WO2013168824A1 - Near infrared absorptive liquid composition, near infrared cut filter using the same, method of manufacturing the same, and camera module and method of manufacturing the same - Google Patents

Near infrared absorptive liquid composition, near infrared cut filter using the same, method of manufacturing the same, and camera module and method of manufacturing the same Download PDF

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Publication number
WO2013168824A1
WO2013168824A1 PCT/JP2013/063613 JP2013063613W WO2013168824A1 WO 2013168824 A1 WO2013168824 A1 WO 2013168824A1 JP 2013063613 W JP2013063613 W JP 2013063613W WO 2013168824 A1 WO2013168824 A1 WO 2013168824A1
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group
compound
near infrared
liquid composition
formula
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PCT/JP2013/063613
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English (en)
French (fr)
Inventor
Shinichi Kanna
Seongmu BAK
Seiichi Hitomi
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Fujifilm Corporation
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Priority to CN201380024372.1A priority Critical patent/CN104272146A/zh
Priority to KR20147032280A priority patent/KR20150003830A/ko
Publication of WO2013168824A1 publication Critical patent/WO2013168824A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B11/00—Filters or other obturators specially adapted for photographic purposes

Definitions

  • the present invention relates to a near infrared absorptive liquid composition, a near infrared cut filter using the same and a method of manufacturing the same, and, a camera module and a method of manufacturing the same.
  • CCD and CMOS image sensors have been used as a solid state image sensing device for color imaging, while being incorporated into video camera, digital still camera, and mobile phone with camera function and so forth.
  • These solid state image sensing devices use, in the light receiving sections thereof, a silicon photodiode which is sensitive in the near infrared region, and therefore need luminosity correction.
  • Near infrared cut filter has often been used for this purpose.
  • Near infrared absorptive composition has been known as a material for composing such near infrared cut filter (Patent Literature 1) .
  • the near infrared absorptive composition is formed into a layer typically by vacuum evaporation, to thereby form a near infrared shielding layer.
  • a near infrared absorptive liquid composition which may be formed into a film by coating.
  • Patent Literature 1 International Patent W099/26952, Pamphlet SUMMARY OF THE INVENTION
  • the present invention was conceived to address the problems described above, and an object thereof is to provide a near infrared absorptive liquid composition which may be formed into a layer by coating, and is excellent in near infrared shielding performance.
  • the present inventors found out from our extensive investigations that the problems may be solved by using a copper phosphate compound as a near infrared absorber. More specifically, the problems were solved by the configuration ⁇ 1>, preferably by configurations ⁇ 2> to ⁇ 16> below .
  • a near infrared absorptive liquid composition comprising a copper compound, a compound having a polymerizable group, and 50 to 80% by mass of a solvent.
  • ⁇ 2> The near infrared absorptive liquid composition of ⁇ 1>, wherein the copper compound is a phosphorus-containing copper compound or copper sulfonate compound.
  • ⁇ 3> The near infrared absorptive liquid composition of ⁇ 1>, wherein the copper compound is a copper phosphate compound.
  • ⁇ 4> The near infrared absorptive liquid composition of any one of ⁇ 1> to ⁇ 3>, wherein the compound having a polymerizable group is a multifunctional monomer.
  • n respectively represents 0 to 14
  • m respectively represents 1 to 8.
  • R represents an oxyalkylene group
  • T represents an oxyalkylene group
  • the carbon terminal thereof is bound to R.
  • At least one of (R) s is a polymerizable group.
  • ⁇ 6> The near infrared absorptive liquid composition of any one of ⁇ 1> to ⁇ 4>, wherein the compound having a polymerizable group is has the polymerizable group at the side chain thereof.
  • ⁇ 7> The near infrared absorptive liquid composition of any one of ⁇ 1> to ⁇ 6>, further comprising a polymerization initiator.
  • R 2 represents a Ci_ 18 alkyl group, C 6 -i8 aryl group, Ci-18 aralkyl group, or Ci_i 8 alkenyl group, or -OR 2 represents a C4-100 polyoxyalkyl group, C4-100
  • ⁇ 11> The near infrared absorptive liquid composition of any one of ⁇ 1> to ⁇ 10>, used in the form of film coated on an image sensor for solid state image sensing device.
