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    • 专利摘要:
    The present invention relates to organic compounds having a molecular weight of less than 1,000, comprising at least one structural unit of formula (I). Formula I In the above formula, R 1 is an aromatic or heteroaromatic radical capable of absorbing light at wavelengths of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds. Compounds are photoinitiators for base-catalytic reactions. The present invention also provides a base-catalytic or crosslinkable composition comprising a compound having a structural unit of formula (I), a method of conducting a photochemically induced base-catalyzed reaction and a photocatalyst for base-catalyzed reactions. It relates to the use of a compound as a reagent.
    公开号:KR20000076332A
    申请号:KR1019997008433
    申请日:1998-03-07
    公开日:2000-12-26
    发明作者:터너씬컴；바우딘지젤레
    申请人:에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러；시바 스페셜티 케미칼스 홀딩 인크.；
    IPC主号:
    专利说明:

    Photoactivatable nitrogen-containing bases based on α-amino alkenes
    [1] The present invention relates to α-amino alkenes that can be photochemically converted into amidine derivatives, methods for their preparation, and methods for the photochemical preparation of amidine derivatives. The present invention also provides a base-polymerizable or crosslinkable composition comprising these α-amino alkenes, a method for carrying out a photochemically induced, base-catalyzed reaction and a photoinitiator for base-catalyzed reactions. As to the use of α-amino alkenes.
    [2] Various types of photolabile compounds, such as carbamate, see Cameron et al., US Pat. No. 5,545,509 and the references cited therein; Cameron and Frechet, J. Am. Chem. Soc. (1991) 113, 4303], α-keto carbamate (Cameron et al., J. Am. Chem. Soc. (1996), 118, 12925], O-acyl oximes [Tsunooka et al., J. Polymer Sci .: Part A: Polymer Chem. (1994), 32, 2177], formamide [Nishikubo et al., Polym. J. (1993) 25, 421; idem, J. Polymer Sci .: Part A: Polymer Chem. (1993), 31, 3013], co-amine complexes (C. Kutal et al., J. Electrochem. Soc. (1987), 134, 2280, photodegradation production of bases and photopolymerization reactions using these bases have already been described.
    [3] Photochemical intramolecular γ-hydrogen removal reactions of olefins are known, but the corresponding reactions of carbonyl compounds are not described. See V. Sreedhara Rao, A. K. Chandra, J. Photochem. Photobiol. A Chem. 101 (1996), 189 and references cited therein]. The corresponding thermal reactions of olefins are very well described (see J. L. Ripoll, Y. Vallee in Synthesis (1993), 659 and references cited therein).
    [4] It has been surprisingly found that certain α-amino alkenes comprising structural units of formula I emit amidine groups upon exposure to visible or ultraviolet light. Such amidine groups are sufficiently basic to initiate many base-catalytic reactions, in particular polymerization reactions. The compound is sensitive and the absorption spectrum can be varied within a wide range through the selection of substituent R 1 .
    [5]
    [6] The compounds make it possible to produce so-called one-pot systems using base-catalyzed oligomers or monomers with extremely long shelf life. For example, the polymerization reaction starts only after exposure to light. The system can be formulated in the absence of solvent or in the presence of some solvent as the compound can be dissolved in monomers or oligomers that do not affect. The active catalyst is formed only after exposure to light. These systems using base-catalyzed oligomers or monomers can be used for a variety of applications, such as finishes, coatings, molding compounds or photographic plate regeneration.
    [7] Accordingly, the present invention provides organic compounds having a molecular weight of less than 1,000 comprising at least one structural unit of formula (I).
    [8] Formula I
    [9]
    [10] In the above formula,
    [11] R 1 is an aromatic or heteroaromatic radical capable of absorbing light at wavelengths of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds.
    [12] Aromatic or heteroaromatic radicals R 1 are meant to satisfy the Huckel 4n + 2 law.
    [13] The absorption maximum can vary within wide ranges through the selection of aromatic or heteroaromatic radicals R 1 , and the photosensitivity of the compound can shift from the UV region to the sunlight region.
    [14] Preference is given to organic compounds in which the structural unit of formula (I) comprises the compound of formula (II).
    [15]
    [16] In the above formula,
    [17] R 1 is an aromatic or heteroaromatic radical capable of absorbing light at a wavelength of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds,
    [18] R 2 and R 3 are independently of each other hydrogen, C 1-18 alkyl, C 3-18 alkenyl, C 3-18 alkynyl or phenyl,
    [19] When R 2 is hydrogen or C 1-18 alkyl, R 3 is further a group —CO—R 14 ,
    [20] R 14 is C 1-18 alkyl or phenyl,
    [21] R 5 is C 1-18 alkyl or NR 15 R 16 ,
    [22] R 4 , R 6 , R 7 , R 15 and R 16 are independently of each other hydrogen or C 1-18 alkyl,
    [23] R 4 and R 6 together form a C 2-12 alkylene bridge, or
    [24] R 5 and R 7 , independently of R 4 and R 6 , together form a C 2-12 alkylene bridge,
    [25] When R 5 is NR 15 R 16 , R 16 and R 7 together form a C 2-12 alkylene bridge,
    [26] R 17 is hydrogen or C 1-18 alkyl,
    [27] R 18 is hydrogen, C 1-18 alkyl, or C 1-18 alkyl, vinyl, C 3-18 alkenyl, C 3-18 alkynyl, C 1-18 haloalkyl, phenyl, NO 2 , OH, CN, OR 10 , SR 10 , C (O) R 11 , C (O) OR 12 or phenyl substituted by halogen,
    [28] R 10 , R 11 and R 12 are hydrogen or C 1-18 alkyl.
    [29] Alkyl having 18 or less carbon atoms in various radicals is a straight or branched chain radical such as methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n -Pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl , 3-methylheptyl, n-octyl, 2-ethyl-hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, Dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl. Preference is given to alkyl having 1 to 12 carbon atoms, in particular 1 to 6 carbon atoms.
    [30] Alkenyl having 3 to 18 carbon atoms is a straight or branched chain radical such as propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-part Tenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Alkenyl having 3 to 12 carbon atoms, especially 3 to 6 carbon atoms, is preferred.
    [31] Alkynyl having 3 to 18 carbon atoms may be a straight or branched chain radical such as propynyl ( ), 2-butynyl, 3-butynyl, n-2-octynyl or n-2-octadecynyl. Preference is given to alkynyl having 3 to 12, especially 3 to 6, carbon atoms.
    [32] Examples of C 2-12 alkylene bridges are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene.
    [33] R 1 is unsubstituted or C 1-18 alkyl, C 3-18 alkenyl, C 3-18 alkynyl, C 1-18 haloalkyl, NO 2 , NR 8 R 9 , N 3 , OH, CN, OR 10 Phenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro substituted one or more times by SR 10 , C (O) R 11 , C (O) OR 12 or halogen -2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, tiathrenyl, dibenzo Furyl, chromenyl, xanthenyl, thioxanthyl, phenoxatiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolinyl, isoindoleyl, indolyl, Indazolyl, furinyl, quinolinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, putridinyl, carbazolyl, β-carbolinyl , Phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazole , Furanyl janil, terphenyl, stilbenyl, fluorenyl or Fe noksa or possess, and R 1 is a radical of formula A or B, R 8, R 9, R 10, R 11 and R 12 is hydrogen or C 1- Preferred are compounds of formula II, which are 18 alkyl. Examples of C 1-18 alkyl, C 3-18 alkenyl and C 3-18 alkynyl are as described above.
    [34]
    [35]
    [36] In the above formula,
    [37] R 13 is C 1-18 alkyl, C 2-18 alkenyl, C 2-18 alkynyl, C 1-18 haloalkyl, NO 2 , NR 8 R 9 , OH, CN, OR 10 , SR 10 , C ( O) R 11 , C (O) OR 12 or halogen,
    [38] n is 0 or a number of 1, 2 or 3.
    [39] Examples of C 1-18 alkyl, C 3-18 alkenyl and C 3-18 alkynyl are as defined above.
    [40] Halogen is fluorine, chlorine, bromine or iodine.
    [41] Examples of the C 1-18 haloalkyl are fully or partly halogenated C 1-18 alkyl. Halogen (halo) herein is F, Cl, Br or I. Examples thereof include positional isomers of mono- to decafluoropentyl, mono- to octafluorobutyl, mono- to hexafluoropropyl, mono- to tetrafluoroethyl and mono- and difluoromethyl and also corresponding chloro , Bromo and iodo compounds. Perfluorinated alkyl radicals are preferred. Examples thereof are perfluoropentyl, perfluorobutyl, perfluoropropyl, perfluoroethyl and especially trifluoromethyl.
    [42] Examples of NR 8 R 9 amino groups are the respective monoalkyl or dialkylamino groups, for example methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, octadecylamino, dimethylamino, diethyl Amino, dipropylamino, diisopropylamino, di-n-butylamino, di-isobutylamino, dipentylamino, dihexylamino or dioctadecylamino. In addition, dialkylamino groups are groups in which two radicals are independently branched or straight chained from one another, for example methylethylamino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutyl Amino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl tert-butylamino, isopropyl-n-butylamino or isopropylisobutylamino.
    [43] Alkoxy group OR 10 having 18 or less carbon atoms is a straight or branched chain radical such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, hep Oxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having 1 to 12, especially 1 to 8, for example 1 to 6 carbon atoms.
    [44] Examples of thioalkyl group SR 10 are thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl, thioheptyl, thiooctyl or thiooctadecyl, wherein the alkyl radical may be straight or branched.
    [45] Examples of radicals R 1 are phenyl, naphthyl, phenanthryl, anthracyl, biphenylyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro -1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, titranil, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxatiy Neil, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolinyl, isoindoleyl, indolyl, indazolyl, furinyl, quinolzinyl, isoquinolyl, quinolyl , Phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, putridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenantholinyl , Phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, stilbenyl, terphenyl, fluorenyl, phenoxazinyl, methoxyphenyl, 2,4-dimethoxyphenyl, 2, 4,6-trimethoxyphenyl, 3,4,5-trimeth Cyphenyl, bromophenyl, tolyl, xylyl, mesityl, nitrophenyl, dimethylaminophenyl, diethylaminophenyl, aminophenyl, diaminophenyl, thiomethylphenyl, 1-naphthyl, 2-naphthyl, 1-phenyl Amino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl, 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1 , 2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1,2-dimethyl-7-naphthyl, 1,3-dimethyl-6-naphthyl, 1,4-dimethyl-6 -Naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl, 1,4- Dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthate Neyl, 2-phenoxatiinyl, 2,7-phenoxatiinyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imi Zolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 3-pyrazolyl, 1 -Methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2 -Methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7 -Dimethyl-8-furinyl, 2-methoxy-7-methyl-8-furinyl, 2-quinolinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthala Genyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6 -Quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quina Linil, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pterridinyl, 6 , 7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carboline-3 -Yl, 1-methyl-β-carboline-3-yl, 1-methyl-β-carboline-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-ferri Midinyl, 1-methyl-5-ferimidinyl, 5-phenantholinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-iso Thiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-fura Zanyl, 2-phenoxazinyl or 10-methyl-2-phenoxazinyl.
