US 6,190,824 B1Granted

Photosensitive composition

AssigneeFuji Photo Film Co., Ltd.

InventorsYuuichi Fukushige, Masanobu Takashima

Life of this patent

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Abstract

Disclosed is a photosensitive composition useful for preparation of various imaging materials and having good stability over time and a high sensitivity. The composition comprises a polymerizable monomer, a photopolymerization initiator, and a diazonium salt having a specific, borate anion portion represented by the general formula (I-1) or (I-2) given below, or the like. A combination of a specific borate compound and a general-purpose diazonium salt can also be used in place of the above-mentioned diazonium salt.

Claims2

Dependent claims

A photosensitive composition comprising a polymerizable monomer, a photopolymerization initiator, and a diazonium salt compound containing an anion portion represented by the general formula (I-1), (I-2), or (II) given below:

wherein, in the general formulas (I-1) and (I-2), R1 and R2 each independently represent a phenyl group, an aromatic hydrocarbyl group that may contain a heteroatom and is a group other than the phenyl group, an alkyl group that has 1 to 20 carbon atoms and is substituted by —Si(R9)(R10)(R11), or a group represented by the formulae (ii), (iia), or (iib) given below, and the phenyl group and the aromatic hydrocarbyl group may each be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11) B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN, so that at least one ortho position of the phenyl group and the aromatic hydrocarbyl group is substituted by a substituent group;
and
R2a represents a phenylene group or another divalent aromatic hydrocarbyl group that may contain a heteroatom, wherein the aromatic hydrocarbyl group may be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, CN, and a group represented by the formula (a) given below:
wherein, in the formula (a), Ra represents an alkylene group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted alkylene group bearing a substituent selected from the group consisting of R6OCO, CN, and a halogen atom;
and
in the formulae (ii), (iia), and (iib), the aromatic ring may be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN;
and Y represents (CH2)n, CH═CH, CO, NR5, O, S(O)p, or a group represented by the formula given below:
wherein, R3 represents an alkyl group that has 1 to 20 carbon atoms and is substituted by —Si(R9)(R10)(R11), a phenyl group, or an aromatic hydrocarbyl group that is other than the phenyl group and may contain a heteroatom, and the phenyl group and the aromatic hydrocarbyl group may be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN;
and
R4 represents a group selected from the group consisting of a phenyl group, an aromatic hydrocarbyl group that is other than the phenyl group and may contain a heteroatom, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and a group represented by the formula (a) or (b) given below:
wherein, in the formulas (a) and (b), Ra and Rb each independently represent an alkylene group or a as substituted alkylene group bearing a substituent selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
the substituent group represented by R4 may be substituted by a group selected from the group consisting of OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN;
n is an integer of 0, 1, or 2;
m is an integer of 2 or 3;
p is an integer of 0, 1, or 2;
and q is an integer of 0 or 1;
R5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a group represented by the formula (a), wherein the phenyl group and the group represented by the formula (a) may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
wherein R6 represents an alkyl group having 1 to 12 carbon atoms and a phenyl group, each of which may be substituted by a halogen atom;
R7 and R8 each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a group represented by the formula (a), wherein the phenyl group and the group represented by the formula (a) may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
and R7 and R8 may form together with a nitrogen atom to which R7 and R8 are linked a 5-membered or 6-membered ring, which may contain O or S;