  • ⁇ 12> A near infrared cut filter manufactured using the near infrared absorptive liquid composition described in any one of ⁇ 1> to ⁇ 11>.
  • a camera module comprising a substrate of solid state image sensing device, and the near infrared cut filter described in ⁇ 12>, disposed on the light receiving side of the substrate of solid state image sensing device.
  • a method of manufacturing a camera module which comprises a substrate of solid state image sensing device, and a near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device, the method comprising:
  • ⁇ 15> The method of manufacturing a camera module of ⁇ 14>, wherein the film is formed on microlenses on the light receiving side of the substrate of solid state image sensing device.
  • ⁇ 16> The method of manufacturing a camera module of ⁇ 14> or ⁇ 15>, comprising curing, by irradiation of light, the film formed by coating the infrared absorptive liquid composition.
  • a near infrared absorbing layer is now formable by coating.
  • FIG. 1 A schematic cross sectional view illustrating a configuration of a camera module provided with a solid state image sensing device according to an embodiment of the present invention .
  • FIG. 2 A schematic cross sectional view illustrating a substrate of solid state image sensing device according to the embodiment of the present invention.
  • any numerical range expressed by wording "to” means a numerical range which includes the numerals placed before and after "to” as a lower limit value and an upper limit value.
  • (meth ) acrylate means acrylate and methacrylate
  • (meth) acryl means acryl and methacryl
  • (meth) acryloyl means acryloyl and methacryloyl .
  • the monomer in the context of the present invention is
  • polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • Polymerizable functional group means a group which takes part in polymerization reaction. Note, in this specification, that the term of "group (group of atoms)" preceded by neither "substituted” nor
  • alkyl group not only includes alkyl group having no substituent ( unsubstituted alkyl group) , but also alkyl group having substituent
  • Near infrared radiation in the context of the present invention means light in the wavelength range from 700 to 2500 nm.
  • the near infrared absorptive liquid composition of the present invention the near infrared cut filter, the camera module having such near infrared cut filter and such substrate of solid state image sensing device, and the method of manufacturing such camera module will be detailed below.
  • the description below on the constituents may otherwise be made on representative embodiments of the present invention, but not intended to limit the present invention to these
  • composition of the present invention characteristically contains a copper compound, a compound having a polymerizable group (occasionally referred to as “polymerizable compound”) , and 50 to 80% by mass of a solvent.
  • the copper compound used in the present invention is not specifically limited, so long as it shows a maximum absorption wavelength in the range from 700 nm to 1000 nm (near-infrared region) .
  • the copper compound used in the present invention may be a copper complex or not be a copper complex, wherein the copper complex is preferable.
  • ligand L is not specifically limited so long as it can coordinate on a copper ion.
  • the ligand include compounds having sulfonic acid, phosphoric acid, phosphate ester, phosphonic acid, phosphonate ester,
  • sulfonic acid, phosphoric acid, phosphate ester, phosphonic acid, phosphonate ester, phosphinic acid and phosphinate ester are preferable, and sulfonic acid, phosphate ester, phosphonate ester, and phosphinate ester are more preferable.
  • the copper compound used in the present invention are preferably phosphorus-containing copper compound, copper sulfonate compound, copper carboxylate compound, or copper compound represented by the formula (A) below.
  • the phosphorus-containing compound may be referred to the compounds described in O2005/030898 , from line 27 on page 5 to line 20 on page 7, the contents of which are incorporated herein by reference.
  • the copper phosphate compound used in the present invention will be detailed below.
  • composition of the present invention preferably contains a copper phosphate compound, a polymerizable compound, and 50 to 80% by mass of a solvent.
  • the composition of the present invention contains a copper phosphate compound, the content of which relative to the solid content of the composition is preferably 20 to 95% by mass, and more preferably 30 to 80% by mass.
  • the copper phosphate compound may be composed of a single species or two or more species. When the copper phosphate is composed of two or more species, the total content falls within the
  • the copper phosphate compound used in the present invention is preferably formed by using a phosphate ester compound, and more preferably by using a compound represented by the formula (1) below:
  • each R 2 represents a Ci-is alkyl group, C 6 _i 8 aryl group, Ci_i 8 aralkyl group, or Ci-ie alkenyl group, or each -OR 2 represents a C4-100 polyoxyalkyl group, C -100
  • (R 2 )s may be same with, or different from each other.