    [46] Especially preferably, R 1 is phenyl unsubstituted or substituted one or more times by C 1-18 alkyl, C 1-18 haloalkyl, NR 8 R 9 , CN, NO 2 , N 3 , SR 10 or OR 10 . , Naphthyl, pyrenyl, thioxanthyl, thianthrenyl or phenothiazinyl, or R 1 is a radical of the formula A or B above.
    [47] In addition, R 1 is phenyl, pyrenyl or naphthyl unsubstituted or substituted one or more times by CN, NR 8 R 9 , NO 2 , CF 3 , SR 10 or OR 10 , or R 1 is as defined above Particular preference is given to compounds which are radicals of A or B.
    [48] Very particularly preferably R 1 is phenyl, 4-aminophenyl, 4-methylthiophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 2,4,6-trimethoxyphenyl, 2,4-dimethoxy Phenyl, naphthyl, anthracyl, pyrenyl or a radical of formula A or B as defined above.
    [49] R 2 and R 3 independently of one another are preferably hydrogen or C 1-6 alkyl. It is preferred that R 4 and R 6 together are a C 2-6 alkylene bridge.
    [50] Preferably, R 5 and R 7 are C 2-6 alkylene bridges or when R 5 is NR 15 R 16 , R 16 and R 7 together are C 2-6 alkylene bridges.
    [51] Preferably, R 17 is hydrogen or C 1-4 alkyl and R 18 is hydrogen, C 1-4 alkyl or phenyl.
    [52] Particularly preferred groups of compounds of formula II are
    [53] R 1 is phenyl, naphthyl or pyrenyl unsubstituted or substituted one or more times by CN, NR 8 R 9 , NO 2 , CF 3 , SR 10 or OR 10 , or R 1 is as defined above; Is a radical of B,
    [54] n is 0,
    [55] The radicals R 8 , R 9 , R 10 and R 13 are hydrogen or C 1-6 alkyl,
    [56] R 2 and R 3 are hydrogen or C 1-6 alkyl,
    [57] R 4 , R 6 and R 7 are independently of each other hydrogen or C 1-6 alkyl,
    [58] R 5 is C 1-6 alkyl or NR 15 R 16 ,
    [59] R 15 and R 16 are hydrogen or C 1-6 alkyl
    [60] R 4 and R 6 together form a C 2-6 alkylene bridge, or
    [61] R 5 and R 7 , independently of R 4 and R 6 , together form a C 2-6 alkylene bridge, or
    [62] When R 5 is NR 15 R 16 , R 16 and R 7 together form a C 2-6 alkylene bridge,
    [63] R 17 is hydrogen or C 1-4 alkyl,
    [64] R 18 is hydrogen, C 1-4 alkyl or phenyl.
    [65] R 1 is phenyl or naphthyl unsubstituted or substituted one or more times by CN, NR 8 R 9 , NO 2 , CF 3 , SR 10 or OR 10 , or R 1 is a radical of formula A,
    [66] n is 0,
    [67] The radicals R 8 , R 9 and R 10 are hydrogen or C 1-6 alkyl,
    [68] R 2 and R 3 are hydrogen or C 1-6 alkyl,
    [69] R 4 and R 6 together form a C 2-6 alkylene bridge,
    [70] R 5 and R 7 together form a C 2-6 alkylene bridge,
    [71] R 17 is hydrogen,
    [72] Especially preferred are organic compounds of formula II, wherein R 18 is hydrogen or C 1-4 alkyl.
    [73] Formula A
    [74]
    [75] The present invention also provides a first step of reacting a compound comprising a structural unit of formula III with a compound comprising a structural unit of formula IV and a second step of reacting the obtained reaction product with a phosphonium salt by Wittig. Provided is a process for preparing a compound having a structural unit of formula I as defined above.
    [76]
    [77]
    [78] In the above formula,
    [79] Halogen is F, Cl, Br or I,
    [80] R 1 is as defined in claim 1.
    [81] A process for preparing a compound of formula (II) comprising a first step of reacting a compound of formula (V) with a compound of formula (VI) and a second step of reacting the obtained reaction product with a phosphonium salt of formula (VII-1) This is preferred.
    [82]
    [83]
    [84] R 17 R 18 CH-P (phenyl) 3 + X -
    [85] In the above formula,
    [86] The radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 17 and R 18 are as defined above including their preferred meanings,
    [87] Halogen is F, Cl, Br or I,
    [88] X is F, Cl, Br, I or tetrafluoroborate.
    [89] Suitable Bittich reagents (phosphonium salts) are commercially available and are mentioned, for example, in the Lancaster Chemical Catalogue, Appendix 1, pages A2-A6. Examples thereof include methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, n-propyltriphenylphosphonium bromide , n-butyltriphenylphosphonium chloride, n-butyltriphenylphosphonium bromide, isobutyltriphenylphosphonium bromide, n-amyltriphenylphosphonium bromide, isoamyltriphenylphosphonium bromide, n-hexyltriphenylphosphate Phonium bromide, n-heptyltriphenylphosphonium bromide, n-octyltriphenylphosphonium bromide, n-nonyltriphenylphosphonium bromide, n-decyltriphenylphosphonium bromide, n-undecyltriphenylphosphonium bromide , n-dodecyltriphenylphosphonium bromide, n-tetradecyltriphenylphosphonium bromide, n-hexadecyltri Phenylphosphonium bromide, trimethylsilylmethyltriphenylphosphonium iodide, 2-dimethylaminoethyltriphenylphosphonium bromide, 2-chloroethyltriphenylphosphonium bromide, 2-hydroxyethyltriphenylphosphonium bromide, 1, 3-bromopropyltriphenylphosphonium bromide, 4-bromobutyltriphenylphosphonium bromide, 2- (1,3-dioxan-2-yl) ethyltriphenylphosphonium bromide, cyclopropylmethyltriphenylphosphonium Bromide, 4-carboxybutyltriphenylphosphonium bromide, 4-carboethoxybutyltriphenylphosphonium bromide, 4-pentenyltriphenylphosphonium bromide, 5-hexenyltriphenylphosphonium bromide, 3-phenylpropyltriphenyl Phosphonium bromide, ethylenebis (triphenylphosphonium bromide), trimethylenebis (triphenylphosphonium bromide), tetramethylenebis (t Phenylphosphonium bromide), pentamethylenebis (triphenylphosphonium bromide), isopropyltriphenylphosphonium iodide, 2-butyltriphenylphosphonium bromide, 2-amyltriphenylphosphonium bromide, cyclopropyltriphenylphosph Phonium bromide, cyclopentyltriphenylphosphonium bromide, cyclohexyltriphenylphosphonium bromide, cycloheptyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide, 2-methylallyltriphenylphosphate Phonium chloride, 3-methylallyltriphenylphosphonium chloride, 3,3-dimethylallyltriphenylphosphonium bromide, 2-butene-1,4-bis (triphenylphosphonium chloride), cinnamiltriphenylphosphonium chloride, Cinnamiltriphenylphosphonium bromide, propargyltriphenylphosphonium bromide, benzyl Triphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium iodide, 2-methylbenzyltriphenylphosphonium chloride, 2-methylbenzyltriphenylphosphonium bromide, 3-methylbenzyltriphenylphosphonium Chloride, 4-methylbenzyltriphenylphosphonium chloride, 4-methylbenzyltriphenylphosphonium bromide, 2-hydroxybenzyltriphenylphosphonium bromide, 4-methoxybenzyltriphenylphosphonium chloride, 4-ethoxybenzyltri Phenylphosphonium bromide, 4-butoxybenzyltriphenylphosphonium bromide, 4-fluorobenzyltriphenylphosphonium chloride, 4-chlorobenzyltriphenylphosphonium chloride, 4-bromobenzyltriphenylphosphonium bromide, 4- Cyanobenzyltriphenylphosphonium chloride, 4-carbomethoxybenzyltriphenylphosphonium bromide, 2-nitrobenzyltriphenylforce Bromide hydrate, 4-nitrobenzyltriphenylphosphonium bromide, o-xylenebis (triphenylphosphonium bromide), p-xylenebis (triphenylphosphonium chloride), p-xylenebis (triphenylphosphonium bromide), 1-naphthylmethyltriphenylphosphonium chloride, benzhydryltriphenylphosphonium chloride, hydroxymethyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium chloride, chloromethyltriphenylphosphonium iodide, methylthio Methyltriphenylphosphonium chloride, phenylthiomethyltriphenylphosphonium chloride, 1,3-ditian-2-yltriphenylphosphonium chloride, formylmethyltriphenylphosphonium chloride, acetonyltriphenylphosphonium chloride, aceto Nyltriphenylphosphonium bromide, phenacyltriphenylphosphonium bromide, α-methylphenacyl Phenylphosphonium bromide, carbomethoxymethyltriphenylphosphonium chloride, carbomethoxymethyltriphenylphosphonium bromide, carboethoxymethyltriphenylphosphonium chloride, carboethoxymethyltriphenylphosphonium bromide, 1-carboethoxy Ethyltriphenylphosphonium bromide, methyl 4- (triphenylphosphonio) crotonate bromide, 1-carboethoxycyclopropyltriphenylphosphonium tetrafluoroborate, cyanomethyltriphenylphosphonium chloride, 2- ( Triphenylphosphoranylidene) succinic anhydride, 9-fluorenyltriphenylphosphonium bromide, vinyltriphenylphosphonium bromide, or 1,2-vinylenebis (triphenylphosphonium bromide).
