WO2003068785A1 - Derives de mono- et bisacylphosphine - Google Patents

Derives de mono- et bisacylphosphine Download PDF

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WO2003068785A1
WO2003068785A1 PCT/EP2003/001070 EP0301070W WO03068785A1 WO 2003068785 A1 WO2003068785 A1 WO 2003068785A1 EP 0301070 W EP0301070 W EP 0301070W WO 03068785 A1 WO03068785 A1 WO 03068785A1
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het
alkyl
acyl
bisacylphosphine
groups
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PCT/EP2003/001070
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Ralf Noe
Erich Beck
Matthias Maase
Andreas Henne
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Basf Aktiengesellschaft
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    • 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
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/36—Amides thereof
    • 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
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
    • C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (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
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/44—Amides thereof
    • C07F9/4403—Amides thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/443—Amides of acids containing the structure -C(=Y)-P(=X)(XR)-N or NC-(P(=X)(XR)-N )
    • 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
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
    • 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
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4

Definitions

  • the invention relates to special mono- and bisacylphosphine derivatives, processes for their preparation and their use as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.
  • Monoacylphosphine oxides are known as photoinitiators e.g. from EP-A 7508.
  • Bisacylphosphine oxides and their use as photoinitiators are known, for example, from EP-A 184 085.
  • WO 00/17212 describes organophosphorus compounds in which acylphosphine oxides are connected via a spacer group to an N-acryloyl radical.
  • WO 99/52515 describes their use as pharmaceuticals.
  • this spacer group can also contain an ether or a keto group.
  • EP-A 413 657 describes mono- and diacylphosphine oxides, in which a substituted or unsubsti- Acylphosphinoxidiser about tutechnischs phenylene, xylylene, cyclohexyl or Ci-C ⁇ alkylene with a different, for example, acrylic substituted Phosphinoxidein- is connected integral.
  • EP-A 670 323 discloses dimeric bisacylphosphine oxides in which the phosphine oxide structures are connected to one another by spacers. The spacer is always bound to a phosphorus atom with a carbon atom.
  • EP-A 62 839 describes acylphosphine compounds which carry acryloxy substituents in an associated ammonium ion.
  • DE-A 195 24 812 describes radiation-curable (meth) acrylates in which (meth) acrylic groups are linked to aceto or benzophenone units.
  • JP 8-151404 describes (meth) acrylates which are connected via a spacer group to aceto-, benzo- or phosphinoxophenones.
  • EP-A 281 941 describes co-reactive photoinitiators, RG-A-IN, in which a functional reactive group RG, e.g. Vinyl or acrylic, but also OH, NH, NCO etc. via a spacer A with a photoinitiator basic structure IN, e.g. Aceto-, benzo- or acylphosphine oxophenone, and their use in photopolymerization.
  • RG functional reactive group
  • IN e.g. Aceto-, benzo- or acylphosphine oxophenone
  • EP-A 281 941 does not name acylphosphine oxides for which this concept is applicable, nor does it disclose a process for their preparation.
  • WO 00/24527 describes the use of photoinitiators e.g. of the RG-A-IN type, wherein
  • A is a spacer group or single bond
  • RG is at least one functional, ethylenically unsaturated group
  • Radical sites are generated on the substrate, for example by discharge or radiation, the organic photoinitiators with at least one ethylenically unsaturated group are applied to the substrate and are allowed to react there with the radical sites generated, the substrate thus precoated with at least one ethylenically unsaturated monomer or Oligomers are coated and cured by means of UV / VIS radiation and a metal, semimetal or metal oxide is deposited from the gas phase in the presence of UV light.
  • WO 00/24527 gives no technical teaching for the production of such photoinitiators of the phosphine oxide type and gives no indication of the reduction in migration when using such photoinitiators in radiation-curable mixtures.
  • JP-A 08-167172 mentions vinyl pivaloylphenylphosphinate and methyl (meth) acryloylphenylphosphinate as photopolymerization initiators in radiation-curable adhesives.
  • JP-A 08-167172 does not recognize the lower tendency of such phosphine oxides to migrate and gives no indication of their production.
  • the object of the present invention was to develop build-in photoinitiators which have a lower tendency to migrate than the conventional photoinitiators of the phosphine oxide type, but have a similar reactivity.
  • R 1 , R 2 Ci - Ci 8 ⁇ alkyl optionally by one or more
  • Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C 2 - cis alkyl, C 2 - Ci ⁇ -alkenyl, C 6 - C ⁇ -aryl, C 5 - C ⁇ 2 cycloalkyl or a five to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, where the radicals mentioned can each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, R 2 also optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-alkoxy or R 1 - (C Y) -,
  • R 3 is hydrogen, Ci to C 4 alkyl, S0 3 H, phenyl or acetyl,
  • R 4 is hydrogen, C 1 to C -alkyl, COOR 3 or C 6 -C 8 -aryl or arylsulfonyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • X is a spacer substituted n times with groups RG,
  • RG is a radical or cationically polymerizable group or a group which can interact with the polymer being formed and
  • n is a natural number from 1 to 10 and
  • X can also be unsubstituted or halogen, Ci-Cs-alkyl, C 2 -Cs-alkenyl, carboxy, carboxy-Ci-Cs-alkyl, -C-C 2 o ⁇ acyl, Ci-Cs-alkoxy, C 6 - -C aryl, hydroxyl, hydroxy-substituted Ci-C ⁇ -alkyl or n-fold substituted by groups RG C 6 -C ⁇ 2 -arylene, C 3 -C ⁇ -cycloalkylene, C ⁇ -C 2f j -alkylene or by one or more Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -0 (C0) 0-, - (NH) (CO) 0-, -0 ( CO) (NH) -, -0 (C0) - or -
  • Radically polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinyl aromatic groups, vinyl and vinylidene chloride groups, N-vinyl amides, vinyl pyrrolidones, vinyl lactams, vinyl esters, (meth) acrylic esters or acrylonitriles.