  • At least one -OR 2 preferably represents a C4-100 (meth) acryloyloxyalkyl group, or C 4 - 10 o
  • (meth) acryloylpolyoxyalkyl group and more preferably represents a C4-100 (meth) acryloyloxyalkyl group.
  • (meth) acryloylpolyoxyalkyl group preferably has 4 to 20 carbon atoms, and more preferably has 4 to 10 carbon atoms.
  • R 2 is preferably a Ci_i 8 alkyl group or C 6 -i8 aryl group, more preferably a Ci-10 alkyl group or C 6 -i 0 aryl group, furthermore preferably a C io aryl group, and particularly a phenyl group.
  • R 2 when n is 1, one of R 2 exists preferably in the form of -OR 2 which preferably represents a C4-100 (meth) acryloyloxyalkyl group, or C4-100
  • (meth) acryloylpolyoxyalkyl group and the other of R 2 preferably exists in the form of -OR 2 or represents alkyl group.
  • the copper phosphate complex exists in the form of a copper complex (copper compound) in which phosphate esters coordinate on copper as the center metal. Copper in the copper phosphate complex is a divalent copper, and may typically be produced by a reaction between a copper salt and a phosphate ester. It is therefore predicted that any near infrared absorptive compound, containing copper and the phosphate ester compound, has a copper phosphate complex formed therein.
  • the copper phosphate compound used in the present invention preferably has a molecular weight of 300 to 1,500, and more preferably 320 to 900.
  • phosphate ester compound as sources for the copper phosphate compound preferably used in the present invention will be listed below.
  • the present invention is, of course, not limited thereto.
  • R 1 and R 2 represent those in the formula below.
  • R 1 and R 2 represent those in the formula below.
  • R 1 and R 2 indicates a bonding site for an oxygen atom in the formula below.
  • JP-A-2001-354945 paragraph [0059] of correspondent U.S. Patent No. 2003/0160217 Al ) , the contents of which are incorporated herein by reference.
  • phosphonic acid products such as Phosmer M, Phosmer PE, Phosmer PP (from Unichemical Co. Ltd.) may be used.
  • R 1 represents R 1 in the formula below.
  • Tables indicates a bonding site for the COOH group in the formula below.
  • the copper compound used in the present invention may al be a compound represented by the formula (A) below: Cu(L) ni - (X) n2 Formula (A)
  • L represents a ligand which can coordinate on copper
  • X is absent, or represents a halogen atom, H 2 0, N0 3 , C10 4 , S0 4 , CN, SCN, BF 4 , PF 6 , BPh 4 (Ph represents a phenyl group) or alcohol.
  • nl and n2 independently represents an integer of 1 to 4.
  • the ligand L has a substituent which contains C, N, 0 or S as an atom capable of coordinating on copper, and more preferably has a group containing N, 0 or S having thereon lone pair(s) .
  • Preferable ligands L are synonymous to the ligands L described above.
  • the coordinatable group contained in the molecule is not only limited to a single species, but also two or more species, and may be either in a dissociated form or a non-dissociated form. If the group has a non-dissociated form, X is absent.
  • composition of the present invention contains a polymerizable compound.
  • Family of this sort of compound is widely known in this industrial field, and they may be used in the present invention without special limitation. They may have any chemical form of, for example, monomer, oligomer, prepolymer and polymer.
  • the polymerizable compound may be either monofunctional or polyfunctional , where it is preferably polyfunctional .
  • the composition may further be improved in the near infrared shielding performance and heat resistance.
  • the number of functional groups is preferably 2 to 8, although not specifically limited.
  • a first preferable embodiment of the composition of the present invention contains a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (the
  • polymerizable monomer and the polymerizable oligomer may collectively be referred to as "polymerizable monomer, etc.”, hereinafter) , as the polymerizable compound.
  • Examples of the polymeri zable monomer, etc. include unsaturated carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and preferably include ester formed between unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and amide formed between unsaturated carboxylic acid and aliphatic multi-valent amine compound.