    [90] The reaction of the compound of formula V with the compound of formula VI can be carried out in a manner known per se. Advantageously, a solvent or solvent mixture, for example hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, etc.), alkanols (e.g. methanol, ethanol) , Ethylene glycol monomethyl ether, and the like) and ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, etc., and mixtures of these solvents are used.
    [91] The reaction may suitably be carried out in the temperature range of -10 to 100 ℃. Preference is given to reaction temperatures of 10 to 50 ° C.
    [92] The Wittich reaction can be carried out in a conventional manner. Solvents or solvent mixtures, for example hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, etc.), alkanols (e.g. methanol, ethanol, ethylene glycol mono It is advantageous to use ethers such as methyl ethers) and ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, and mixtures of these solvents.
    [93] The reaction can be carried out at a temperature range of -10 to 100 ℃. The range of 10-70 degreeC is preferable.
    [94] During the preparation of the photolatent base of the invention, an isomeric mixture may be formed. These can be separated by conventional methods familiar to the skilled person. Alternatively, certain resulting isomeric mixtures can be used directly as photolatent bases.
    [95] The present invention also provides a method of preparing a compound of formula (VII), including exposing the compound of formula (II) to light having a wavelength of 200 to 650 nm.
    [96]
    [97] Formula II
    [98]
    [99] In the above formula,
    [100] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 17 and R 18 are as defined above including their preferred meanings.
    [101] The reaction is advantageously carried out in a solvent or solvent mixture. The concentration of the compound of formula II advantageously adjusts such that virtually all light is absorbed in the reaction vessel.
    [102] The reaction solution is preferably stirred and optionally cooled during exposure.
    [103] Suitable solvents are as described above.
    [104] According to the invention, organic compounds comprising structural units of formula (I) can be used as the photolatent base.
    [105] Accordingly, the present invention further provides compositions comprising A) at least one compound with structural units of formula (I) and B) at least one organic compound capable of reacting base-catalyzed addition or substitution.
    [106] Preference is given to organic compounds of the formula (II) as described above.
    [107] Base-catalyzed addition or substitution reactions can be carried out using low molecular weight compounds (monomers), oligomers, polymeric compounds or mixtures of these compounds. Examples of reactions that can be performed with both monomers and oligomers / polymers using novel photoinitiators are the Knoevenagel reaction or the Michael addition reaction.
    [108] Of particular interest are compositions in which component B) is an anionic polymerizable or crosslinkable organic material. The organic material may be in the form of mono- or polyfunctional monomers, oligomers or polymers.
    [109] Particularly preferred oligomeric / polymeric systems are binders customary in the field of coatings.
    [110] Examples of such base-catalytic binders are as follows:
    [111] a) acrylate copolymers having alkoxysilanes or alkoxysiloxane side chain groups, for example the polymers described in US-A 4,772,672 or US-A 4,444,974,
    [112] b) two-component systems comprising hydroxyl-containing polyacrylates, polyesters and / or polyethers and aliphatic or aromatic polyisocyanates,
    [113] c) two-component systems comprising functional polyacrylates and polyepoxides in which the polyacrylate contains carboxyl and anhydride groups,
    [114] d) two-component systems comprising fluorine-modified or silicone-modified hydroxyl-containing polyacrylates, polyesters and / or polyethers and aliphatic or aromatic polyisocyanates,
    [115] e) two-component systems comprising (poly) ketimines and aliphatic or aromatic polyisocyanates,
    [116] f) two-component systems comprising (poly) ketimines and unsaturated acrylate resins or acetoacetate resins or methyl α-acrylamidomethylglycolates,
    [117] h) two-component systems comprising (poly) oxazolidine and polyacrylate-containing anhydride groups or unsaturated acrylate resins or polyisocyanates,
    [118] i) a two-component system comprising an epoxy-functional polyacrylate and a carboxyl- or amino-containing polyacrylate,
    [119] l) polymers based on allyl glycidyl ether,
    [120] m) two-component systems comprising (poly) alcohols and (poly) isocyanates,
    [121] n) the α, β-ethylenically unsaturated carbonyl compound and, as described, for example, in EP-B 0 161 697, the activated CH 2 group for the (poly) malonate group is the main chain or the side chain or both A two-component system comprising a polymer containing an activated CH 2 group which may be present in. Still other compounds having an activating CH 2 group are (poly) acetoacetates and (poly) cyanoacetates.
    [122] Of these base-catalytic binders the following are particularly preferred:
    [123] b) two-component systems comprising hydroxyl-containing polyacrylates, polyesters and / or polyethers and aliphatic or aromatic polyisocyanates,
    [124] c) two-component systems comprising functional polyacrylates and polyepoxides in which the polyacrylate contains carboxyl and anhydride groups,
    [125] i) a two-component system comprising an epoxy-functional polyacrylate and a carboxyl- or amino-containing polyacrylate,
    [126] m) two-component systems comprising (poly) alcohols and (poly) isocyanates, and
    [127] n) α, β- unsaturated carbonyl compound and the activated CH 2 groups are two-component systems comprising a polymer containing activated CH 2 groups which may be present in both the main chain or side chain thereof.
    [128] Two-component systems comprising α, β-ethylenically unsaturated carbonyl compounds and (poly) malonates and methods for their preparation are described in EP-B 0 161 687. Malonate groups may be bonded to the main or side chain of polyurethane, polyester, polyacrylate, epoxy resin, polyamide or polyvinyl polymer. The α, β-ethylenically unsaturated carbonyl compound used may be a double bond activated by a carbonyl group. Examples thereof are esters or amides of acrylic acid or methacrylic acid. In ester groups, further hydroxyl groups may be present. Diesters and triesters are also possible.
    [129] Typical examples are hexanediol diacrylate or trimethylolpropane triacrylate. Instead of acrylic acid, other acids and esters or amides thereof may be used, such as crotonic acid or cinnamic acid.
    [130] Under base catalysis, the components of the system react with each other at room temperature to form a crosslinked coating system suitable for many applications. Due to its good inherent weather resistance, it is suitable for outdoor applications, for example, and may optionally be further stabilized by UV absorbers and other light stabilizers.
    [131] Other systems suitable as component B) in the novel compositions are epoxy systems. Epoxy resins are suitable for preparing novel curable mixtures comprising epoxy resins as long as component B) is customary in epoxy resin technology, examples of which are:
    [132] I) Polyglycidyl and poly (β-methylglycidyl) esters obtained by reacting a compound having at least two carboxyl groups in the molecule with epichlorohydrin or β-methyl-epichlorohydrin. The reaction is suitably carried out in the presence of a base. As a compound having two or more carboxyl groups in a molecule, aliphatic carboxylic acids can be used. Examples of such polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or dimeric or trimeric linoleic acid. However, alicyclic polycarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid can also be used. In addition, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid can be used.
    [133] II) A compound having at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups is reacted with epichlorohydrin or β-methylepichlorohydrin under alkaline conditions or in the presence of an acidic catalyst followed by alkali Polyglycidyl or poly (β-methylglycidyl) ether obtainable by treatment. Glycidyl ethers of this type are, for example, acrylic alcohols such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol or poly (oxypropylene) glycols, propane- 1,3-diol, butane-1,4-diol, poly (oxytetramethylene) glycol, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol , 1,1,1-trimethylolpropane, pentaerythritol, sorbitol) and polyepichlorohydrin. They can also be derived from alicyclic alcohols such as 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane or have an aromatic nucleus For example, N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane. Glycidyl ethers are also derived from mononuclear phenols such as resorcinol or hydroquinone, or polynuclear phenols such as bis (4-hydroxyphenyl) methane, 4,4'-dihydroxybiphenyl , Bis (4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( Based on 3,5-dibromo-4-hydroxyphenyl) propane and aldehydes such as formaldehyde, acetaldehyde, chloral or furfuraldehyde are phenols such as phenol or nucleus chlorine atom Or novolacs obtainable by condensation with phenols substituted by C 1-9 alkyl groups, for example 4-chlorophenol, 2-methylphenol or 4-tert-butylphenol or bisphenols of the abovementioned type Can be derived from.
    [134] III) Poly (N-glycidyl) compounds obtainable by dechlorination of reaction products of epichlorohydrin with amines containing two or more amine hydrogen atoms. These amines are, for example, aniline, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane. Poly (N-glycidyl) compounds also include triglycidyl isocyanurate, N, N'-diglycidyl derivatives of cycloalkyleneureas such as ethyleneurea or 1,3-propyleneurea and Diglycidyl derivatives of hydantoin, such as 5,5-dimethylhydantoin.
    [135] IV) di-S-glycidyl derived from poly (S-glycidyl) compounds, for example dithiol (eg ethane-1,2-dithiol) or bis (4-mercaptomethylphenyl) ether derivative.
    [136] V) alicyclic epoxy resins such as bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) Ethane or 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate.
    [137] Alternatively, epoxy resins in which 1,2-epoxide groups are bonded to different hetero atoms and / or functional groups can be used. These compounds are, for example, N, N, O-triglycidyl derivatives of 4-aminophenol, glycidyl ether glycidyl esters of salicylic acid, N-glycidyl-N '-(2-glycidyl Oxypropyl) -5,5-dimethylhydantoin or 2-glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoin-3-yl) propane.
    [138] Mixtures of epoxy resins can be used as component B).
    [139] According to the invention, there is also provided a composition comprising as component B) an epoxy resin or a mixture of different epoxy resins.
    [140] The composition comprises photoinitiator, component A), preferably in an amount of 0.01 to 10% by weight, based on component B).
    [141] In addition to the photoinitiator which is component A), the photopolymerizable mixture may comprise various additives. Examples thereof include thermal inhibitors to prevent premature polymerization, for example hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol or sterically hindered phenols such as 2,6-di (tert-butyl) -p-cresol). To increase dark storage stability, copper compounds (eg copper naphthenate, stearate or octoate), phosphorus compounds (eg triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl Phosphite or tribenzyl phosphite), quaternary ammonium compounds (eg tetramethylammonium chloride or trimethylbenzylammonium chloride) or hydroxylamine derivatives (eg N-diethyl-hydroxylamine). To exclude atmospheric oxygen during the polymerization, paraffin or similar wax-like materials may be added which, due to their lack of solubility in the polymer, form a transparent surface layer that migrates to the surface at the start of the polymerization and prevents the ingress of air. It is also possible to apply oxygen-impermeable layers. Light stabilizers that can be added in small amounts are in the form of UV absorbers, for example hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine. Individual compounds or mixtures of these compounds can be used in the presence or absence of sterically hindered amines (HALS).