  • Cationically polymerizable groups are, for example, isobutylene units or vinyl ethers.
  • C 1 -C 8 alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, 2, 4, 4-trimethyl-5-pentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1,1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3, 3 -Tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-
  • Ci - Ci 8 alkoxy for example methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert. -Butyloxy, 6-hydroxy-l, 4-dioxo-hexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-l, 4, 7, 10-tetraoxo-
  • 35 dodecyl, 6-methoxy-l, 4-dioxohexyl, 9-methoxy-l, 4, 7-trioxononyl, 12-methoxy-l, 4,7, 10-tetraoxododecyl, 6-ethoxy-l, 4-dioxohexyl, 9 -Ethoxy-l, 4, 7-trioxononyl, 12-ethoxy-l, 4,7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl, 12-hydroxy-l, 5, 9-trioxooctyl, 16-hy droxy-1, 5,9, 13-tetraoxohexadecyl, 8-methoxy-l, 5-dioxooctyl,
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule it is not more than 5 in the rest, preferably not more than 4 and very particularly preferably not more than 3.
  • Substituted and unsubstituted imino groups can be, for example, imino, methyli ino, iso-propylimino, n-butylimino or tert-butylimino.
  • C 2 - cis alkenyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example vinyl, 1-propenyl, allyl, methallyl, 1, 1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl , Dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
  • Ce - -C aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Me- thylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert.
  • C 5 -C 2 -cycloalkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methoxycyclohexyl, diethylcyclohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
  • a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrylidyl, dimethylpyrylidyl Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert.
  • -Butylthiophenyl
  • Ci to C 4 alkyl for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert. -Butyl and
  • aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 6 -C 2 aryl or arylsulfonyl, for example phenyl, 2, 6-dinitrophenyl, 2, 4-dinitrophenyl, 2-nitrophenyl, 4-nitrophenyl, Formyl, acetyl, propionyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl.
  • radicals having one to three carbon atoms it is up to 3 substituents, preferably up to 2 and particularly preferably up to one.
  • radicals with four to six carbon atoms it is generally up to 4 substituents, preferably up to 3 and particularly preferably up to one.
  • radicals with more than seven carbon atoms it is generally up to 6 substituents, preferably up to 4 and particularly preferably up to two.
  • X can be, for example, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl- l, 3-propylene, 2, 2-dimethyl-l, 3-propylene, 2,2-dimethyl-l, 4-butylene, 1-oxa-l, 3-propylene, 1, 4-dioxa-l, 6-hexylene,
  • X can furthermore represent a spacer group, as is essentially described in WO 00/24527. Accordingly, X can be used for
  • Z 1 , Z 2 , and Z 3 each independently for a single bond, -0-, -S-, -N (R 8 ) -, - (CO) -, - (CO) O-, - ( CO) N (R 8 ) -, -O- (CO) -, -N (R 8 ) - (CO) - or -N (R 8 ) - (CO) 0-,
  • Ci - C alkylene C 3 - C ⁇ 2 cycloalkylene, phenylene, phenylene-Ci - C -alkylene or Ci - C -alkylene-phenylene-Ci - C 4 -alkylene and
  • a, b, c, d independently of one another represent the numbers 0 to 4.
  • R 8 is hydrogen, Ci to Cis-alkyl or phenyl.
  • Ci - C alkylene therein denotes linear or branched alkylene, e.g. Methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,1-dimethyl-1,2-ethylene or 1,2 -Dime- 1, 2-ethylene,
  • C 1 -C 2 -cycloalkylene for example cyclopropylene, cyclopentylene,
  • Cyclohexylene, cyclooctylene, cyclododecylene, Phenylene-Ci-C-alkylene stands for phenylene which is substituted in one position of the aromatic ring with Ci-C-alkylene, for example 1 ', 4-tolylene or 1', 1 '-dimethyl-1', 4-Toluy- len,
  • Ci - C -alkylene-phenylene-C ⁇ -C -alkylene stands for phenylene, which is substituted in two positions of the aromatic ring with Ci - C -alkylene, for example 2, 4-dimethylphenyl-l ', 1' '-en or 1 ', 1' -dimethyl-2, 4-dimethylphenyl-l ', 1 "' s.
  • Z 1 , Z 2 , Z 3 , a, b, c and d are as defined above.