  • Other examples usable herein include compounds obtained by replacing the above-described unsaturated carboxylic acid with unsaturated phosphonic acid, vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
  • the polymerizable monomer, etc. is also preferably a compound having at least one addition-polymerizable ethylene group, and having an ethylenic unsaturated group and showing a boiling point under normal pressure of 100°C or above.
  • monofunctional acrylate and methacrylate such as polyethylene glycol mono (meth) acrylate , polypropylene glycol
  • (meth) acrylate such as polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentylglycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth ) acrylate , hexanediol (meth) acrylate, trimethylolpropane
  • urethane (meth ) acrylates such as those described in JP-B-S 8-41708, JP-B-S50-6034 and
  • JP-A-S51-37193 polyester acrylates such as those described in JP-A-S48-64183, JP-B-S49-43191 and JP-B-S52-30 90 ; and epoxy acrylates obtained by reacting epoxy polymer with (meth) acrylic acid.
  • polyfunctional (meth) acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenic unsaturated group, such as glycidyl (meth ) acrylate .
  • preferable polymerizable monomer usable herein include compounds having a fluorene ring and two or more ethylenic polymerizable groups , and cardo polymer, such as those described in JP-A-2010-160418, JP-A-2010-129825, Japanese Patent No. 4364216 and so forth.
  • polymerizable monomer examples include the compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol, followed by conversion into (meth) acrylate, such as those represented by the formulae (1) and (2) and specifically enumerated in JP-A-H10- 62986.
  • the polymerizable monomer used in the present invention is more preferably polymerizable monomers represented by the formulae (MO-1) to (MO-5) below: [Chemical Formula 2]
  • eachn 0 to 14
  • each m 1 to 8.
  • a plurality of each of (R) s, (T) s and ( Z ) s in a single molecule may be same with, or different from each other.
  • T represents an oxyalkylene group
  • the carbon terminal thereof is bound to R.
  • At least one of (R)s represents a polymerizable group .
  • n is preferably 0 to 5, and more preferably 1 to 3.
  • m is preferably 1 to 5, and more preferably 1 to 3.
  • R preferably represents below:
  • radical polymerizable monomers represented by the formulae (MO-1) to (MO-5) are specifically exemplified by those described in paragraphs [0248] to [0251] of JP-A-2007-269779, which are also preferably used in the present invention.
  • the polymerizable monomer, etc. is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; from Nippon Kayaku Co. Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; from Nippon Kayaku Co. Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; from Nippon Kayaku Co. Ltd.), dipentaerythritol
  • hexa (meth) acrylate commercially available as KAYARAD DPHA; from Nippon Kayaku Co. Ltd.
  • structures having these (meth ) acryloyl groups bound via a ethylene glycol or propylene glycol residue are also usable .
  • the polymerizable monomer, etc. may also be a
  • any polymerizable monomer having an unreacted carboxyl group such as for the case where the ethylenic compound is a mixture as described above, may be used in its intact form, or if necessary, the ethylenic compound may be introduced with an acid group by allowing a hydroxyl group thereof to react with a non-aromatic carboxylic anhydride
  • the non-aromatic carboxylic anhydride usable herein include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.
  • the monomer having an acid group is an ester formed between an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a multifunctional monomer introduced with an acid group by allowing an unreacted hydroxyl group of an aliphatic polyhydroxy compound to react with a non-aromatic carboxylic anhydride, and is particularly such ester obtained by using pentaerythritol and/or dipentaerythritol as the aliphatic polyhydroxy compound.
  • Examples of commercially available polybasic acid-modified acrylic oligomer include Aronix Series M-305, M-510 and M-520 from Toagosei Co. Ltd.
  • the multifunctional monomer having an acid group preferably has an acid value of 0.1 to 40 mg KOH/g, and particularly 5 to 30 mg KOH/g. If the acid value of the multifunctional monomer is too small, the solubility in the process of development may degrade, whereas if it is too large, manufacturing and handling become difficult,
  • photopolymerization performance may degrade, and curing performance characterized by surface smoothness of pixels may degrade. Accordingly, when two or more species of
  • the composition also preferably contains, as the polymerizable monomer, etc., a polyfunctional monomer having a caprolactone structure.
  • the polyfunctional monomer having a caprolactone structure is not specifically limited so long as it has in the molecule thereof a caprolactone structure.