    [142] Examples of such UV absorbers and light stabilizers are as follows:
    [143] 1. 2- (2'-hydroxyphenyl) benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-3 Tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-( 1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2 -(3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2 ' -Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxy Phenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'- Hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl-5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-[2- (2-ethylhexyloxy) carbo Nylethyl] -2'-hydroxyphenyl) -5- Chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl-5-chlorobenzotriazole, 2- (3'-3 Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenylbenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2- Octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzo Triazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '-(2- Mixture of isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], Transesterification product of 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300, [R-CH 2 CH 2 -COO (CH 2) 3] 2 - ( wherein, R represents 3'-tert-butyl-4'-hydroxy -5'-2H- benzotriazol-2-ylphenyl C).
    [144] 2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy-, 4-octoxy-, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
    [145] 3. Esters of substituted and unsubstituted benzoic acid, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert) -Butyl-benzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl, 3,5-di-tert-butyl-4-hydroxy-benzoate, hexadecyl 3,5 -Di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
    [146] 4. Acrylate, for example ethyl or isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl and butyl α-cyano-β-methyl-p- Methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindolin.
    [147] 5. Steric hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis ( 1,2,2,6,6-pentamethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert- Butyl-4-hydroxybenzylmalonate, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2,2 Condensation product of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2, 2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetra Oate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperi Dine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl Ferridyl) 2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 , 3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy- 2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino Condensation products with -2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl ) -1,3,5-triazine condensation product of 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2, Condensation product of 2,6,6-pentamethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4- Piperidyl) pyrrolidine-2,5-di , 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione.
    [148] 6. Oxalamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-3 Tert-butyloxanide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyloxanide, 2-ethoxy-2'-ethyloxanide, N, N ' -Bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanide and 2-ethoxy-2'-ethyl-5,4'-di Mixtures with -tert-butyloxanide, mixtures of o- and p-methoxy and mixtures of o- and p-ethoxy-substituted oxanilides.
    [149] 7. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5 -Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-di Hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2 , 4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine , 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- ( 2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl / tridecyloxy -(2-hydroxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine.
    [150] 8. phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Erythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-isodecyloxy pentaerythritol diphosphite, bis (2,4-di-3 Tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4 -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10- Tra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12- Methyldibenzo [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-3 Tert-butyl-6-methylphenyl) ethyl phosphite.
    [151] Examples of additional additives are as follows:
    [152] Fillers and reinforcing agents such as powders or fibers of calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural products , Synthetic fiber. Other additives such as plasticizers, lubricants, emulsifiers, pigments, flow additives, catalysts, leveling aids, brighteners, flame retardants, antistatic agents, foaming agents. In addition to the additives described above, additional open reagents may be present. In general, they are dyes that improve the overall quantum yield, for example using energy transfer or electron transfer. Examples of suitable dyes which can be added as open reagents are triarylmethanes, for example malachite green, indolin, thiazine, for example methylene blue, xanthone, thioxanthone, oxazine, acridine or phena Gin, for example safranin, and chemical formulas Rhodamine, wherein R is alkyl or aryl and R 'is a hydrogen, alkyl or aryl radical, for example rhodamine B, rhodamine 6G or violamine R and also sulforhodamine B or sulfor Hodamine G.
    [153] Preference is given to thioxanthone, oxazine, acridine, phenazine and rhodamine.
    [154] In this regard, combinations of dyes and borate are described, for example, in US Pat. No. 4,772,530, GB 2 307 474, GB 2 307 473, GB 2 307 472 and EP 775 706.
    [155] In addition to component B) which is the base-catalytic (curable) binder described above, the composition may also comprise other binders. Further olefinically unsaturated compounds are also possible, for example. The unsaturated compound may comprise one or more olefinic double bonds. They may be low molecular weight (monomeric) or high molecular weight (oligomeric). Examples of monomers having double bonds are alkyl or hydroxyalkyl acrylates or methacrylates such as methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate, methyl Methacrylate or ethyl methacrylate. Silicone acrylates are also interesting. Further examples include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides, vinyl esters (eg vinyl acetate), vinyl ethers (eg isobutyl vinyl ether), styrene, alkyl- and Halostyrene, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.
    [156] Examples of monomers having two or more double bonds include diacrylates of ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenol A, 4,4'-bis (2-acryloyloxyethoxy) diphenyl Propane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris ( 2-acryloylethyl) isocyanurate.
    [157] Examples of relatively high molecular weight (oligomeric) polyunsaturated compounds are polyesters, polyurethanes and polyethers containing acrylated epoxy resins, acrylated polyesters or vinyl ether groups or epoxy groups. Further examples of unsaturated oligomers are unsaturated polyester resins which are mostly made from maleic acid, phthalic acid and one or more diols and have a molecular weight of about 500 to about 3000. It is also possible to use vinyl ether monomers and oligomers and also maleate-terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy backbones. In particular, combinations of vinyl ether-functional oligomers and polymers are described in WO 90/01512 as being very suitable. However, copolymers of vinyl ether and maleic acid-functionalized monomers are also suitable. Unsaturated oligomers of this kind are called prepolymers.
    [158] Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the chain or side chain groups, such as unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, Alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers and polymers and copolymers having (meth) acryl groups in the side chains and mixtures of one or more such polymers.
    [159] In addition, when using such free-radically curable monomers, oligomers / polymers, it is suitable to add additional photoinitiators that dissociate into free radicals. Such photoinitiators are known and commercially available. Examples are benzophenones, benzophenone derivatives, acetophenones, acetophenone derivatives such as α-hydroxycycloalkyl phenyl ketones, dialkoxyacetophenones, α-hydroxy- or α-aminoacetophenones, 4-aroyl -1,3-dioxolane, benzoin alkyl ether and benzyl ketal, monoacyl phosphine oxide, bisacylphosphine oxide, ferrocene or titanocene.
    [160] Examples are specified in EP-A 284 561. Polymer systems of this kind in which curing / crosslinking is carried out with different mechanisms are called hybrid systems.
    [161] The novel compositions can add non-reactive binders, especially when the photopolymerizable compound is a liquid or viscous material. The amount of non-reactive binder can be, for example, from 5 to 95% by weight, preferably from 10 to 90% by weight, in particular from 40 to 90% by weight, based on the total solids content. The choice of non-reactive binder depends on the field of use and the properties required for using it, for example developability in aqueous and organic solvent systems, adhesion to substrates and sensitivity to oxygen.
    [162] Examples of suitable binders are polymers having a molecular weight of about 5,000 to 2,000,000, preferably 10,000 to 1,000,000. Examples are homopolymeric and copolymeric acrylates and methacrylates such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkyl methacrylates), poly (alkyl acrylates), Cellulose esters and ethers such as cellulose acetate, cellulose acetate butyrate, methylcellulose, ethylcellulose, polyvinylbutyral, polyvinylformal, cyclic rubber, polyethers such as polyethylene oxide, polypropylene oxide, Polytetrahydrofuran, polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, polyvinyl chloride, copolymer of vinyl chloride / vinylidene chloride, copolymer of vinylidene chloride and acrylonitrile, methyl methacrylate and vinyl acetate, Polyvinyl acetate, copoly (ethylene / Vinyl acetate), polymers such as polycaprolactam and poly (hexamethylene adipamide) and polyesters such as poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate).
    [163] In addition, the present invention
    [164] A) at least one compound having structural units of formula I and
    [165] B) providing a method for carrying out a base-catalyzed reaction, comprising irradiating with one or more organic compounds capable of reacting base-catalyzed, ie a composition as described above, with light having a wavelength of 200 to 650 nm. do.
    [166] Formula I
    [167]
    [168] In the above formula,
    [169] R 1 is an aromatic or heteroaromatic radical capable of absorbing light at wavelengths of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds.
    [170] Component A) is preferably an organic compound of formula (II) as described above comprising the preferred meanings described.
    [171] Examples and preferred meanings of base-catalyzed reactions have already been described above.
    [172] In some cases it may be beneficial to heat during or after exposure to light. In this way in most cases it is possible to promote the crosslinking reaction.
    [173] In addition, the methods described above for producing coatings, molding compositions or photostructured layers are in accordance with the present invention.
    [174] The sensitivity to light of the novel compositions generally extends from about 200 nm to the infrared region (about 20,000 nm, especially 1,200 nm) through the UV region and therefore over a very wide range. Suitable radiation includes, for example, light from daylight or artificial light sources. Thus, many very different types of light sources can be used. Both clerks and flat throwers (lamp carpets) are suitable. Examples are carbon arc lamps, xenon arc lamps, medium, high and low pressure mercury lamps, optionally doped with metal halides (metal halide lamps), produced using synchrotron or laser plasma, microwave-stimulated metal vapor lamps, excimers Lamps, super-ray fluorescent tubes, fluorescent lamps, incandescent argon lamps, electron flashes, photo flood lamps, electron beams and X-rays. The distance between the lamp and the substrate according to the invention to be exposed may vary depending on the application and the type and intensity of the lamp, for example 2 to 150 cm. Also suitable are laser light sources, for example excimer lasers. Lasers in the visible or IR region may also be used. The high sensitivity of the novel materials and dye suitability as open reagents for laser lines are very beneficial here. By this method, printed circuits can be manufactured in the electronics industry, lithographic offset printing plates or relief printing plates, and photographic image recording materials.
    [175] The novel compositions are suitable for various applications, for example printing inks, transparent coatings, for example white paints for wood or metals, in particular coating materials for paper, wood, metals or plastics, powder coatings, buildings and roads. Preparation of printing plates that can be developed using sun-curable coatings for marking, photo reproducing processes, holographic recording materials, image recording processes or organic solvents or aqueous-alkaline media, preparation of masks for screen printing, tooth filling Materials, adhesives including pressure sensitive adhesives, laminated resins, corrosion resists or permanent resists and solder masks for electronic circuits, mass curing (UV curing in transparent molds) or solids as described, for example, in US Pat. No. 4,575,330. Preparation of three-dimensional articles by lithographic processes, which may contain composite materials such as glass fibers and / or other fibers and other auxiliaries Styrene polyester) and other producing a thin layer composition can be used as a coating or encapsulation or coating of the optical fibers of the electronic component.
