Patent ES-8601494-A1 (ES)
Title: Photopolymerisable composition, material coated therewith, and process for obtaining relief images.
IPC: C08G73/10
Filed: 1984-02-10
Abstract: Compsn. contains, in addn. to standard additives, (a) a pre-polymer contg. identical or different structural units of formula (I) which reacts, on heating, to a heat-stable ring structure, (b) a photoinitiator and opt. (c) an acrylic- or methacrylic acid ester, allyl ether or -ester or a partial ester of these acids with a polyol. - Novelty consists in using, as photoinitiator (b), a metallocene of formula ToR1R2R3R4 (II) R1 each = opt. substd. cyclopentadienyl or indenyl, R1 together = an opt. substd. gp. of formula (III). R2 = carboxylic or a 5- or 6-membered heterocyclic aromatic ring, substd. by anF atom in at least one of the 2 o-positions to the metal-C bond and opt. contg. further substits. R3 = 3-5 C alkynyl, opt. substd. phenyl- 3-5 C-alkynyl, N3, CN, Si(R7)3 or Sn(R7)3, or is an R2 gp., or R2 + R3 = a gp. of formula -Q-Y-Q- (IV) R7 = 1-12 C alkyl, 5-12 C cycloalkyl, 6-16 C aryl or 7-16 C aralkyl X = -(CH2)n- with n = 1, 2 or 3 2-12 C alkylidene, 5-7 C ring C atom-contg. cycloalkylidene, Si(R7)2 or Sn(R7)2 Q = carbocyclic or heterocyclic 5- or 6-membered aromatic ring, provided the 2 bonds are each in the 0-position to Gp. Y and the m-position to Y is substd. by F, and Q may be further substd. Y = CH2, 2-12 C alkylidene, 5-7 ring C-contg. cycloalkylidene, a covalent bond, NR7, O, S, SO, SO2, CO, Si(R7)2. In the prepolymer units (I), R4 = a tetravalent aromatic gp. after removing 4 functional gps., provided that 2 functional gps. are adjacent and arrow denotes structural isomers R5 = divalent, aliphatic, cycloaliphaticor mono- or poly-nuclear aromatic gp., and aromatic R5 gps. can contain a -CONH2 orCOOH gp. in the o-position to the bond to Z' R6 = gp. contg. a photopolymerisable olefinic double bond Z = covalent or ionic bonding agent Z' = covalent member, provided that Z and Z' form a heat-stable ring structure opt. together with the -CONH2 or -COOH gps. in R5, with the dissociation of R6, on heating EPAB- EP-119162 B A photopolymerisable composition which comprises in addition to conventional ingredients, (a) a prepolymer which contains identical or different recurring structural elements of the formula (I) and which reacts, when heated, to form a thermally stable ring structure, (b) a photoinitiator, and optionally (c) an ester of acrylic or methacrylic acid, an allyl ether or an allyl ester or a partial ester of said acids with a polyol, wherein the photoinitiator (b) is a metallocene of the formula (II) wherein both R1s independently of one another are unsubstituted or substituted cyclopentadienyl-, indenyl-, or both R1s together are an unsubstituted or substituted radical of the formula (III) R2 is a carbocyclic or 5- or 6-membered heterocyclic aromatic ring which is substituted in at least one of the two ortho-positions relative to the metal-carbon bond by a fluorine atom and which may contain further substituents, R3 is C3-C5 alkynyl, substituted or unsubstituted phenyl-alkynyl containing 3 to 5 carbon atoms in the alkynyl moiety, N3, CN, Si(R7)3 or Sn(R7)3, or has the meaning of R2, or R2 and R3 together are a radical of the formula -Q-Y-G-(IV) R4 is a tetravalent aromatic radical after removal of four functional groups, with any two functional groups being adjacent and an arrow denoting structural isomers, R5 is a divalent aliphatic, cycloaliphatic or mononuclear or polynuclear aromatic radical, and aromatic radicals R5 may contain a -CONH2 or -COOH group in the ortho-position to the bond to Z', R6 is a radical containing a photopolymerisable olefinic double bond, R7 is C1-C12 alkyl, C5-C12 cycloalkyl, C6-C16 aryl or C7-C16 aralkyl, Z is a covalent or ionic bond and Z' is a covalent bond with the proviso that, on heating the photopolymerisable composition to remove the