  • (meth) acrylate which is obtainable by esterifying a polyhydric alcohol such as trimethylolethane , di-trimethylolethane , trimethylolpropane , di-trimethylolpropane , pentaerythritol, di-pentaerythritol , tri-pentaerythritol , glycerin,
  • a polyhydric alcohol such as trimethylolethane , di-trimethylolethane , trimethylolpropane , di-trimethylolpropane , pentaerythritol, di-pentaerythritol , tri-pentaerythritol , glycerin,
  • R 1 represents a hydrogen atom or methyl group
  • m represents an integer of 1 or 2, and indicates an atomic bonding .
  • R 1 represents a hydrogen atom or methyl group, and Nx *" indicates an atomic bonding.
  • a single species of the polyfunctional monomer having a caprolactone structure may be used alone, or two or more species may be used in a mixed manner.
  • the polymerizable monomer, etc. in the present invention is also preferably at least one species selected from the group consisting of compounds represented by the formula (i) or (ii) below .
  • each E independently represents - ( (CH 2 ) y CH 2 0 ) - , or - ( (CH 2 ) y CH (CH 3 ) 0) -, each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, methacryloyl group, hydrogen atom, or carboxyl group.
  • the total number of acryloyl group and methacryloyl group is 3 or 4, each m independently represents an integer of 0 to 10, and the individual (m) s add up to an integer of 0 to 40. When the individual (m) s add up to 0, any one of (X) s represents a carboxyl group.
  • the total number of acryloyl group and methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the individual (n) s add up to an integer of 0 to 60. When the individual (n) s add up to 0, any one of (X) s represents a carboxyl group.
  • m preferably represents an integer of 0 to 6, and more preferably of 0 to 4.
  • the individual (m) s preferably add up to an integer of 2 to 40, more preferably to an integer of 2 to 16, and particularly to an integer of 4 to 8.
  • n preferably represents an integer of 0 to 6, and more preferably 0 to 4.
  • the individual (n) s preferably add up to an integer of 3 to 60, more preferably to an integer of 3 to 24, and particularly to an integer of 6 to 12.
  • a single species of the compound represented by the formula (i) or (ii) may be used alone, or two or more species thereof may be used in combination.
  • a compound having acryloyl groups for all of six (X) s in the formula (ii) is preferable.
  • the compound represented by the formula (i) or (ii) may be synthesized by publicly known processes, such as a process of proceeding a ring-opening addition polymerization of pentaerytyritol or dipentaerytyritol with ethylene oxide or propylene oxide to thereby combine the ring-opened skeleton, and a process of allowing, for example, (meth) acryloyl chloride to react with the terminal hydroxyl group of the ring-opened skeleton, to thereby introduce a (meth) acryloyl group.
  • the individual processes have been well-known, so that those skilled in the art will readily synthesize the compound represented by the formula (i) or (ii).
  • Examples of the polymerizable monomer, etc. represented by the formulae (i), (ii) which are commercially available include SR-494 from Sartomer, which is a tetrafunctional acrylate having four ethyleneoxy chains, DPCA-60 which is a hexafunctional acrylate having six pentylenoxy chains, and TPA-330 which is a trifunctional acrylate having three isobutylenoxy chains, the both from Nippon Kayaku Co. Ltd.
  • polymerizable monomer etc.
  • urethane acrylates described in JP-B-S48-41708 , JP-A-S51-37193, JP-B-H2-32293 and JP-B-H2-16765
  • urethane compounds having an ethylene oxide-based skeleton described in JP-B-S58-49860, JP-B-S56-1765 , JP-B-S62-39417 and JP-B-S62-39418.
  • an addition polymerizable monomer having in the molecule thereof an amino structure or sulfide structure, described in JP-A-S63-277653, JP-A-S 63-260909 and
  • Examples of the polymerizable monomer, etc. which are commercially available include urethane oligomer UAS-10, UAB-140 (from Sanyo-Kokusaku Pulp Co. Ltd.), UA-7200 (from Shin-Nakamura Chemical Co . Ltd.), DPHA-4 OH ( from Nippon Kayaku Co. Ltd.), and UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (from Kyoeisha Chemical Co. Ltd.) .
  • polyfunctional thiol compound having in the molecule thereof two or more mercapto (SH) groups is preferable as the polymerizable monomer, etc.
