
  • R 6 is hydrogen, a branched or straight chain having one or more substituents of C r C 24 , an alkyl group having or not containing a C 3 -C 12 ring structure or an alkoxy group satisfying such conditions Or an alkyl or silane group, an unsubstituted or substituted 1-4 aryl group (phenyl, naphthyl, anthracenyl, or biphenyl) or a heteroaryl group having a C 6 -C 24 carbon number or A phenolic or thiophenol group satisfying such conditions.
  • the segment of R 6 may be interrupted by 1-6 non-contiguous oxygen atoms, halogen atoms, nitrogen atoms, silicon atoms, sulfur atoms, double bonds, or triple bonds.
  • R 8 , R 9 , and R 1Q have the same definitions as R 2 , and .
  • Ru is defined the same as R 6 .
  • Q is a p-valent group.
  • Q is the form of a CR 13 R 14 (R 15 :) monovalent substituent, where 3 and 4 are each independently hydrogen or C r C 6 alkyl, preferably, Q is CH 2 (R 15 );
  • p takes an integer greater than or equal to 3
  • Q is a p-valent linking group satisfying the R 15 condition.
  • R 15 is an unsubstituted straight or branched alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms; or a straight or branched chain having one or more substituents
  • An alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms, these one or more substituents may be a halogen atom, -NCO group, -CN group, oxirane group, N- Alkyl (C r C 8 alkyl) substituted imide, -OR 16 group, -CO- 16 group, -CON 16 Ri group, -N 16 Ri group, -Si 16 Ri Ri8 group, -OSi 16 Ri Ri8 group, - NR-CO-R 16 group, -NR-CO-OR 16 group, -NR-COR 16 R 17 group, -SR 16 group, -S0 2 R 16 group, - S0 2 -OR 16 group , -S0
  • R 16, R 17, R 18 independently of one another are hydrogen, C r C 2 4 alkyl group, or a plurality of discontinuous oxygen or nitrogen atom or a sulfur interrupted C 2 -C 24 group, or containing a Substituents for a plurality of vinyl alcohol units, 3 - 24 cyclic alkyl, 2-furyl, tetrahydrofuranyl, phenyl-C r C 4 -alkylene, phenyl-C r C 4 -alkenyl, containing Halogen or cyclohexyl or cyclopentyl or tetrahydrofuranyl or furanyl c r c 6 alkyl, c 2 -c 18 alkenyl, phenyl, unsubstituted naphthyl or biphenyl, containing one to five C r C a phenyl or naphthyl or biphenyl group of 8 alkyl or ( ⁇ -0 8 alkoxy or c r
  • ⁇ ⁇ 2 is a metal cation or ammonium salt cation independently of each other;
  • Ri 5 is -CO-, -COO-, -OCO-, -OCOO-, -CO-N ie- , -NR 16 -CO-, - N i 6 -CO-N i6- , -N jg- COO-, -COO-d-ds - alkylene, -COS-d-ds - alkylene, - S0 2 -, -S0 2 -0-, -S0 2 -N i 6 -, -SiR 16 R 17 -, -SiOR 16 R 17 -, -SiOR 16 OR 17 -, -PO- 0R 16 -, - ⁇ -( ⁇ -, -P0-(0M!)(0M 2 ), -P0-R 16 -, -phenyl-C C4-alkylene-, -C 6 H 4 - , naphthalene ring, biphenyl ring, C 5
  • R 15 is phenyl-dC 4 -alkyl, phenyl, naphthyl, biphenyl, 5 12 cycloalkyl, or a five- or six-membered heterocyclic ring containing an oxygen or sulfur or nitrogen atom; May contain one or more ( ⁇ -0 8 alkyl or ( ⁇ - ⁇ alkoxy or C r C 8 alkylthio or chlorine atom or -NR 16 R 17 substituent;
  • R 7 is a divalent linking group in the form of CR 13 R 14 , and preferably, R 7 is CH 2 .
  • R 12 is a divalent linking group satisfying the R 15 condition.