radical R6, Z and Z', optionally together with -CONH2 or -COOH groups contained in R5, form a thermally stable ring structure, X is (CH2)n, in which n is 1, 2 or 3, alkylidene containing 2 to 12 carbon ato - EP-119162 B Compsn. contains, in addn. to standard additives, (a) a pre-polymer contg. identical or different structural units of formula (I) which reacts, on heating, to a heat-stable ring structure, (b) a photoinitiator and opt. (c) an acrylic- or methacrylic acid ester, allyl ether or -ester or a partial ester of these acids with a polyol. - Novelty consists in using, as photoinitiator (b), a metallocene of formula ToR1R2R3R4 (II) R1 each = opt. substd. cyclopentadienyl or indenyl, R1 together = an opt. substd. gp. of formula (III). R2 = carboxylic or a 5- or 6-membered heterocyclic aromatic ring, substd. by anF atom in at least one of the 2 o-positions to the metal-C bond and opt. contg. further substits. R3 = 3-5 C alkynyl, opt. substd. phenyl- 3-5 C-alkynyl, N3, CN, Si(R7)3 or Sn(R7)3, or is an R2 gp., or R2 + R3 = a gp. of formula -Q-Y-Q- (IV) R7 = 1-12 C alkyl, 5-12 C cycloalkyl, 6-16 C aryl or 7-16 C aralkyl X = -(CH2)n- with n = 1, 2 or 3 2-12 C alkylidene, 5-7 C ring C atom-contg. cycloalkylidene, Si(R7)2 or Sn(R7)2 Q = carbocyclic or heterocyclic 5- or 6-membered aromatic ring, provided the 2 bonds are each in the 0-position to Gp. Y and the m-position to Y is substd. by F, and Q may be further substd. Y = CH2, 2-12 C alkylidene, 5-7 ring C-contg. cycloalkylidene, a covalent bond, NR7, O, S, SO, SO2, CO, Si(R7)2. In the prepolymer units (I), R4 = a tetravalent aromatic gp. after removing 4 functional gps., provided that 2 functional gps. are adjacent and arrow denotes structural isomers R5 = divalent, aliphatic, cycloaliphaticor mono- or poly-nuclear aromatic gp., and aromatic R5 gps. can contain a -CONH2 orCOOH gp. in the o-position to the bond to Z' R6 = gp. contg. a photopolymerisable olefinic double bond Z = covalent or ionic bonding agent Z' = covalent member, provided that Z and Z' form a heat-stable ring structure opt. together with the -CONH2 or -COOH gps. in R5, with the dissociation of R6, on heating USAB- US4548891 A A photopolymerisable compsn. consists of A) pref. 50-97.5 wt.% of a prepolymer contg. (different)structures (1), forming a thermostable ring structure on heating, B) pref. 0.1-20 wt.% of a metallocene TiR2R'R" and pref. also C), esp. 2.5-50 wt.%, of an ester of (meth)acrylic acid, an allyl ester or ether or a partial ester of the above acids. - Each R is independently (substd). cyclopentadienyl-, indenyl- or together form a (substd.) radical (2) R' is a carbocyclyl or 5 or 6 membered heterocyclyl substd. by F in at least 1 of the positions o- to the metal-C bond R" is R', 3-5C alkynyl, (substd.) phenyl (3-5C) alkynyl, N3,CN, Si(X')3 or Sn(X')3 R' and R" together can form -X"-Y-X"- Q is a tetravalent aromatic radical after removal of 4 functional gps., any 2 functional gps. are adjacent and the arrow denotes structural isomers Q' is a divalent (cyclo)aliphatic or mono- or polycyclic aromatic radical contg. -CONH2 or -COOH o- to the bond to Z' Q" is a radical contg. a photopolymerisable double bond X is (CH2)n, 2-12C alkylidene, 5-7 ring C cycloalkylidene, Si(X')2 or Sn(X')2 X' is 1-12C alkyl, 5-12C cycloalkyl, 6-16C aryl or 7-16C aralkyl X" is carbocyclyl or 5 or 6 membered heterocyclyl, each of the 2 bonds being o- to Y and each m-position to Y substd. with F,X" opt. contg. other substituents Y is CH2,2-12C alkylidene, 5-7 ring C cycloalkylidene, a direct bond, NX', O,S,SO,SO2,CO, Si(X')2 or Sn(X')2 Z is -COO-, -CONH-, -O-, -NH-, -COOH/NZ"2 or (3), where 1/1 denotes an ionic bond Z' is -CONH-, -NHCO-, NH-CO-NH- or -O-CO-NH each Z" is independently 1-6C alkyl or alkenyl. A proviso is, that on heating the compsn. to remove Q", either Z and Z' together with the CONH2 or -COOH contained in Q' form a thermostable ring system.