  • a compound represented by the formula (I) below is preferable.
  • R 1 represents an alkyl group
  • R 2 represents an aliphatic group with a valency of n, which may contain atom ( s ) other than carbon atom
  • R° represents an alkyl group but not H
  • n represents 2 to 4.
  • the polyfunctional thiol compound represented by the formula (I) is exemplified, together with structural formula, by 1 , 4-bis ( 3-mercaptobutyryloxy) butane [formula (II)], 1, 3, 5-tris ( 3-mercaptobutyloxyethyl ) -1, 3, 5-triazine—2 , 4, 6 ( 1H, 3H, 5H) -trione [formula (III)], and pentaerythritol tetrakis ( 3-mercaptobutyrate ) [formula (IV)]. Only a single species of these polyfunctional thiols may be used alone, or two or more species thereof may be used in combination. [0061]
  • composition of the present invention it is also preferable to use, as the polymeri zable monomer, etc., a polymeri zable monomer or oligomer having in the molecule thereof two or more epoxy groups or oxetanyl groups.
  • a polymeri zable monomer or oligomer having in the molecule thereof two or more epoxy groups or oxetanyl groups Specific examples of these compounds will be described in the section of "Polymer Having Polymerizable Group in Side Chain" in the next .
  • a second preferable embodiment of the composition of the present invention relates to a composition which contains, as the polymerizable compound, a polymer having a polymerizable group in the side chain thereof.
  • Examples of the polymerizable group include ethylenic unsaturated double bond group, epoxy group, and oxetanyl group .
  • the polymer having an ethylenic unsaturated bond in the side chain thereof is preferably a polymer having, as the unsaturated double bond moiety thereof, at least one functional group selected from those represented by the formulae (1) to (3) below.
  • each of R 1 to R 3 independently represents a hydrogen atom or monovalent organic group.
  • R 1 is preferably exemplified by hydrogen atom or alkyl group which may have a substituent, and in particular, hydrogen atom and methyl group are preferable by virtue of their high radical reactivity.
  • R 2 and R 3 is independently exemplified by hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent, and arylsulfonyl group which may have a substituent.
  • hydrogen atom, carboxyl group, alkoxycarbonyl group, alkyl group which may have a substituent, and aryl group which may have a substituent are preferable by virtue of their high radical reactivity.
  • X represents an oxygen atom, sulfur atom, or -N(R 12 )-
  • R 12 represents a hydrogen atom or monovalent organic group.
  • R 12 is exemplified by an alkyl group which may have a substituent, among which a hydrogen atom, methyl group, ethyl group, and isopropyl group are preferable by virtue of their high radical reactivity .
  • Examples of the substituent which may be introduced herein include alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, halogen atom, amino group, alkylamino group, arylamino group, carboxyl group,
  • alkoxycarbonyl group sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, and arylsulfonyl group.
  • each of R 4 to R 8 independently represents a hydrogen atom or monovalent organic group.
  • Each of R 4 to R 8 is preferably a hydrogen atom, halogen atom, amino group, dialkylamino group, carboxy group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent, and arylsulfonyl group which may have a substituent.
  • hydrogen atom, carboxy group, alkoxycarbonyl group, alkyl group which may have a substituent, and aryl group which may have a substituent are preferable.
  • Y represents an oxygen atom, sulfur atom, or -N(R 12 )-.
  • R 12 is synonymous to R 12 in the formula (1), the same will also apply to the preferable examples thereof.
  • R 9 is preferably exemplified by hydrogen atom or alkyl group which may have a substituent.
  • hydrogen atom and methyl group are preferable by virtue of their high radical reactivity.
  • Each of R 10 and R 11 independently represents a hydrogen atom, halogen atom, amino group, dialkylamino group, carboxy group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent, and arylsulfonyl group which may have a substituent.
  • Z represents an oxygen atom, sulfur atom, -N(R 13 )-, or phenylene group which may have a substituent.
  • R 13 is exemplified by an alkyl group which may have a substituent. Among them, methyl group, ethyl group and isopropyl group are preferable by virtue of their high radical reactivity.
  • the polymer having an ethylenic unsaturated bond in the side chain thereof, in the present invention is preferably a compound which contains, in one molecule thereof, 20 moll or more and less than 95 mol% of a structural unit having the functional group represented by the formulae (1) to (3) .