  • RG means a residue of the formula
  • R 5 , R 6 , R 7 therein mean C 1 -C 4 -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 -C 3 -alkyl, Ci-Cia -Alkoxy, C 2 - cis-alkenyl, C 6 - -CC aryl, C 5 - C 2 cycloalkyl or a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms, the radicals mentioned in each case can be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • RG can, for example, vinyl, vinyloxy, 1-propen-1-yl, 1-propen-2-yl, 2-buten-2-yl, 3-methyl-2-buten-2-yl, 2-vinylphen-1 -yl, 3-vinylphen-l-yl, 3-vinylphen-l-yl, 2-phenylethen-l-yl, 2- (4-methoxyphenyl) ethen-1-yl, acrylic, methacrylic, crotonyl, acryloxy , Acrylamido, methacryloxy or crotonyloxy.
  • RG can be a group
  • R 9 each identically or differently hydrogen or -CC-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, seJ-butyl or tert. -Butyl, can be.
  • the groups X-RG n can furthermore be, for example,
  • Such XRG n can be, for example, 2-dimethylaminoethoxy, 2-aminoethoxy, l-aza-3-aminoprop-l-yl, 1,4-diaza-6-aminohexyl, 4-aza-l-oxa-6-aminohexyl, 4- Aza-l-oxa-6-hydroxyhexyl, l-aza-3-hydroxy-1- (2 'hydroxyethyl) propyl, piperazin-1-yl, 4-methyl-piperazine-l-yl or 2' -Piperazinoethoxy.
  • X can also be, for example
  • XRG n bears several RG groups, it can be, for example where Z 4 , Z 5 , Z 6 single bond, O, S, NH, NR 10 , CH 2 , CHR 10 , CR 10 2 , - (CO) -, - (CO) O-, - ( CO) N (R 10 ) -, -O- (CO) -, -N (R 10 ) - (CO) - or -N (R 10 ) - (CO) O-,
  • A, A 4 , A 5 single bond Ci - C 4 alkylene, C 3 - C 2 cycloalkylene, phenylene, phenylene-Ci - C 4 alkylene or Ci - C 4 alkylene-phenylene-C - C 4 alkylene .
  • e an integer between 0 and 20 and
  • R 10 each independently of one another hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 alkoxy, hydroxy, hydroxy C 1 -C 4 alkyl, carboxyl, C 1 -C 4 -acyl, carboxy C 1 -C 4 alkyl, C 6 -C ⁇ 2 aryl, -O-RG, -CH 2 OH or -CH 2 0-RG.
  • R 1 is preferably phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 2- 3- or 4-chlorophenyl, 2,6- or 2, 4-dichlorophenyl, 2,4,6-trichlorophenyl, 2- , 3- or 4-methylphenyl, 2,6- or 2, -dimethylphe- nyl, 2, 4, 6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2, 4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4 -tert.-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2, 4-dimethoxyphenyl, 2,6- or 2, 4-diethoxyphenyl, methylnaph- 5 thyl, 2, 6-dimethylphenyl, 2 , 4, 6-trimethylphenyl, 2, 6-dimeth
  • R 1 is particularly preferably phenyl, tolyl, ⁇ -naphthyl, ⁇ -naphthyl,
  • R 1 is very particularly preferably phenyl, 2-methylphenyl, 2-methoxyphenyl, 2-chlorophenyl, ⁇ -naphthyl, 2, 6-dichlorophenyl, 2,4, 6-trichlorophenyl, 2, 6-dimethylphenyl, 2 , 4, 6-trimethylphenyl, 2,6-diethylphenyl, 2, 6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2, 6-dimethylphenyl, 2, 4, 6-trimethylphenyl, 2, 6-dimethoxyphenyl, 2nd , 6-dense
  • R 1 is in particular phenyl, 2, 6-dichlorophenyl, 2, 4, 6-trichlorophenyl, 2, 6-dimethylphenyl, 2, 4, 6-trimethylphenyl or 2,6-dimethoxyphenyl.
  • R 2 is preferably 2, 4, 4-trimethylpentyl, benzyl, p-chlorobenzyl,
  • 40 iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert. -Butyloxy, 6-hydroxy-l, 4-dioxohexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-l, 4,7, 10-tetraoxododecyl, 6-methoxy-l, 4-dioxohexyl, 9 -Methoxy-l, 4, 7-trioxononyl, 12-methoxy-l, 4,7, 10-tetraoxododecyl, 6-ethoxy-l, 4-dioxohexyl, 9-ethoxy-l, 4, 7-trioxononyl,
  • R 2 is particularly preferably benzyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert.
  • R 2 is very particularly preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, 6-hydroxy-l, 4-dioxohexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-1, 4, 7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl, 12-hydroxy-1, 5, 9-trioxooctyl, 16-hydroxy- l, 5,9,13-tetraoxohexadecyl, 10-hydroxy-l, 6-dioxodecyl, 15-hydroxy-l, 6, 11-trioxopentadecyl, phenyl, xylyl, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, 2- , 3-
  • R 2 is in particular methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, phenyl, 4-diphenylyl, 2-, 3- or 4- Chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl or 2-, 3- or 4-ethoxyphenyl.