    [176] In surface coatings it is customary to use mixtures of prepolymers and polyunsaturated monomers which also contain monounsaturated monomers. Since the prepolymer here mainly affects the properties of the coated film, the skilled person changes it to affect the properties of the cured film. Polyunsaturated monomers act as crosslinkers to render the coating film insoluble. Monounsaturated monomers act as reactive diluents in a way to reduce their viscosity in the absence of solvent.
    [177] Unsaturated polyester resins are mostly used in two-component systems with monounsaturated monomers, preferably styrene. In photoresists, polymaleimide, polychalcones or polyimides are often used, as described in certain one-component systems, for example DE-A 2 308 830.
    [178] The novel photocurable compositions provide a variety of substrates, such as wood, textiles, paper, ceramics, glass, plastics (e.g. polyesters), polyethylene tere, which are particularly susceptible to the application of protective coatings or to image exposure. Suitable as coating material for phthalates, polyolefins or cellulose acetates and metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2 .
    [179] The substrate may be coated by applying a solution or suspension, which is a liquid composition, to the substrate. The choice and concentration of solvent depends mainly on the form of the composition and the coating process. The solvent should be inert. That is, it should not be chemically reacted with the components and should be able to be removed by a drying method after coating. Examples of suitable solvents are ketones, ethers and esters such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxy Ethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate.
    [180] Using known coating processes such as spin coating, dip coating, knife coating, curtain coating, blushing, spraying-in particular electrostatic spraying- and reverse roll coating and electrophoretic deposition, the solution is homogenized to the substrate. Apply. In addition, the photosensitive layer may be applied to a temporary, flexible support, and then the final substrate, such as a copper-plywood circuit board, may be coated using a method of transitioning the layer through lamination.
    [181] The amount applied (layer thickness) and the nature of the substrate (layer support) are a function of the desired field of application. The thickness of the layer generally includes a numerical value of at least about 0.1 to 100 μm.
    [182] The novel radiation-sensitive composition can be exposed visually. In this case they are used as negative resists. They are suitable for the manufacture of electronic engineering (current resists, etch resists and solder resists), printing plates such as offset printing plates, flexors and relief printing plates or screen printing plates, the production of marking stamps, It can be used as a micro resist in the manufacture of milling or integrated circuits. Thus, a wide variety of variations are possible in the process conditions of possible layer supports and coated substrates.
    [183] The term “imaginary” exposure refers to exposure through a predetermined pattern, for example a photomask containing a slide, for example exposure by a laser beam that is moved under computer control over a surface of a coated substrate to produce an image. Relates to irradiation with a controlled electron beam.
    [184] Following imaging exposure of the material and prior to development, it may be beneficial to perform a simple heat treatment in which only the exposed portions are heat cured. The temperature used is generally 50 to 150 ° C., preferably 80 to 130 ° C., and the heat treatment duration is generally 0.25 to 10 minutes.
    [185] A further field of use for photocuring is photocuring for metal coatings, for example surface-coatings and polymer coatings on top of metal panels and tubes, cans or bottles, for example floor or wall coverings based on PVC. .
    [186] Examples of photocuring of paper coatings are colorless varnishing of labels, record sheaves or book covers.
    [187] The use of new compounds for curing molded articles made from composite compositions is of interest. The composite composition is made of a self-supporting matrix material, for example glass-fiber fabrics, or plant fibers, for example infused in photocurable formulations. KP Mieck, T. Reussmann in Kunststoffe 85 (1995) , 366-370. Molded articles made from composite compositions using the compounds according to the invention have high mechanical stability and resistance. The compounds of the invention can also be used as photocuring agents in molding, injecting and coating compositions as described, for example, in EP-A 7086. Examples of such compositions are fine coating resins or fiber-reinforced molded articles, such as flat or vertically or horizontally corrugated light diffusion panels, which have stringent regulations on their curing activity and yellowing resistance.
    [188] The present invention also provides the use of a compound as described above comprising the structural unit of formula (I) as a photoinitiator for photochemically induced base-catalyzed addition or substitution reactions.
    [189] Examples of preferred compounds comprising structural units of formula (I) and substrates suitable for base catalyzed addition or substitution reactions are as described above.
    [190] The present invention provides a method for generating a photograph of a relief image in which at least one surface is coated with a composition as described above and the coated substrate and the coated substrate are imaged and then the unexposed areas are removed using a solvent. In particular in this regard, the above-mentioned exposure using a laser beam is of interest. The present invention also provides a polymerized or crosslinked composition as described above.
    [191] The following examples illustrate the invention.
    [192] Example A: Preparation of Photoinitiator
    [193] General manufacturing method
    [194] a) A solution of the corresponding α-bromoketone in toluene is added to a solution of 1,5-diazabicyclo [4.3.0] nonane in toluene with stirring and further stirred at room temperature overnight. The reaction mixture is filtered, washed with deionized water and then dried over MgSO 4 . Further drying in vacuo affords a yield of about 85% of the corresponding α-aminoketone.
    [195] b) Methyltriphenylphosphonium bromide and sodium amide are stirred in dichloromethane for 15 minutes, a solution of α-amino ketone prepared in a) in dichloromethane is added and the mixture is stirred at room temperature for 18 hours. The solution is filtered and the filtrate is concentrated in vacuo. The crude yield of the resulting α-amino ketone is 65 to 85%.
    [196] In the examples the molar extinction coefficient ε has a dimension of l / mol cm.
    [197] Example A1
    [198] R 1 = biphenylyl, R 2 = R 3 = H, R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [199]
    [200] Elemental Analysis for C 22 H 26 N 2 :
    [201] Calc .: C 82.97; H 8.23; N 8.80.
    [202] Found: C 82.83; H 8.26; N 8.59.
    [203] UV (CHCl 3 ) max 275 nm (ε 21600).
    [204] IR (KBr) 1625 and 1600 cm −1 (C = C).
    [205] 1 H NMR (CDCl 3 ): 7.66-7.28 (9H, m, ArH), 5.51 (1H, s, = CH), 5.29 (1H, s, = CH), 3.83 (1H, d, J 13.3 Hz, NCH 2 C (CH 2) Ph), 3.07 (3H, m, NCH 2 ), 2.89 (1H, d, J 13.3 Hz, NCH 2 C (CH 2 ) Ph), 2.38-1.12 (10H, m, CH 2).
    [206] 13 C NMR (CDCl 3 ): 144.14, 141.02, 140.27, 139.31, 128.82, 127.25, 127.08, 126.99, 126.92, 115.43, 85.08, 58.92, 52.33, 51.92, 51.19, 29.52, 24.75 and 19.55.
    [207] m / z (EI) 318 (M +)
    [208] Example A2
    [209] R 1 = 2-naphthyl, R 2 = R 3 = H, R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [210]
    [211] Elemental Analysis for C 20 H 24 N 2 :
    [212] Calc .: C 82.15; H 8.27; N 9.58.
    [213] Found: C 82.25; H 8.25; N 9.24.
    [214] UV (CHCl 3 ) max 247 nm (ε 35600) and 287 nm (ε 8600).
    [215] IR (KBr) 1625 and 1595 cm <-1> (C = C).
    [216] 1 H NMR (CDCl 3 ): 7.95 (1H, s, ArH), 7.85-7.65 (4H, m, ArH), 7.45-7.35 (2H, m, ArH), 5.58 (1H, s, = CH), 5.39 (1H, s, = CH), 3.88 (1H, d, J 13.6 Hz, NCH 2 C (CH 2 ) Ph), 3.07 (3H, m, NCH 2 ), 2.97 (1H, d, J 13.7 Hz, NCH 2 C (CH 2 ) Ph), 2.44-1.45 (10H, m, CH 2 ).
    [217] 13 C NMR (CDCl 3 ): 144.57, 137.84, 133.41, 132.97, 128.37, 127.68, 127.53, 125.96, 125.78, 125.15, 124.94, 115.79, 84.94, 58.65, 52.21, 52.09, 51.12, 29.49, 24.58 and 19.58.
    [218] m / z (EI) 292 (M &lt; + &gt;).
    [219] Example A3
    [220] R 1 = 4-diethylaminophenyl, R 2 = R 3 = H, R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [221]
    [222] UV (CHCl 3 ) max 245 nm (ε 3700) and 305 nm (ε 16100).
    [223] IR (KBr) 1610 cm -1 and 1520 cm -1 (C = C).
    [224] 1 H NMR (CDCl 3 ): 7.48 (2H, d, ArH), 6.58 (2H, d, ArH), 5.32 (1H, s, = CH), 5.05 (1H, s, = CH), 3.74 (1H, d, J 13.1 Hz, NCH 2 C (CH 2 ) Ph), 3.32 (4H, q, J 7.1 Hz, NCH 2 CH 3 ), 3.06 (3H, M, NCH 2 ), 2.80 (1H, d, J 13.1 Hz, NCH 2 C (CH 2 ) Ph, 2.36 1.23 (10H, m, CH 2 ) and 1.13 (6H, t, J 7.1 Hz, CH 3 ).
    [225] 13 C NMR (CDCl 3 ): 147.21, 143.63, 131.43, 127.36, 111.34, 110.07, 84.21, 59.02, 52.30, 51.81, 51.24, 44.40, 29.42, 24.75, 19.53 and 12.71.
    [226] m / z (EI) 313 (M &lt; + &gt;).
    [227] Example A4
    [228] R 1 = 4-thiomethylphenyl, R 2 = R 3 = H, R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [229]
    [230] UV (CHCl 3 ) max 280 nm (ε 13800).
    [231] IR (KBr) 1670, 1625 and 1595 cm -1 (C = C).
    [232] 1 H NMR (CDCl 3 ): 7.48 (2H, d, ArH), 7.16 (2H, d, ArH), 5.41 (1H, s, = CH), 5.21 (1H, s, = CH), 3.74 (1H, d, J 13.2 Hz, NCH 2 C (CH 2 ) Ph), 3.05 (3H, m, NCH 2 ), 2.83 (1H, d, J 13.2 Hz, NCH 2 C (CH 2 ) Ph), 2.44 (3H, s, SCH 3 ), 2.30-1.4 (10H, m, CH 2 ).
    [233] 13 C NMR (CDCl 3 ): 143.83, 137.46, 137.16, 126.89, 126.49, 114.93, 84.99, 58.85, 52.25, 51.78, 51.12, 29.42, 24.67, 19.48 and 15.97.
    [234] m / z (EI) 288 (M &lt; + &gt;).
    [235] Example A5
    [236] R 1 = phenyl, R 2 = H, R 3 = H, R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [237]
    [238] Elemental Analysis for C 17 H 24 N 2 :
    [239] Calc .: C 79.64; H 9.43; N 10.93.