  • Compounds of formula (I) include, but are not limited to, the following exemplary structures:
  • Compounds of formula (III) include, but are not limited to, the following exemplary structures: Surprisingly, in some known monomeric acylphosphine oxides, even the strongly electron-withdrawing acylphosphine-C(0)-P(0)-functional group significantly deactivates the aroyl ring system it contains, The application has now found that direct haloalkylation of its aroyl ring system can still be achieved under suitable conditions, thereby achieving a series of general formulas.
  • the preparation of the compound of the formula (I) has the following general formula: Starting from the monomeric acylphosphine oxide compound 4 known in the literature, Friedel-Crafts alkylation reaction is carried out under the action of acid and formaldehyde to obtain a chloromethylated intermediate ⁇ .
  • the acid here may be a Lewis acid such as aluminum trichloride, zinc dichloride, magnesium dichloride, ferric chloride, indium trichloride, and a rare earth metal in the form of LaHal 3 (La represents a rare earth element, and Hal represents a halogen
  • the atomic halide or form is a sulfonate of La(OTf) 3 or the like, or an inorganic or organic protic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, sulfonic acid.
  • a chemical functional group conversion reaction well known to those skilled in the art is that ⁇ can react with or undergo a substitution reaction; and (may undergo an esterification reaction with 3, and an addition reaction with ⁇ and 5, and ⁇ ⁇ Oxidation ring-opening reaction occurs.
  • C can also be derivatized into a suitable polymerizable unsaturated ester or unsaturated olefin or chlorosilane unit containing an acylphosphine oxide structure, and then a polymer type can be prepared by radical or hydrolysis polymerization ( I) Structure.
  • C and an unsaturated acid chloride or an unsaturated carboxylic acid are esterified to obtain a structure, which can be polymerized in the presence of a radical initiator to obtain a polymer type (I) target molecule.
  • the preparation reaction of the general formula ( ⁇ ) compound is as follows: Starting from the bisacylphosphine oxide monomer compound known in the literature, the Friedel-Crafts alkylation reaction is sequentially carried out on the two aromatic rings by the action of acid and formaldehyde.
  • the acid may be a Lewis acid such as aluminum trichloride, zinc dichloride, magnesium dichloride, ferric chloride, indium trichloride, and a rare earth metal in the form of LaHal 3
  • La represents a rare earth element
  • Hal represents a halide of a halogen atom or a sulfonate of the form La(OTf) 3
  • an inorganic or organic protic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, sulfonic acid .
  • a key molecular block type intermediate G (wherein Z is Cl, OH, SH, NH 2, etc.) is obtained by Friedel-Crafts haloalkylation, and G and 7-6 are polymerized to give structure (11).
  • the preparation of the compound of the formula an) is as follows: Starting from the acylphosphine oxide monomer compound H known in the literature, two successive Friedel-Crafts alkylation reactions on the same aromatic ring under the action of acid and formaldehyde are key. Molecular block type intermediates / (wherein Z is Cl, OH, SH, NH 2 , etc.), / and - 6 are polymerized to give structure (11).
  • the acid here may be a Lewis acid such as aluminum trichloride, zinc dichloride, magnesium dichloride, ferric chloride, indium trichloride, and a rare earth metal in the form of LaHal 3 (La represents a rare earth element, and Hal represents a single atom.
  • the compound or form is a sulfonate of La(OTf) 3 or the like, or an inorganic or organic protic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, sulfonic acid.
  • Such a system comprises at least one polymerizable ethylenically unsaturated component and comprises at least one compound of the formula ( ⁇ - ⁇ ) as one of a photoinitiator or a photoinitiator component.
  • a suitable amount of the compound of the formula ( ⁇ - ⁇ ) contained is 0.01 to 25 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight based on the total amount of the ethylenically unsaturated component in the system.
  • Suitable radiation curable systems disclosed in the present application comprise a polymerizable ethylenically unsaturated component which is a compound or mixture which can be crosslinked by free radical polymerization of the double bond.
  • the ethylenically unsaturated component can be It is a monomer, oligomer or prepolymer, or a mixture or copolymer thereof.