  • R 2 is specifically phenyl, methoxy or ethoxy.
  • Y is preferably 0, S or NR 3 .
  • Y is particularly preferably 0 or S and very particularly preferably 0.
  • Z is preferably 0, S, NR 3 or a free electron pair, particularly preferably 0, S or a free electron pair, very particularly preferably 0 or S and in particular 0.
  • R 3 is preferably hydrogen, methyl, tert. -Butyl, phenyl or S0 3 H, particularly preferably hydrogen, tert. -Butyl, phenyl or S0 3 H and very particularly preferably hydrogen, tert. -Butyl or phenyl.
  • R 4 is preferably hydrogen, methyl, phenyl, 2, 4-dinitrophenyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl, particularly preferably hydrogen, phenyl, 2, 4-dinitrophenyl or phenylsulfonyl, very particularly preferably hydrogen, 2, 4-dinitrophenyl or phenylsulfonyl and especially hydrogen or 2,4-dinitrophphenyl.
  • R 5 is preferably hydrogen, methoxy, methyl or ethyl.
  • R 5 is particularly preferably hydrogen or methyl.
  • R 5 is very particularly preferably hydrogen.
  • R 6 is preferably hydrogen, methoxy, phenyl, methyl or ethyl, particularly preferably hydrogen, phenyl or methyl and very particularly preferably hydrogen.
  • R 7 is preferably hydrogen, methoxy, phenyl, methyl or ethyl, particularly preferably hydrogen, phenyl or methyl and very particularly preferably hydrogen.
  • R 8 is preferably hydrogen, methyl, ethyl, n-butyl or phenyl, particularly preferably hydrogen or methyl and very particularly preferably hydrogen.
  • n is preferably from 1 to 10, particularly preferably from 1 to 5, very particularly preferably from 1 to 3 and in particular 1.
  • R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seic-butoxy, iso -Butoxy or tert-butoxy.
  • R 1 are ortho-substituted, for example 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
  • the present invention furthermore relates to a process for the preparation of acyl and bis-acylphosphine derivatives of the formula (I), in which a substance HX-RG n or ⁇ X-RG n with a compound of the formula (III),
  • FG a leaving group of the structure -F, -Cl, -I, -CN, -OCN, -SCN, -N + R 15 R 16 R 17 , -0 (C0) R 14 , -0 (CO) OR 14 , - 0 (C0) NR 14 , -N (C0) NR 14 , -0 (S0) C1, -0 (S0 2 ) C1, -0 (S0 2 ) R 14 , -0 (S0 2 ) OR 14 , -0 (C0) C1, -0 (NO) OR 14 , -SR 14 , -Br, - (NR 12 ) -NR 13 R 18 or
  • R 12 is hydrogen, Ci to C 4 alkyl, S0 3 H, phenyl or acetyl,
  • R 13 is hydrogen, Ci to C 4 alkyl, COOR 3 or C ⁇ -Cj-aryl or arylsulfonyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • R 14 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Ci ⁇ alkyl, optionally interrupted by one or more oxygen, nitrogen and / or sulfur atoms C 2 - cis alkyl, optionally by aryl, Alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted Ci - Cis-alkoxy, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C - Ci ⁇ -alkenyl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ⁇ , - C ⁇ 2 -aryl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted C 5 - C ⁇ 2 cycloalkyl
  • R 17 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-alkyl or optionally interrupted by one or more oxygen, nitrogen and / or sulfur atoms C 2 - Ci ⁇ -alkyl and
  • Rl8 is hydrogen or Ci to C alkyl
  • the present invention furthermore relates to dimeric acyl and bisacylphosphine oxides of the formula (II),
  • R 1 , R 2 , Y and Z have the meanings given above and R 1 ', R 2 ', Y 'and Z' have the same meanings as R 1 , R 2 , Y and Z, but can be different from these ,
  • X has the above meaning and Het 1 and Het 2 independently of one another mean 0, S or NR 9 .
  • the phosphine derivatives of the formula (III) can be prepared by a process in which a substance of the formula
  • R 1 , R 2 , Y and Z have the meaning given above and
  • X ' is hydrogen or a cation
  • Cations can be, for example, those as listed in EP-A 62 839, that is, equivalents of a cation of the 1st to 3rd main group of the periodic table with a molecular weight below 138 or ammonium ions derived from quaternary ammonium ions or triethylene diammonium ions.
  • Agents which convert the group -OX 'into the group -FG are known per se to the person skilled in the art. Examples include phosgene (C0C1 2 ), thionyl chloride (S0C1 2 ), sulfuryl chloride (S0 2 C1 2 ), phosphorus trichloride (PCl 3 ), phosphorus oxychloride (P0C1 3 ), phosphorus pentachloride (PC1 5 ), oxalyl chloride ((C0C1) 2 ), hydrogen chloride (HC1), chlorine gas (Cl 2 ), N-chlorine compounds such as N-chlorosuccinimide, alkali fluoride, cobalt (III) fluoride, halogen fluoride, antimony fluoride, molybdenum fluoride, hydrogen fluoride, hydrogen fluoride / pyridine mixtures, xenon fluoride and other noble gas compounds, gaseous fluorine, sulfur tetrafluoride
  • Examples of compounds of the formula H-Het x -X-Het 2 -H, or their anions, are polyethylene glycols with a molecular weight between 106 and 898, especially ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, poly-1, 2-propylene glycol with a molecular weight between 134 and 1178, 1, 3-propylene glycol, poly-1, 3-propylene glycol with a molecular weight between 134 and 1178, 1, 4- Butanediol, poly-THF with a molecular weight between 162 and 1458, 1, 6-hexanediol, 1, 8-0ctanediol, 1,10-decanediol, 1, 12-dodecanediol, 2-ethylhexan-l, 3-diol, 2 , 4-Diethyloc- tan-1, 3-diol, trimethylolpropane,
  • Polether and polyesterols with an average OH functionality of 2 to 10, which preferably have a molecular weight of 200 to 2000, are also conceivable.