    [240] Found: C 79.64; H 9.46; N 10.75.
    [241] UV (CHCl 3 ) max 244 nm (ε 6700).
    [242] IR (KBr) 1630, 1600 and 1575 cm -1 (C = C).
    [243] 1 H NMR (CDCl 3 ): 7.50-7.17 (5H, m, ArH), 5.35 (0.75H, s, = CH), 5.24 (0.25H, s, = CH), 5.15 (0.75H, s, = CH ), 5.10 (0.25H, s, = CH), 4.06 (1H, q, J 6.8 Hz, NCHCH 3 ), 2.94 (3H, m, NCH 2 ), 2.63 (1H, m, NCH 2 ), 2.2-1.2 (9H, m, CH 2 ), 1.36 (0.75H, d, J 7.0 Hz, CH 3 ) and 1.13 (2.25H, d, J 6.8 Hz, CH 3 ).
    [244] 13 C NMR (CDCl 3 ): 150.38, 142.89, 128.16, 127.04, 126.93, 114.95 (subdiastereomers), 114.48 (major diastereomers), 82.18 (subdiastereomers), 82.03 (major diastereomers), 56.37, 52.24, 51.60, 43.27, 28.99 (subdiastereomers), 28.73 (major diastereomers), 25.62 (major diastereomers), 25.14 (major diastereomers), 19.36 and 9.35.
    [245] m / z (DCI) 256 (M &lt; + &gt;).
    [246] Example A6
    [247] R 1 = 4-biphenyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [248]
    [249] UV (CHCl 3 ) max 266 nm (ε 19200).
    [250] IR (KBr) 1625, 1600, 1580 cm -1 (C = C).
    [251] 1 H NMR (CDCl 3 ): 7.49-7.14 (9h, m, ArH), 5.29 (0.8H, s, = CH), 5.18 (0.2H, s, = CH), 5.05 (0.8H, s, = CH ), 5.00 (0.2H, s, = CH), 4.00 (1H, q, J 6.5 Hz, NCHCH 3 ), 2.91 (2H, m, NCH 2 ), 2.75 (1H, m, NCH 2 ), 2.52 (1H , m, NCH), 2.1-1.2 (9H, m, CH 2 ) and 1.04 (3H, d, J 6.8 Hz CH 3 ).
    [252] 13 C NMR (CDCl 3 ): 150.00, 141.80, 141.18, 139.88, 128.83, 128.74, 127.46, 127.33, 127.11, 127.02, 126.90, 126.85, 114.51, 82.18, 57.33 (subdiastereomers), 56.30 (major diastereomers) ), 52.28 (major diastereomer), 51.96 (subdiastereomer), 51.63 (major diastereomer), 51.34 (subdiastereomer), 46.18 (subdiastereomer), 43.27 (major diastereomer), 29.10 (subdiastereomers), 28.76 (major diastereomers), 25.64 (subdiastereomers), 25.19 (major diastereomers), 19.36 (major diastereomers), 18.74 (subdiastereomers), 15.35 (subdiastereomers) Minor diastereomers), 9.27 (major diastereomers).
    [253] m / z (EI) 332 (M &lt; + &gt;).
    [254] Example A7
    [255] R 1 = 1-naphthyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [256]
    [257] UV (CHCl 3 ) max 271 nm (ε 26900) and 280 nm (ε 6000).
    [258] IR (KBr) 1620, 1590, 1570 cm <-1> (C = C).
    [259] 1 H NMR (CDCl 3 ): 7.77-7.52 (5H, m, ArH), 7.42-7.30 (2H, m ArH), 5.54 (0.75H, s, = CH), 5.40 (0.25H, s, = CH) , 5.31 (0.75H, s, = CH), 5.29 (0.25H, s, = CH), 4.14 (1H, q, J 6.8 Hz, NCHCH 3 ), 2.87 (3H, m, NCH 2 ), 2.62 (1H , m, NCH), 2.1-1.0 (12H, m, CH 2 and CH 3 ).
    [260] 13 C NMR (CDCl 3 ): 150.84, 140.43, 133.48, 132.80, 128.11, 127.75, 127.65, 127.54, 127.49, 126.09, 125.80, 125.62, 125.60, 114.86, 82.18 (subdiastereomers), 81.95 (major diastereomers) ), 57.22 (subdiastereomers), 56.33 (major diastereomers), 52.08 (major diastereomers), 51.89 (subdiastereomers), 51.46 (major diastereomers), 51.28 (subdiastereomers), 46.00 (subdiastereomers), 43.41 (major diastereomers), 29.02 (subdiastereomers), 28.78 (major diastereomers), 25.60 (subdiastereomers), 25.00 (major diastereomers), 19.39 (major diastereomers) Major diastereomers), 19.07 (subdiastereomers), 9.43.
    [261] m / z (EI) 306 (M &lt; + &gt;).
    [262] Example A8
    [263] R 1 = 2-naphthyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [264]
    [265] UV (CHCl 3 ) max 245 (ε 5660).
    [266] IR (KBr) 1625, 1600, 1570 cm -1 (C = C).
    [267] 1 H NMR (CDCl 3 ): 7.83-7.72 (4H, m ArH), 7.60 (1H, m ArH), 7.47-7.24 (2H, m ArH), 5.46 (0.75H, s, = CH), 5.37 (0.25 H, s, = CH), 5.25 (075H, s, = CH), 5.20 (0.25H, s, = CH), 4.20 (1H, q, J 6.8 Hz, NCHCH 3 ), 3.01-2.65 (4H, m ), 2.18-1.43 (9H, m) and 1.18 (3H, d, J 6.8 Hz, CH 3 ).
    [268] 13 C NMR (CDCl 3 ): 150.81, 140.45, 133.49, 132.81, 128.12, 127.53, 125.77, 125.62, 125.48, 114.88, 82.18 (subdiastereomer), 81.95 (main diastereomer), 56.32, 52.07 (main part Stereoisomers), 51.88 (subdiastereomers), 51.45 (major diastereomers), 51.28 (subdiastereomers), 43.40, 29.08 (subdiastereomers), 28.78 (major diastereomers), 25.41 (partial isomers) Stereoisomers), 25.00 (major diastereomers), 19.39, 9.45.
    [269] m / z (EI) 306 (M &lt; + &gt;).
    [270] Example A9
    [271] R 1 = 2-Tianthrenyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [272]
    [273] UV (CHCl 3 ) max 262 nm (ε 29800).
    [274] IR (KBr) 1625, 1580 cm −1 (C = C).
    [275] H NMR (CDCl 3 ): 7.47-7.17 (7H, m ArH), 5.32 (0.9H, s, = CH), 5.24 (0.1H, s, = CH), 5.15 (0.9H, s, = CH), 5.11 (0.1H, s, = CH), 4.00 (1H, q, J 6.7 Hz, NCHCH 3 ), 3.03-2.60 (4H, m), 2.26-1.16 (9H, m) and 1.12 (3H, d, J 6.7 Hz, CH 3 ).
    [276] 13 C NMR (CDCl 3 ): 149.46, 142.80, 135.82, 135.75, 135.07, 133.80, 128.73, 128.69, 128.37, 127.59, 127.54, 127.10, 126.43, 115.63 (subdiastereomers), 115.10 (major diastereomers), 82.00 (subdiastereomers), 81.80 (major diastereomers), 57.37 (subdiastereomers), 56.25 (major diastereomers), 52.12 (major diastereomers), 51.83 (subdiastereomers), 51.40 (subdiastereomers) Major diastereomers), 51.21 (subdiastereomers), 46.65 (subdiastereomers), 43.26 (major diastereomers), 29.75 (major diastereomers), 28.81 (major diastereomers), 25.57 (partial isomers) Stereoisomers), 25.03 (major diastereomers), 19.38 (major diastereomers), 18.27 (subdiastereomers), 14.16 (subdiastereomers), 9.21 (major diastereomers).
    [277] m / z (EI) 394 (M &lt; + &gt;).
    [278] Example A10
    [279] R 1 = 2- Thioxanthyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [280]
    [281] UV (CHCl 3 ) max 391 nm (ε 4000) and 266 nm (ε 28700).
    [282] IR (KBr) 1640, 1592 cm -1 (C = C).
    [283] 1 H NMR (DMSO-d6): 8.49 (1H, d, ArH), 8.47 (1H, d, ArH), 7.89 (1H, dd, ArH), 7.85 (1H, d, ArH), 7.79 (1H, d , ArH), 7.77 (1H, t, ArH), 7.59 (1H, t, ArH), 5.51 (0.9H, s, = CH), 5.45 (0.1H, s, = CH), 5.26 (0.9H, s , = CH), 5.18 (0.1H, s, = CH), 4.19 (1H, q, J 5 Hz, NCHCH 3 ), 2.85-2.80 (4H, m), 2.10-1.19 (9H, m) and 1.16 (3H , d, J 7 Hz, CH 3 ).
    [284] 13 C NMR (CDCl 3 ): 178.8, 149.2, 140.6, 136.5, 135.75, 134.9, 132.9, 131.7, 129.1, 128.3, 128.0, 126.8, 126.6, 126.1, 115.3, 81.1, 55.1, 51.5, 50.5, 42.5, 28.0, 24.5, 19.0, 8.5.
    [285] m / z (EI) 390 (M &lt; + &gt;).
    [286] Example A11
    [287] R 1 = 3,4,5-trimethoxyphenyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [288]
    [289] Elemental Analysis for C 20 H 30 N 2 O 3 :
    [290] Calc .: C 69.33; H 8.73; N 8.09.
    [291] Found: C 69.14; H 8.71; N 8.06.
    [292] UV (CHCl 3 ) max 319 nm (e 1000) and 250 nm (e 7100).
    [293] IR (KBr) 1681, 1578 cm -1 (C = C).
    [294] 1 H NMR (CDCl 3 ): 6.65 (1.6H, s, ArH), 6.51 (0.4H, s, ArH), 5.29 (0.8H, s, = CH), 5.24 (0.2H, s, = CH), 5.10 (0.8H, s, = CH), 5.06 (0.2H, s, = CH), 4.04 (1H, q, J 6.8 Hz, NCHCH 3 ), 3.81 (9H, s, OCH 3 ), 2.98-2.79 ( 3H, m), 2.62 (1H, m), 2.18-1.17 (9H, m) and 1.12 (3H, d, J 6.7 Hz, CH 3 ).