  • Such a suitable radiation curing system may also contain inorganic or organic fillers and/or colorants (such as pigments or dyes, etc.) added as needed, as well as other additives (eg, ultraviolet absorbers, light stabilizers, flame retardants, Any component such as a leveling agent, or an antifoaming agent, and a solvent.
  • inorganic or organic fillers and/or colorants such as pigments or dyes, etc.
  • other additives eg, ultraviolet absorbers, light stabilizers, flame retardants, Any component such as a leveling agent, or an antifoaming agent, and a solvent.
  • Suitable free-radically polymerizable monomers are, for example, ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated diolefins, styrene, maleic anhydride, fumaric anhydride, Vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth)acrylic acid, (meth)acrylic acid derivatives such as (meth)acrylamide, vinyl halide, vinylidene halide, and the like.
  • ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated diolefins, styrene, maleic anhydride, fumaric anhydride, Vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth)acrylic acid, (meth)acryl
  • Suitable prepolymers and oligomers include, but are not limited to, (meth)acryloyl functional (meth)acrylic copolymers, urethane (meth) acrylates, polyester (meth) acrylates, Unsaturated polyester, polyether (meth) acrylate, siloxane (meth) acrylate, epoxy (meth) acrylate, etc.
  • Suitable number average molecular weights thereof may vary, for example, from 500 to 10,000, preferably from 500 to 5,000.
  • the compounds disclosed herein have outstanding structural novelty, simple and efficient preparation methods, mild reaction conditions, and high efficiency and environmental friendliness of photoinitiated activity.
  • Embodiment 1 The gist of the present invention will be further described below in conjunction with specific embodiments.
  • Embodiment 1
  • Example 1 compound The 214 gram of the Example 1 compound and 120 gram of potassium carbonate were placed in a 5 liter 1/1 volume ratio of tetrahydrofuran/water solvent, and the reaction was stirred at room temperature and was monitored by TLC until the disappearance of the starting material (about 2 hours). The solvent was removed, and the residue was combined with a 1/1 volume ratio of dichloromethane/water. The organic phase was separated and the aqueous phase was extracted twice with dichloromethane. The organic phase was combined, dried over magnesium sulfate, filtered and evaporated. The residue was subjected to EtOAc EtOAc m. HRMS high resolution mass spectrum: calculated C 23 H 24 0 3 P ( M + H): 379.1463; Found: 379.1471.
  • Example 6 Under a nitrogen atmosphere, 76 mg of the compound of Example 4 was placed in 4 ml of toluene, and after adding 7 mg of AIBN, the mixture was stirred at 60 ° C for 2 hours. The target product of the pale yellow powder was quantitatively obtained after the solvent was removed under reduced pressure.
  • Example 6
  • Example 8 With reference to the reaction conditions of Example 1, a reaction of 420 mg of BAP0 in 5 ml of chloroform and 150 mg of paraformaldehyde and 280 mg of anhydrous aluminum trichloride was carried out to obtain 137 mg of a yellow solid product by silica gel column chromatography. HRMS high resolution mass spectrum: calculated C 53 H 55 0 6 P 2 (M + H): 849.3474; Found: 849.3479.
  • Example 8 Example 8:
  • Example 10 Under nitrogen protection, 78 mg of the compound of Example III and 98 mg of perfluorooctanoyl chloride were placed in 15 ml of dry dichloroethane, and after cooling to zero, 35 ⁇ l of fresh distillation was sequentially added thereto with stirring. Triethylamine and 5 mg of DMAP (dimethylaminopyridine) catalyst. After the reaction solution was slowly returned to room temperature, the reaction was further stirred for 3 hours. The reaction mixture was concentrated to give 147 mg (yield of pale-yellow liquid).
  • Example 16 A photoradiation test sample was prepared according to the following weight percentages: 28 parts: epoxy acrylate; 35 parts: poly Ester acrylate; 5 parts: hexanediol diacrylate; 5 parts: pentaerythritol triacrylate; 23 parts: titanium dioxide pigment; 4 parts: Selected acylphosphine oxide photoinitiator compound of the present invention.
  • a part of the above mixture was sufficiently ground and sprayed on a white substrate to form a coating of about 20 ⁇ m under air.