  • R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seJc-butoxy, iso -Butoxy or tert-butoxy.
  • R 1 are ortho-substituted, for example 2-methylphenyl, 2, 6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethyl-1 -phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
  • R 1 ', R 2 ', X, Y ', Z', Het 1 and Het 2 are as defined above,
  • R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seic-butoxy, iso -Butoxy or tert-butoxy.
  • R 1 are ortho-substituted, for example 2-methylphenyl, 2, 6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethoxy-1, are also preferred -phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
  • reaction of (III) with H-Het 1 -X-Het 2 -H or the corresponding anions or the reaction of (III) with (IV) is carried out, for example, as follows:
  • the reaction with (III) is usually carried out in the presence of 0.9 to 1.5 molar equivalents of an acid scavenger, such as pyridine or a tertiary amine, e.g. Triethylamine, tributylamine, benzyldimethylaamine, dimethyla inopyridine etc., at temperatures between 0 ° C and 100 ° C, preferably between 10 ° C and 80 ° C, the substrate to be reacted, optionally dissolved in a suitable solvent, e.g.
  • an acid scavenger such as pyridine or a tertiary amine, e.g. Triethylamine, tributylamine, benzyldimethylaamine, dimethyla inopyridine etc.
  • (III) can also be used dissolved in a suitable solvent, e.g. the solvents mentioned. If necessary, stirring can be continued, for example 30 to 600 minutes, preferably 60 to 300 minutes, it being possible for the reaction temperature to be raised gradually.
  • the resulting reaction product can be further processed in raw or processed form. If further use in pure form is desired, the product can be purified, for example, by crystallization and solid / liquid separation or by distillation or rectification under reduced pressure.
  • the yields are usually over 75%, mostly over 80% and often over 90%.
  • the mono- and diacyl or dimeric phosphine derivatives described can be used as photoinitiators in photopolymerizable compositions, e.g. Coating agents, lacquers, printing inks, recording materials, aqueous solutions, dispersions and emulsions.
  • radicals R 'and R'' cannot tolerate functionalities which react with an acid chloride R 1 (C0) C1, such as, for example, hydroxyl or amino functions.
  • the functionalized phosphine derivatives according to the invention can be synthesized by reacting a reactive derivative of the formula (III) as described above.
  • R stands for any of the substitutions listed above and the numbers n for any of the numbers described above.
  • the gentle reaction makes it possible to obtain compounds with heteroatom substitution which are more soluble or compatible in various lacquer mixtures, are less migrable with several potential radical centers owing to the polarity of the chain or a higher molecular weight, or can also be incorporated in the polymer due to a copolymerizable structural unit.
  • acylphosphinic acid This can be converted to the derived hydroxyalkyl derivatives using various epoxides.
  • Both acylphosphinic acid, its anions and its hydroxyalkyl derivatives can be reacted with reactive substrates [e.g. B. isocyanates (monoisocyanates, diisocyanates, such as methane diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), both as 2,4- and 2,6-isomer, and mixtures thereof, isophorone diisocyanate (IPDI), both Mono- and diaducts, and polyisocyanates), acid chlorides, alkylene oxides, epichlorohydrin, etc.] can be functionalized.
  • isocyanates monoisocyanates, diisocyanates, such as methane diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), both as 2,4- and 2,6-isomer, and mixtures thereof, is
  • the isocyanate grouping still present in monoadducts can be used for further functionalization. Hydrolysis to photoinitiators with a primary amine functionality and thus Michael addition to the acrylate functionality of a radiation-curable resin (see e.g. EP-A 950 219) is possible. Acrylate-functionalized acylphosphine oxide photoinitiators are also available via this synthetic route.
  • the invention furthermore relates to compounds which can be obtained by reacting (I) or (IV), preferably by reacting (IV), with compounds containing reactive groups.
  • Reactive groups are those which are able to form a chemical bond with the group RG or -Het 2 "H of the compounds (I) or (IV).
  • These can be, for example, isocyanate, epoxy, anhydride, acid chloride, ester, acid, carbonate, aldehyde, ⁇ , ⁇ -unsaturated carbonyl, chloroalkyl, bromoalkyl, iodoalkyl or nitrile groups.
  • acid here means, for example, carboxylic acids or sulfonic acids, preferably carboxylic acids.