R9, R10 and R11 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a group represented by the formula (a), wherein the phenyl group and the group represented by the formula (a) may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
R12 and R13 each represent the same groups as those defined for R9˜R11, provided R12 and R13 may form together with the boron atom to which R12 and R13 are linked a 5-membered or a 6-membered ring, which may contain O or S;
R14, R15 and R16 each independently represent a group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, and a group represented by the formula (a), wherein the alkyl group, the alkenyl group, and the cycloalkyl group may be substituted by R6OCO or CN;
and the phenyl group and the group represented by the formula (a) maybe substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
and
E represents P(R14)(R15), S(R6), or N(R7)(R8), wherein R6˜R15 are as previously defined;
and
wherein, in the general formula (II), R1 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a group represented by the formula (a) or (b) given below, and the substituent group represented by R1 may contain in the structure thereof O, S(O)p, or NR5 as a bridging group;
wherein, in the formulas (a) and (b), Ra and Rb each independently represent an alkylene group or a substituted alkylene group bearing a substituent selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom, wherein R6 is as previously defined;
the substituent group represented by R1 may be further substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, OR6, R7S(O)p, R7SO3, N(R8)(R9), Si(R10)(R11)(R12), B(R13)(R14), a halogen atom, and (R15)(R16)P(O)q;
and
R2˜R4 each independently represent a phenyl group or a biphenyl group;
wherein the substituent groups represented by R2˜R4 may be further substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms (this alkyl group may be substituted by OR6, N(R8)(R9), or a halogen atom), OR6, R7S(O)p, R7SO3, N(R8)(R9), Si(R10)(R11)(R12), B(R13)(R14), a halogen atom, (R15)(R16)P(O)q, and a group represented by the formula given below:
wherein, the sum of Hammett σ constants of R2˜R4 is +0.36˜+2.58;
X represents O, S, or NR21;
R5 may be a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or the substituent group represented by the formula (a), wherein the substituent group represented by the formula (a) may have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R6˜R7 each independently represent a group selected from the group consisting of an alkyl group, which has 1 to 12 carbon atoms and may be substituted by a halogen atom, a phenyl group, and the group represented by the formula (a), wherein the phenyl group and the substituent group represented by the formula (a) may each have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R8˜R16 each independently represent a group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, and the group represented by the formula (a), wherein the phenyl group and the substituent group represented by the formula (a) may each have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R8˜R9 may form together with the nitrogen atom to which R8 and R9 are linked an aliphatic 6-membered ring, which may further contain another heteroatom, such as O or S;
R17˜R20 each independently represent a group selected from the group consisting of hydrogen, an alkyl group that has 1 to 12 carbon atoms and may be substituted by an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and a group represented by the formula (a), wherein the phenyl group and the substituent group represented by the formula (a) may each have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R21 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms;
R22˜R24 each independently represent a group selected from the group consisting of:
hydrogen;
an alkyl group that has 1 to 12 carbon atoms and may be substituted by an alkoxy group having 1 to 12 carbon atoms, an hydroxy group, or a halogen atom;
and a phenyl group that may be substituted by an alkoxy group having 1 to 12 carbon atoms, an hydroxy group, or a halogen atom;
and
q is an integer of 0 to 1, and r is an integer of 0 to 5.