  • the 250 W high-pressure mercury lamp was used as a light source to irradiate at a distance of 12 cm from the sample.
  • a finger-scratch method determines the complete cure of the coating.
  • Example 17 A photoradiation test sample was prepared in accordance with the following weight percentages: 19.0 parts: urethane acrylate (Sartomer CN999); 19.0 parts: ethoxy bisphenol A diacrylate (Sartomer SR601); 31 parts: Sartomer SR492; 24 parts: Sartomer SR355; 2.60 parts: Hydroxyketone photoinitiator Irgacure 184; 2.28 parts: Hydroxybenzotriazole type light absorber UV-320; 2.12 parts: Selected Inventive Example acylphosphine oxide photoinitiator compound; A part of the above mixture was sufficiently ground and sprayed on a white substrate to form a coating of about 20 ⁇ m under air.
  • the 250 W high-pressure mercury lamp was used as a light source to irradiate at a distance of 12 cm from the sample.
  • a finger-scratch method determines the complete cure of the coating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention concerne un oxyde d'acylphosphine à groupes multifonctionnels ou polymérisé dérivé d'un composé à système cyclique aroylique, son procédé de préparation, et un matériau composite durcissant le contenant. L'oxyde d'acylphosphine à groupes multifonctionnels ou polymérisé est utilisé comme photo-initiateur pour l'irradiation, la polymérisation et le durcissement d'un système de composé à insaturation oléfinique.
PCT/CN2012/086789 2011-12-20 2012-12-17 Oxyde d'acylphosphine à groupes multifonctionnels ou polymérisé dérivé d'un système cyclique aroylique Ceased WO2013091521A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110432953.1 2011-12-20
CN201110432953.1A CN103172770B (zh) 2011-12-20 经由芳酰环系衍生的多官能团或聚合型酰基膦氧化合物

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018143912A1 (fr) * 2017-01-31 2018-08-09 Hewlett-Packard Development Company, L.P. Dispersions réactives de polyuréthane
WO2018143923A1 (fr) * 2017-01-31 2018-08-09 Hewlett-Packard Development Company, L.P. Synergistes amines
WO2019243039A1 (fr) 2018-06-19 2019-12-26 Agfa Nv Amorceurs à base d'oxyde d'acyle phosphine
US10590264B2 (en) 2016-09-07 2020-03-17 Fujifilm Corporation Photopolymerization initiator, polymerizable composition, ink jet recording method, and acylphosphine oxide compound

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1304940A (zh) * 1999-12-08 2001-07-25 西巴特殊化学品控股有限公司 新型氧化膦光引发体系及浅色可固化组合物
CN101878191A (zh) * 2007-11-29 2010-11-03 爱克发印艺公司 可共聚光引发剂的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304940A (zh) * 1999-12-08 2001-07-25 西巴特殊化学品控股有限公司 新型氧化膦光引发体系及浅色可固化组合物
CN101878191A (zh) * 2007-11-29 2010-11-03 爱克发印艺公司 可共聚光引发剂的制备方法

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KUNIO IKEMURA ET AL.: "A review of the development of radical photopolymerization initiators used for designing light-curing dental adhesives and resin composites", DENTAL MATERIALS JOURNAL, vol. 295, no. 5, 2010, pages 481 - 501 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10590264B2 (en) 2016-09-07 2020-03-17 Fujifilm Corporation Photopolymerization initiator, polymerizable composition, ink jet recording method, and acylphosphine oxide compound
WO2018143912A1 (fr) * 2017-01-31 2018-08-09 Hewlett-Packard Development Company, L.P. Dispersions réactives de polyuréthane
WO2018143923A1 (fr) * 2017-01-31 2018-08-09 Hewlett-Packard Development Company, L.P. Synergistes amines
US10907057B2 (en) 2017-01-31 2021-02-02 Hewlett-Packard Development Company, L.P. Reactive polyurethane dispersions
WO2019243039A1 (fr) 2018-06-19 2019-12-26 Agfa Nv Amorceurs à base d'oxyde d'acyle phosphine
US12325723B2 (en) 2018-06-19 2025-06-10 Agfa Nv Acylphosphineoxide initiators

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