  • Compounds containing such reactive groups can be, for example, 1,6-hexamethylene diisocyanate (HDI), 2,4- and 2,6-toluenediisocyanate (TDI), 4,4'-methylenedi (phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI) , Bisphenol A mono- and diglycidyl ether, bisphenol B mono- and diglycidyl ether, bisphenol F mono- and diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) propane mono- and diglycidyl ether, maleic anhydride, phthalic anhydride, ⁇ -caprol ⁇ -caprolactam, vinyloxirane, epichlorohydrin and Adipic acid, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and the esters of these acids.
  • HDI 1,6-hexamethylene diisocyanate
  • TDI 2,4- and 2,6-to
  • R 11 for example 1,6-hexylene, 3, 5, 5-trimethyl-l, 3-cyclohexylene, 1-methyl-2, 4-phenyl, 1-methyl-2, 6-phenyl, 4, 4 '-diphenylmethy- len, 2, 4 '-diphenylmethylene or 2', 4-diphenylmethylene and
  • R 11 is hydrogen or methyl
  • R 2 ′ 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, isopropoxy, n-butoxy, seTc-butoxy, are so-butoxy or tert-butoxy.
  • R 1 is ortho-substituted, for example 2-methylphenyl, 2,6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethyl- 1-phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
  • the low migration of the compounds according to the invention is based on interactions of polar groups in the compounds with the radiation-curable or radiation-hardened mass. As a result of these interactions, the compounds according to the invention are more strongly bound in the polymer than is the case with the commercially available photoinitiators mentioned at the outset.
  • Polar groups that can interact are those that e.g. electrostatic interactions, dipole-dipole interactions, induction (Debye) interactions or hydrogen bonds.
  • hydroxyl, mono-, di- and unsubstituted amino, carboxylic acid, sulfonic acid, ammonium, carboxylate, sulfonate or amide groups preferably hydroxy, mono-, di- and unsubstituted amino, carboxylic acid -, Ammonium, carboxylate or sulfonate groups.
  • Reactive centers are those which are able to form a chemical bond in the radiation-curable composition with groups such as hydroxy, mono- and unsubstituted amino, carboxylic acid, sulfonic acid, carboxylate, sulfonate or amide groups.
  • reactive centers can be, for example, isocyanate, epoxy, anhydride, acid chloride, ester, acid, carbonate, aldehyde, ⁇ , ⁇ -unsaturated carbonyl, chloroalkyl, bromoalkyl, iodoalkyl or Be nitrile groups.
  • Isocyanate, epoxy, ester, acid, carbonate, aldehyde and ⁇ , ⁇ -unsaturated carbonyl groups are preferred.
  • Isocyanate, epoxy, ester and ⁇ , ⁇ -unsaturated carbonyl groups are particularly preferred.
  • Isocyanate, epoxy and ⁇ , ⁇ -unsaturated carbonyl groups are very particularly preferred.
  • the acyl and bisacylphosphine derivatives of the formula (IV) according to the invention can also be incorporated if the corresponding complementary groups which can react with the group -Het 2 -H, for example isocyanate, are present in the radiation-curable composition.
  • cc ⁇ -unsaturated carbonyl compounds, epoxies and the like.
  • the compounds of the formula (Va to c) according to the invention can be processed in radiation-curable compositions if the isocyanate or epoxy functions react with polar groups in the composition.
  • Both mechanisms cause the compounds according to the invention to be anchored in the radiation-curable composition and consequently to reduce migration.
  • acyl and bisacylphosphine derivatives of the formula (III) can also be reacted with compounds which contain a different photoinitiator basic structure and reactive groups, for example benzophenones, acetophenones, hydroxyacetophenones, phenylglyoxylic acids, phenylglyoxylic acid esters, anthraquinones or benzoins.
  • compounds which contain a different photoinitiator basic structure and reactive groups for example benzophenones, acetophenones, hydroxyacetophenones, phenylglyoxylic acids, phenylglyoxylic acid esters, anthraquinones or benzoins.
  • the photoinitiators according to the invention can of course also be used in a mixture with other photoinitiators.
  • These can be, for example, photoinitiators known to those skilled in the art, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London
  • mono- or bisacylphosphine oxides such as are described in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2.4 , 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO, BASF AG), ethyl 2, 4, 6-trimethylbenzoylphenylphosphinate (Lucirin ® TPO L, BASF AG), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Irga cure® 819 from Ciba Specialty Chemicals), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and their derivatives or mixtures of these photoinitiators.
  • 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO, BASF AG)
  • Examples include benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, Va lerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberon, 4-morpholinobenzophenone, 4-morpholino-deoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxy-anthracon, methyl-anthronone, antithephthenone, antithephthenone, antithephthenone, antithephtheno, anthracetaminophenone, - Quinone carbonate, benzaldehyde, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthene, 3-acetylindo
  • Non-yellowing or little yellowing photoinitiators of the phenylglyoxalic acid ester type are also suitable, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • the compounds of the formulas (I) or (IV) according to the invention react or interact after mixing with the mass to be hardened with their reactive centers or polar groups and are thus bound in a migration-resistant manner.
  • the coating compositions produced with the installable photoinitiators according to the invention are particularly suitable for use in packaging systems, particularly preferably in the food sector.