    [295] 13 C NMR (CDCl 3 ): 152.8, 150.6, 138.7, 114.2, 104.3, 81.9, 60.7, 56.4, 56.2, 52.1, 51.5, 43.2, 28.8, 25.1, 19.4, 9.3.
    [296] m / z (EI) 346 (M + ).
    [297] Example A12
    [298] R 1 = 4-thiomethylphenyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [299]
    [300] Elemental Analysis for C 18 H 26 N 2 S:
    [301] Calc .: C 71.48; H 8.66; N 9.26; S 10.60.
    [302] Found: C 71.48; H 8.60; N 8.44; S 10.47.
    [303] UV (CHCl 3 ) max 275 nm (e 14100).
    [304] IR (KBr) 1620, 1593 cm -1 (C = C).
    [305] 1 H NMR (CDCl 3 ): 7.43-7.14 (4H, m, ArH), 5.34 (0.75H, s, = CH), 5.22 (0.25H, s, = CH), 5.11 (075H, s, = CH) , 5.06 (0.25H, s, = CH), 4.05 (1H, q, J 6.7 Hz, NCHCH 3 ), 3.06-2.59 (4H, m), 2.44 (3H, s, SCH 3 ), 2.17-1.34 (9H , m) and 1.12 (3H, d, J 6.7 Hz, CH 3 ).
    [306] 13 C NMR (CDCl 3 ): 149.7, 139.7, 136.8, 127.5, 127.4, 126.6, 126.4, 114.1, 82.0, 56.2, 52.2, 51.6, 51.3, 43.2, 28.7, 25.2, 19.3, 9.2.
    [307] m / z (EI) 302 (M + ).
    [308] Example A13
    [309] R 1 = 2-fluorenyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = H
    [310]
    [311] UV (CHCl 3 ) max 281 nm (ε 19500).
    [312] IR (KBr) 1623, 1611 cm -1 (C = C).
    [313] 1 H NMR (CDCl 3 ): 7.78-7.23 (7H, m, ArH), 5.42 (0.75H, s, = CH), 5.32 (0.25H, s, = CH), 5.19 (075H, s, = CH) , 5.14 (0.25H, s, = CH), 4.14 (1H, q, J 6.5 Hz, NCHCH 3 ), 3.88 (2H, m, C 9 fluorenyl), 3.16-2.87 (3H, m), 2.68 ( 1H, q, J 5.6 Hz), 2.20-1.24 (9H, m) and 1.17 (3H, d, J 6.7 Hz, CH 3 ).
    [314] 13 C NMR (CDCl 3 ): 150.8, 143.5, 143.1, 141.7, 140.7, 126.7, 126.4, 125.8, 125.0, 123.5, 119.8, 119.5, 114.8 (subdiastereomers), 114.2 (major diastereomers), 82.2 ( Minor diastereomers), 82.0 (major diastereomers), 57.3 (major diastereomers), 56.5 (major diastereomers), 52.1 (major diastereomers), 52.0 (minor diastereomers), 51.5 (minor partial isomers) Stereoisomers), 51.3 (subdiastereomers), 45.7 (subdiastereomers), 43.4 (major diastereomers), 37.0 (C 9 fluorenyl), 29.0 (subdiastereomers), 28.8 (major diastereomers) Isomers), 25.7 (subdiastereomers), 25.1 (major diastereomers), 19.4, 9.5.
    [315] m / z (EI) 344 (M + ).
    [316] Example A14
    [317] R 1 = phenyl, R 2 = H, R 3 = CH 3 , R 4 / R 6 =-(CH 2 ) 3- , R 5 / R 7 =-(CH 2 ) 3- , R 17 = R 18 = CH 3
    [318]
    [319] 1 H NMR (CDCl 3 ): 7.31-7.10 (5H, m, ArH), 5.70-5.50 (1H, m, = CH), 3.80 (1H, m, NCHCH 3 ), 2.94 (3H, m, NCH 2 ) , 2.61 (1H, m, NCH), 2.1-1.0 (15H, m, CH 2 and CH 3 ).
    [320] Use Example B: Base Catalysis Using Monomeric Compounds
    [321] Example B1-B4
    [322] UV-initiated Michael addition reaction
    [323] 7.4 · 10 −5 mol of photoinitiator (potential amidine base) is dissolved in a mixture of dimethyl malonate and n-butyl acrylate (200 mg corresponding to 1: 1, 7.4 · 10 −4 mol) in a quartz vessel. The mixture is irradiated at a distance of 30 cm with a high pressure mercury lamp (200 W). Monitor the conversion rate as a function of time. The results are shown in Table 1.
    [324] ExampleInitiators from the Examples% Conversion after exposure time 0 minutes 10 minutes 20 minutes 30 minutes 40 minutes 60 minutes 120 minutes B1A10-6-3868100 B2A20-8-355894 B3A40-16-5075100 B4A50196491100 B5A603167818994100 B6A804094100 B7A90568994100 B8A1007498100 B9A11076088100 B10A12018336183100B11A130117694100
    [325] Use Example C: Base catalyst comprising oligomer / polymer compound
    [326] Example C1
    [327] Preparation of urethane acrylates based on isophorone diisocyanate and 4-hydroxybutyl acrylate
    [328] The reaction is carried out under a nitrogen atmosphere and all commercial chemicals used are used without further purification.
    [329] 1566.8 g isophorone diisocyanate (NCO 13.78 mol), 2.3 g dibutyltin dilaurate, 2.3 g 2,5-di-tert-butyl-p-cresol and 802.8 g butyl acetate are equipped with a condenser and a dropping device. Fill a three necked flask. Anhydrous nitrogen is bubbled through the reaction mixture and the temperature is slowly raised to 60 ° C. 1987 g (13.78 mol) of 4-hydroxybutyl acrylate are added while the reaction solution is slowly warmed to 80 ° C. The temperature is maintained at 80 ° C. and the dropping device is flushed with butyl acetate (86.6 g). The reaction is monitored by titration of the residual amount of isocyanate and terminated if the isocyanate content is less than 0.2% based on the solids content. The reaction product obtained has the following physical properties:
    [330] Residual 4-hydroxybutyl acrylate: <0.002% based on solids (HPLC analysis)
    [331] Color: 〈〈 Gardner 1
    [332] Viscosity: 43 cPa s (20 ° C)
    [333] Solids content: 79.3% (1 hour at 140 ° C)
    [334] GPC Data (Polystyrene Standard): Mn 778, Mw 796, d = 1.02
    [335] Preparation of Malonate Polyester
    [336] The reaction is carried out under a nitrogen atmosphere and all commercial chemicals used are used without further purification.
    [337] In a reaction vessel equipped with a stirrer and a condenser, 1045 g of 1,5-pentanediol, 1377.4 g of diethyl malonate and 242.1 g of xylene are carefully refluxed. The maximum temperature of the reaction mixture is 196 ° C. while maintaining the temperature at the top of the condenser at 79 ° C. In this method 862 g of ethanol are distilled off corresponding to a conversion of 97.7%. Xylene is stripped under vacuum at a temperature of 200 ° C. The resulting polymer has a solids content of 98.6%, a viscosity of 2710 mPa s and an acid value of 0.3 mg KOH / g based on the solids content. Mn is 1838, Mw is 3186 and the color is 175 based on the APHA scale ("Hazen color number" -ISO 6271, American Health Association).
    [338] UV Curing
    [339] 6.4 × 10 −5 mol of photoinitiator from Example A5 is dissolved in a 1.3: 1 mixture (400 mg total) of the urethane acrylate and malonate polyesters described above. A 50 μm thick film was stretched on the glass plate and exposed at a distance of 30 cm using a high pressure mercury lamp 200W. The polymer film becomes viscous after 120 minutes.
    权利要求:
    Claims (23)
    [1" claim-type="Currently amended] An organic compound having a molecular weight of less than 1,000, comprising at least one structural unit of formula (I).
    Formula I

    In the above formula,
    R 1 is an aromatic or heteroaromatic radical capable of absorbing light at wavelengths of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds.
    [2" claim-type="Currently amended] An organic compound wherein the structural unit of formula I comprises a compound of formula II.
    Formula II

    In the above formula,
    R 1 is an aromatic or heteroaromatic radical capable of absorbing light at a wavelength of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds,
    R 2 and R 3 are independently of each other hydrogen, C 1-18 alkyl, C 3-18 alkenyl, C 3-18 alkynyl or phenyl,
    When R 2 is hydrogen or C 1-18 alkyl, R 3 is further a group —CO—R 14 ,
    R 14 is C 1-18 alkyl or phenyl,
    R 5 is C 1-18 alkyl or NR 15 R 16 ,
    R 4 , R 6 , R 7 , R 15 and R 16 are independently of each other hydrogen or C 1-18 alkyl,
    R 4 and R 6 together form a C 2-12 alkylene bridge, or
    R 5 and R 7 , independently of R 4 and R 6 , together form a C 2-12 alkylene bridge,
    When R 5 is NR 15 R 16 , R 16 and R 7 together form a C 2-12 alkylene bridge,
    R 17 is hydrogen or C 1-18 alkyl,
    R 18 is hydrogen, C 1-18 alkyl, or C 1-18 alkyl, vinyl, C 3-18 alkenyl, C 3-18 alkynyl, C 1-18 haloalkyl, phenyl, NO 2 , OH, CN, OR 10 , SR 10 , C (O) R 11 , C (O) OR 12 or phenyl substituted by halogen,
    R 10 , R 11 and R 12 are hydrogen or C 1-18 alkyl.
    [3" claim-type="Currently amended] The method of claim 1,
    R 1 is unsubstituted or C 1-18 alkyl, C 3-18 alkenyl, C 3-18 alkynyl, C 1-18 haloalkyl, NO 2 , NR 8 R 9 , N 3 , OH, CN, OR 10 Phenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro substituted one or more times by SR 10 , C (O) R 11 , C (O) OR 12 or halogen -2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, tiathrenyl, dibenzo Furyl, chromenyl, xanthenyl, thioxanthyl, phenoxatiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolinyl, isoindoleyl, indolyl, Indazolyl, furinyl, quinolinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, putridinyl, carbazolyl, β-carbolinyl , Phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazole , Furanyl janil, terphenyl, stilbenyl, fluorenyl or a carbonyl Fe noksa possess, or a radical of formula A or B,
    An organic compound wherein R 8 , R 9 , R 10 , R 11 and R 12 are hydrogen or C 1-18 alkyl.