44 more elements

Dependencies are inferred from the claim text.

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Abstract

wherein, in the general formulas (I-1) and (I-2), R1 and R2 each independently represent a phenyl group, an aromatic hydrocarbyl group that may contain a heteroatom and is a group other than the phenyl group, an alkyl group that has 1 to 20 carbon atoms and is substituted by —Si(R9)(R10)(R11), or a group represented by the formulae (ii), (iia), or (iib) given below, and the phenyl group and the aromatic hydrocarbyl group may each be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11) B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN, so that at least one ortho position of the phenyl group and the aromatic hydrocarbyl group is substituted by a substituent group;
and
R2a represents a phenylene group or another divalent aromatic hydrocarbyl group that may contain a heteroatom, wherein the aromatic hydrocarbyl group may be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, CN, and a group represented by the formula (a) given below:
wherein, in the formula (a), Ra represents an alkylene group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted alkylene group bearing a substituent selected from the group consisting of R6OCO, CN, and a halogen atom;
and
in the formulae (ii), (iia), and (iib), the aromatic ring may be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN;
and Y represents (CH2)n, CH═CH, CO, NR5, O, S(O)p, or a group represented by the formula given below:
wherein, R3 represents an alkyl group that has 1 to 20 carbon atoms and is substituted by —Si(R9)(R10)(R11), a phenyl group, or an aromatic hydrocarbyl group that is other than the phenyl group and may contain a heteroatom, and the phenyl group and the aromatic hydrocarbyl group may be substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN;
and
R4 represents a group selected from the group consisting of a phenyl group, an aromatic hydrocarbyl group that is other than the phenyl group and may contain a heteroatom, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and containing O, S(O)p or NR5, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and a group represented by the formula (a) or (b) given below:
wherein, in the formulas (a) and (b), Ra and Rb each independently represent an alkylene group or a as substituted alkylene group bearing a substituent selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
the substituent group represented by R4 may be substituted by a group selected from the group consisting of OR6, R6S(O)p, R6SO3, N(R7)(R8), R6OCO, CON(R7)(R8), COR9, Si(R9)(R10)(R11), Sn(R9)(R10)(R11), B(R12)(R13), a halogen atom, (R9)(R10)P(O)q, and CN;
n is an integer of 0, 1, or 2;
m is an integer of 2 or 3;
p is an integer of 0, 1, or 2;
and q is an integer of 0 or 1;
R5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a group represented by the formula (a), wherein the phenyl group and the group represented by the formula (a) may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
wherein R6 represents an alkyl group having 1 to 12 carbon atoms and a phenyl group, each of which may be substituted by a halogen atom;
R7 and R8 each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a group represented by the formula (a), wherein the phenyl group and the group represented by the formula (a) may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
and R7 and R8 may form together with a nitrogen atom to which R7 and R8 are linked a 5-membered or 6-membered ring, which may contain O or S;
R9, R10 and R11 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a group represented by the formula (a), wherein the phenyl group and the group represented by the formula (a) may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
R12 and R13 each represent the same groups as those defined for R9˜R11, provided R12 and R13 may form together with the boron atom to which R12 and R13 are linked a 5-membered or a 6-membered ring, which may contain O or S;
R14, R15 and R16 each independently represent a group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, and a group represented by the formula (a), wherein the alkyl group, the alkenyl group, and the cycloalkyl group may be substituted by R6OCO or CN;
and the phenyl group and the group represented by the formula (a) maybe substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom;
and
E represents P(R14)(R15), S(R6), or N(R7)(R8), wherein R6˜R15 are as previously defined;
and
wherein, in the general formula (II), R1 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a group represented by the formula (a) or (b) given below, and the substituent group represented by R1 may contain in the structure thereof O, S(O)p, or NR5 as a bridging group;
wherein, in the formulas (a) and (b), Ra and Rb each independently represent an alkylene group or a substituted alkylene group bearing a substituent selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R6OCO, CN, and a halogen atom, wherein R6 is as previously defined;
the substituent group represented by R1 may be further substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, OR6, R7S(O)p, R7SO3, N(R8)(R9), Si(R10)(R11)(R12), B(R13)(R14), a halogen atom, and (R15)(R16)P(O)q;
and
R2˜R4 each independently represent a phenyl group or a biphenyl group;
wherein the substituent groups represented by R2˜R4 may be further substituted by a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms (this alkyl group may be substituted by OR6, N(R8)(R9), or a halogen atom), OR6, R7S(O)p, R7SO3, N(R8)(R9), Si(R10)(R11)(R12), B(R13)(R14), a halogen atom, (R15)(R16)P(O)q, and a group represented by the formula given below:
wherein, the sum of Hammett σ constants of R2˜R4 is +0.36˜+2.58;
X represents O, S, or NR21;
R5 may be a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or the substituent group represented by the formula (a), wherein the substituent group represented by the formula (a) may have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R6˜R7 each independently represent a group selected from the group consisting of an alkyl group, which has 1 to 12 carbon atoms and may be substituted by a halogen atom, a phenyl group, and the group represented by the formula (a), wherein the phenyl group and the substituent group represented by the formula (a) may each have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R8˜R16 each independently represent a group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, and the group represented by the formula (a), wherein the phenyl group and the substituent group represented by the formula (a) may each have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R8˜R9 may form together with the nitrogen atom to which R8 and R9 are linked an aliphatic 6-membered ring, which may further contain another heteroatom, such as O or S;
R17˜R20 each independently represent a group selected from the group consisting of hydrogen, an alkyl group that has 1 to 12 carbon atoms and may be substituted by an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and a group represented by the formula (a), wherein the phenyl group and the substituent group represented by the formula (a) may each have on the phenyl ring thereof a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom;
R21 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms;
R22˜R24 each independently represent a group selected from the group consisting of:
hydrogen;
an alkyl group that has 1 to 12 carbon atoms and may be substituted by an alkoxy group having 1 to 12 carbon atoms, an hydroxy group, or a halogen atom;
and a phenyl group that may be substituted by an alkoxy group having 1 to 12 carbon atoms, an hydroxy group, or a halogen atom;
and
q is an integer of 0 to 1, and r is an integer of 0 to 5.

44 more elements