  • Suitable radiation-curable compositions are, for example, those having from 0.01 to 1.4 mol of reactive centers per 100 g of substance, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0, 75 mol reactive centers and / or from 0.01 to 1.25 mol polar groups, preferably 0.05 to 1.15, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol polar groups Have groups.
  • Radiation-curable compositions which contain from 0.01 to 1.25 mol, preferably 0.05 to 1.15, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of hydroxyl groups per 100 g of substance and / or from 0.01 to 0.75, preferably 0.05 to 0.66, particularly preferably 0.1 to 0.5 mol of isocyanate groups per 100 g of substance and / or from 0.01 to 1.4 mol, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of epoxy groups per 100 g of substance and / or from 0.01 to 1.4 mol, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of ⁇ , ⁇ -unsaturated carbonyl groups per 100 g of substance.
  • acyl and bisacylphosphine derivatives of the formulas (I) or (IV) according to the invention are generally bound to the reactive centers or polar groups at a temperature between room temperature and the curing temperature of the radiation-curable composition. Typical temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
  • the temperature can remain the same or be raised during the course of the hardening or bonding process.
  • the duration of the thermal treatment is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • the invention accordingly also relates to radiation-curable compositions which comprise radiation-curable compositions which contain at least one reactive center and / or at least one polar group by reacting at least one acyl and bisacylphosphine derivative of the formula (I) or (IV) or prepared by a process according to the invention Composition are available.
  • Another object of the present invention are radiation-curable compositions containing a photoinitiator according to the invention.
  • Radiation curable compositions typically contain
  • compositions are, for example
  • (B) 0-60% by weight, preferably 5-50, particularly preferably 6-40 and in particular 10-30% by weight,
  • the proportion of paint additives (D) can be up to 90% by weight, in this case the proportion of the other components is reduced accordingly.
  • compounds (A) there are radiation-curable, free-radically polymerizable compounds with several, i.e. at least two, copolymerizable, ethylenically unsaturated groups.
  • Compounds (A) are preferably vinyl ether or (meth) acrylate compounds, particularly preferred are the acrylate compounds, i.e. the derivatives of acrylic acid.
  • Preferred vinyl ether and (meth) acrylate compounds (A) contain 2 to 20, preferably 2 to 10 and very particularly preferably 2 to 6 copolymerizable, ethylenically unsaturated double bonds.
  • Such compounds (A) with a content of ethylenically unsaturated double bonds of 0.1-0.7 mol / 100 g are particularly preferred, very particularly preferably 0.2-0.6 mol / 100 g.
  • Suitable reactive diluents are free-radically polymerizable compounds, preferably radiation-curable compounds, with an ethylenically unsaturated, copolymerizable group, or mixtures thereof.
  • Examples include ⁇ , ⁇ -unsaturated carboxylic acids, C 1 -C 20 alkyl (meth) acrylates, vinyl aromatics with up to 20 C atoms, vinyl esters of carboxylic acids containing up to 20 C atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds.
  • (meth) acrylic acid is used in the context of this document for acrylic acid and methacrylic acid.
  • ⁇ , ⁇ -unsaturated carboxylic acids which can be used are acrylic acid, methacrylic acid, maleic acid or its half-ester, 3-acrylicoxypropionic acid, maleic anhydride, fumaric acid or its half-ester or crotonic acid.
  • Preferred (meth) acrylic acid alkyl esters are those having a C 1 -C 8 -alkyl radical, such as methyl methacrylate, methyl acrylate and ethyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
  • vinyl aromatic compounds e.g. Vinyltoluene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene are suitable.
  • nitriles are acrylonitrile and methacrylonitrile.
  • Suitable vinyl ethers are e.g. Vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
  • butadiene, isoprene, as well as ethylene, propylene and isobutylene may be mentioned as non-aromatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds.
  • N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam can also be used.
  • Antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, gloss agents, antistatic agents, flame retardants, thickeners, thixotropic agents, flow control agents, binders, antifoams, for example, can be used as typical paint additives (D) , Fragrances, surface-active agents, viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers.
  • the substrates with the radiation-curable compositions are coated in accordance with customary methods known to the person skilled in the art
  • At least one radiation-curable composition according to the invention for example in the form of a dispersion or without solvent, is applied to the substrate to be coated in the desired thickness and the volatile constituents of the dispersion are removed, if appropriate with heating. If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. B. by spraying, spraying, dipping, filling, knife coating, airblade, brushing, rolling, rolling or pouring.
  • the coating thickness is generally in a range from about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 .
  • a method for coating substrates in which a coating composition containing a substance according to the invention, optionally in the form of a paint formulation with other paint-typical additives and / or thermally curable resins, is applied to the substrate, optionally dried, thermally at the curing temperature specified above treated and then, optionally at temperatures up to the curing temperature, with active radiation in an oxygen-containing atmosphere, such as Air, or preferably cures under inert gas.
  • a coating composition containing a substance according to the invention optionally in the form of a paint formulation with other paint-typical additives and / or thermally curable resins
  • the process for coating substrates can also be carried out in such a way that, after the mixture or coating formulation according to the invention has been applied, it is first cured with active energy radiation in an oxygen-containing atmosphere, such as air, or preferably under an inert gas, and then thermally treated at the curing temperature. Thermal and radiation curing can of course also take place in parallel.