    Formula A

    Formula B

    In the above formula,
    R 13 is C 1-18 alkyl, C 2-18 alkenyl, C 2-18 alkynyl, C 1-18 haloalkyl, NO 2 , NR 8 R 9 , OH, CN, OR 10 , SR 10 , C ( O) R 11 , C (O) OR 12 or halogen,
    n is 0, or a number of 1, 2 or 3.
    [4" claim-type="Currently amended] Organic compound according to claim 2, wherein R 2 and R 3 are independently of each other hydrogen or C 1-6 alkyl, in particular C 1-4 alkyl.
    [5" claim-type="Currently amended] The organic compound of claim 2, wherein R 4 and R 6 together form a C 2-6 alkylene bridge.
    [6" claim-type="Currently amended] The compound of claim 2, wherein R 5 and R 7 form a C 2-6 alkylene bridge, or when R 5 is NR 15 R 16 , R 16 and R 7 together form a C 2-6 alkylene bridge Organic compounds.
    [7" claim-type="Currently amended] The method of claim 2,
    R 1 is phenyl or naphthyl unsubstituted or substituted one or more times by CN, NR 8 R 9 , N 3 , NO 2 , CF 3 , SR 10 or OR 10 , or a radical of formula A,
    n is 0,
    R 8 , R 9 and R 10 are hydrogen or C 1-6 alkyl,
    R 2 and R 3 are hydrogen or C 1-6 alkyl,
    R 4 and R 6 together form a C 2-6 alkylene bridge,
    R 5 and R 7 together form a C 2-6 alkylene bridge,
    R 17 is hydrogen,
    An organic compound of Formula II wherein R 18 is hydrogen or C 1-4 alkyl.
    Formula A

    [8" claim-type="Currently amended] A method according to claim 1, comprising a first step of reacting a compound having a structural unit of formula III with a compound having a structural unit of formula IV and a second step of reacting the obtained reaction product with a phosphonium salt A process for preparing a compound having a structural unit of formula (I).
    Formula I

    Formula III

    Formula IV

    In the above formula,
    R 1 is an aromatic or heteroaromatic radical capable of absorbing light at a wavelength of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds,
    Halogen is F, Cl, Br or I.
    [9" claim-type="Currently amended] A process for preparing a compound of formula (II) comprising a first step of reacting a compound of formula (V) with a compound of formula (VI) and a second step of reacting the obtained reaction product with a phosphonium salt of formula (VII-1) .
    Formula II

    Formula V

    Formula VI

    Formula VII-1
    R 17 R 18 CH-P (phenyl) 3 + X -
    In the above formula,
    R 1 is an aromatic or heteroaromatic radical capable of absorbing light at a wavelength of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds,
    R 2 and R 3 are independently of each other hydrogen, C 1-18 alkyl, C 3-18 alkenyl, C 3-18 alkynyl or phenyl,
    When R 2 is hydrogen or C 1-18 alkyl, R 3 is further a group —CO—R 14 ,
    R 14 is C 1-18 alkyl or phenyl,
    R 5 is C 1-18 alkyl or NR 15 R 16 ,
    R 4 , R 6 , R 7 , R 15 and R 16 are independently of each other hydrogen or C 1-18 alkyl,
    R 4 and R 6 together form a C 2-12 alkylene bridge, or
    R 5 and R 7 , independently of R 4 and R 6 , together form a C 2-12 alkylene bridge,
    When R 5 is NR 15 R 16 , R 16 and R 7 together form a C 2-12 alkylene bridge,
    R 17 is hydrogen or C 1-18 alkyl,
    R 18 is hydrogen, C 1-18 alkyl, or C 1-18 alkyl, vinyl, C 3-18 alkenyl, C 3-18 alkynyl, C 1-18 haloalkyl, phenyl, NO 2 , OH, CN, OR 10 , SR 10 , C (O) R 11 , C (O) OR 12 or phenyl substituted by halogen,
    R 10 , R 11 and R 12 are hydrogen or C 1-18 alkyl,
    Halogen is F, Cl, Br or I,
    X is F, Cl, Br, I or tetrafluoroborate.
    [10" claim-type="Currently amended] A process for preparing a compound of formula VII, comprising exposing the compound of formula II according to claim 2 to light having a wavelength of 200 to 650 nm.
    Formula VII

    Formula II

    In the above formula,
    R 1 is an aromatic or heteroaromatic radical capable of absorbing light at a wavelength of 200 to 650 nm to decompose adjacent carbon-nitrogen bonds,
    R 2 and R 3 are independently of each other hydrogen, C 1-18 alkyl, C 3-18 alkenyl, C 3-18 alkynyl or phenyl,
    When R 2 is hydrogen or C 1-18 alkyl, R 3 is further a group —CO—R 14 ,
    R 14 is C 1-18 alkyl or phenyl,
    R 5 is C 1-18 alkyl or NR 15 R 16 ,
    R 4 , R 6 , R 7 , R 15 and R 16 are independently of each other hydrogen or C 1-18 alkyl,
    R 4 and R 6 together form a C 2-12 alkylene bridge, or
    R 5 and R 7 , independently of R 4 and R 6 , together form a C 2-12 alkylene bridge,
    When R 5 is NR 15 R 16 , R 16 and R 7 together form a C 2-12 alkylene bridge,
    R 17 is hydrogen or C 1-18 alkyl,
    R 18 is hydrogen, C 1-18 alkyl, or C 1-18 alkyl, vinyl, C 3-18 alkenyl, C 3-18 alkynyl, C 1-18 haloalkyl, phenyl, NO 2 , OH, CN, OR 10 , SR 10 , C (O) R 11 , C (O) OR 12 or phenyl substituted by halogen,
    R 10 , R 11 and R 12 are hydrogen or C 1-18 alkyl.
    [11" claim-type="Currently amended] A) at least one compound having a structural unit of formula I according to claim 1 and
    B) A composition comprising one or more organic compounds capable of base-catalyzed addition or substitution reactions.
    [12" claim-type="Currently amended] The composition of claim 11 wherein component (B) is an anionic polymerizable or crosslinkable organic material.
    [13" claim-type="Currently amended] 12. The composition of claim 11 wherein component (B)
    a) an acrylate copolymer having an alkoxysilane or alkoxysiloxane side chain group,
    b) two-component systems comprising hydroxyl-containing polyacrylates, polyesters and / or polyethers and aliphatic or aromatic polyisocyanates,
    c) two-component systems comprising functional polyacrylates and polyepoxides in which the polyacrylate contains carboxyl and anhydride groups,
    d) two-component systems comprising fluorine-modified or silicone-modified hydroxyl-containing polyacrylates, polyesters and / or polyethers and aliphatic or aromatic polyisocyanates,
    e) two-component systems comprising (poly) ketimines and aliphatic or aromatic polyisocyanates,
    f) two-component systems comprising (poly) ketimines and unsaturated acrylate resins or acetoacetate resins or methyl α-acrylamidomethylglycolates,
    h) two-component systems comprising (poly) oxazolidines containing anhydride groups and polyacrylates or unsaturated acrylate resins or polyisocyanates,
    i) a two-component system comprising an epoxy-functional polyacrylate and a carboxyl- or amino-containing polyacrylate,
    l) polymers based on allyl glycidyl ether,
    m) two-component systems comprising (poly) alcohols and (poly) isocyanates and
    n) a composition which is one of a two-component system comprising an α, β-ethylenically unsaturated carbonyl compound and a polymer containing an activated CH 2 group.
    [14" claim-type="Currently amended] The composition of claim 11 wherein component B) is an epoxy resin or a mixture of different epoxy resins.
    [15" claim-type="Currently amended] The composition of claim 11 wherein component A) is present in an amount of from 0.01 to 10% by weight, based on component B).
    [16" claim-type="Currently amended] The composition of claim 11 further comprising a sensitizer selected from the group consisting of thioxanthone, oxazine, acridine, phenazine and rhodamine.
    [17" claim-type="Currently amended] A method for carrying out a base-catalyzed reaction comprising irradiating a composition according to claim 11 with light having a wavelength of 200 to 650 nm.
    [18" claim-type="Currently amended] The method of claim 17, wherein the heating is during or after the light exposure.
    [19" claim-type="Currently amended] Use of the organic compound according to claim 1 as photoinitiator for photochemically induced base-catalyzed addition or substitution reactions.
    [20" claim-type="Currently amended] 20. Use of an organic compound according to claim 19 for producing a coating, molding composition or photostructured layer.
    [21" claim-type="Currently amended] A coated substrate having at least one surface coated with the composition according to claim 11.
    [22" claim-type="Currently amended] Polymerized or crosslinked composition according to claim 11.
    [23" claim-type="Currently amended] 18. The method of claim 17, wherein the coating, molding composition or photostructured layer is made.
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    同族专利:
    公开号 | 公开日
    EP0970085A1|2000-01-12|
    ZA9802233B|1998-09-18|
    DE69806739D1|2002-08-29|
    KR100527614B1|2005-11-15|
    CA2283446C|2008-05-06|
    WO1998041524A1|1998-09-24|
    DE69806739T2|2003-03-13|
    US6087070A|2000-07-11|
    CN1128799C|2003-11-26|
    BR9808899B1|2009-12-01|
    CA2283446A1|1998-09-24|
    AU720834B2|2000-06-15|
    TW466255B|2001-12-01|
    CN1251103A|2000-04-19|
    JP2001515500A|2001-09-18|
    JP4308326B2|2009-08-05|
    BR9808899A|2000-08-01|
    AU7032798A|1998-10-12|
    EP0970085B1|2002-07-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-03-18|Priority to CH65297
    1997-03-18|Priority to CH652/97
    1998-03-07|Application filed by 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러, 시바 스페셜티 케미칼스 홀딩 인크.
    1998-03-07|Priority to PCT/EP1998/001346
    2000-12-26|Publication of KR20000076332A
    2005-11-15|Application granted
    2005-11-15|Publication of KR100527614B1
    优先权:
    申请号 | 申请日 | 专利标题
    CH65297|1997-03-18|
    CH652/97|1997-03-18|
    PCT/EP1998/001346|WO1998041524A1|1997-03-18|1998-03-07|PHOTOACTIVATABLE NITROGEN-CONTAINING BASES BASED ON α-AMINO ALKENES|
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