  • an oxygen-containing atmosphere such as air, or preferably under an inert gas
  • the films formed on the substrate can only be cured thermally. In general, however, the coatings are cured both by irradiation with high-energy radiation and thermally.
  • active energy rays examples include ultraviolet, X-ray and electron beams, ultraviolet and electron beams are preferred.
  • coating of substrates can also be carried out as follows, where:
  • step iii) optionally irradiating the film formed in step ii) with high-energy radiation, the film being prehardened, and then, if appropriate, mechanically processing the object coated with the prehardened film or bringing the surface of the precured film into contact with another substrate,
  • Steps iv) and iii) can also be carried out in the reverse order.
  • H. the film can first be cured thermally and then with high-energy radiation.
  • Typical curing temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
  • the temperature can remain the same or be raised during the course of the hardening process.
  • the curing time is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulsed lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, electron flash devices, which enables radiation curing without a photoinitiator or radiation initiator.
  • High-pressure mercury vapor lamps, lasers, pulsed lamps (flashing light), halogen lamps or excimer lamps are used as radiation sources, for example.
  • the radiation dose usually sufficient for crosslinking in UV curing is in the range from 80 to 3000 mJ / cm 2 .
  • radiation sources can also be used for curing, e.g. two to four.
  • the photoinitiators according to the invention can also be used with a radiation source with little or no UV content. Daylight curing is also possible, although generally slower than curing with active energy rays.
  • the radiation can optionally also in the absence of oxygen, for. B. are carried out under an inert gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Irradiation can also be carried out by covering the coating material with transparent media.
  • Transparent media are e.g. B. plastic films, glass or liquids, eg. B. water. Particularly preferred is radiation in the manner described in DE-A 199 57 900.
  • a general advantage of the compounds according to the invention is that the solubility of the photoinitiators can be optimally and easily matched to the radiation-curable composition used by structural modifications.
  • Another advantage when using e.g. pigmented radiation-curable compositions is that the absorption of the photoinitiator can be matched to the radiation-curable composition used if the absorption of conventional acylphosphine oxides is hidden, for example, by the pigments.
  • compounds according to the invention it is possible to improve the interactions with the radiation-curable coating systems and thus to optimize the solubility, miscibility, homogenization, etc.
  • compounds 1-2 or 1-21 in the examples make it possible to improve the solubility of the photoinitiators in polyetherol acrylates, which was not possible with conventional acylphosphine oxides.
  • the compounds 1-23 and 1-31, for example, incorporate HALS amine structures.
  • HPLC analysis Kontron Instruments HPLC-Pump 422, Lichrosorb 18 7, Bischoff Chromatography, Shimadzu C-R6A Chromatopac, Mition Roy Spectro Monitor 3100 (230 nm), acetonitrile / water / phosphoric acid (ratio 570: 430: 1) 1.1 ml / min.
  • the lacquer film was applied to a film with a defined layer thickness (15 or 100 ⁇ m).
  • the film was passed through the irradiation apparatus several times at a defined belt speed.
  • the compounds according to the invention have activity similar to that of Lucirin TPO, in some cases in deep curing. are even better (column 3).

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Abstract

L'invention concerne des dérivés de mono- et bisacylphosphine de formule (I), dans laquelle X représente un bras espaceur et RG un groupe à polymérisation radicalaire ou cationique ou un groupe pouvant entrer en interaction avec le polymère en formation. Cette invention concerne également des procédés de production desdits dérivés et d'utilisation de ces derniers comme photoamorceurs.
PCT/EP2003/001070 2002-02-13 2003-02-04 Derives de mono- et bisacylphosphine WO2003068785A1 (fr)

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DE10206096A DE10206096A1 (de) 2002-02-13 2002-02-13 Mono- und Bisacylphosphinderivate
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EP1749513A1 (fr) * 2005-08-01 2007-02-07 Ivoclar Vivadent AG Matériau dentaire photopolymérisable avec les oxides de bisacylphosphine comme inhibiteurs
CN101775135B (zh) * 2009-10-20 2012-09-05 苏州科技学院 羧乙基苯基次膦酸哌嗪聚合物及其制备方法
US8492452B2 (en) 2008-12-18 2013-07-23 Agfa Graphics Nv Polymerizable photoinitiators and radiation curable compositions
WO2013178523A1 (fr) 2012-05-30 2013-12-05 Basf Se Composes durcissables par rayonnement
WO2014129213A1 (fr) 2013-02-21 2014-08-28 富士フイルム株式会社 Composition d'encre, procédé d'impression par jet d'encre, matière imprimée et initiateur de polymérisation de masse moléculaire élevée
CN104059170A (zh) * 2014-06-16 2014-09-24 新丰博兴聚合材料有限公司 一种可聚合型芳甲酰基苯基取代膦酸酯光引发剂
US8883873B2 (en) 2009-05-18 2014-11-11 Agfa Graphics Nv Polymerizable polymeric photoinitiators and radiation curable compositions
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