  • the range is more preferably 25 to 90 mol%, and furthermore preferably 30 mol% or more and less than 85 moll.
  • the polymer compound which contains the structural unit having the group represented by the formulae (1) to (3) may be synthesized based on the methods described in paragraphs [0027] to [0057] of JP-A-2003-262958. Among the methods, Method of Synthesis 1) described in the patent literature is preferably used, which will be described in below.
  • the polymer having an ethylenic unsaturated bond is preferably a polymer additionally having an acid group.
  • the acid group in the context of the present invention is a dissociative group with a pKa of 14 or smaller, wherein preferable examples include -COOH, -S0 3 H, -P0 3 H 2 , -OS0 3 H, -OP0 2 H 2 , -PhOH, -S0 2 H, -S0 2 NH 2 , -S0 2 NHCO-, and -S0 2 NHS0 2 - .
  • -COOH, -S0 3 H and -P0 3 H 2 are preferable, and -COOH is more preferable .
  • the polymer containing in the side chain thereof an acid group and an ethylenic unsaturated bond may be obtained, for example, by adding an ethylenic unsaturated group-containing epoxy compound to a carboxy group of a carboxyl
  • the carboxyl group-containing polymer includes 1) polymer obtained by radical polymerization or ion
  • carboxy group-containing, vinyl-based polymer examples include homopolymer obtained by
  • unsaturated carboxylic acid used as the carboxyl group-containing monomer, such as (meth ) acrylic acid, 2-succinoloyloxyethyl methacrylate, 2-malenoloyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate,
  • 2-hexahydrophthaloyloxyethyl methacrylate maleic acid, fumaric acid, itaconic acid, and crotonic acid; and copolymer obtained by polymerization of these unsaturated carboxylic acids with a vinyl monomer having no carboxyl group, such as styrene, -methyl styrene, methyl (meth ) acrylate , ethyl (meth) acrylate , propyl (meth) acrylate, isopropyl
  • (meth) acrylate (meth) acrylate , butyl (meth ) acrylate , vinyl acetate, acrylonitrile , (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethylacrylate , crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl
  • the carboxyl group-containing polymer and in particular, (meth) acrylic acid-containing (meth) acrylic acid (co)polymer is preferable.
  • these copolymers include methyl methacrylate/methacrylic acid copolymer described in JP-A-S60-208748 , methyl
  • the polymer having in the side chain thereof an acid group and a polymerizable group, in the present invention is preferably a polymer having, as the unsaturated double bond moiety thereof, at least one structural unit represented by the formulae (1-1) to (3-1) below.
  • each of A 1 , A 2 and A 3 independently represents an oxygen atom, sulfur atom, or -N(R 21 )-, where R 21 represents an alkyl group which may have substituent.
  • R 21 represents an alkyl group which may have substituent.
  • Each of G 1 , G 2 and G 3 independently represents divalent organic group.
  • Each of X and Z independently represents an oxygen atom, sulfur atom, or -N(R )-, where R represents an alkyl group which may have a substituent.
  • Y represents an oxygen atom, sulfur atom, phenylene group which may have a substituent, or -N(R 23 )-, where R 23 represents an alkyl group which may have a substituent.
  • Each of R to R independently represents a monovalent substituent.
  • each of R 1 to R 3 independently represents a monovalent substituent, which is exemplified by hydrogen atom, and alkyl group additionally having a substituent.
  • each of R 1 and R 2 preferably represents a hydrogen atom
  • R 3 is preferably represents a hydrogen atom or methyl group.
  • R 4 to R 6 independently represents a monovalent substituent.
  • R 4 is exemplified by hydrogen atom or alkyl group which may additionally have a substituent. Among them, hydrogen atom, methyl group, and ethyl group are preferable.
  • Each of R 5 and R 6 independently represents a hydrogen atom, halogen atom, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may additionally have a substituent, aryl group which may additionally have a substituent, alkoxy group which may additionally have a substituent, aryloxy group which may additionally have a substituent, alkylsulfonyl group which may additionally have a substituent, and arylsulfonyl group which may additionally have a substituent .
  • hydrogen atom, alkoxycarbonyl group, alkyl group which may additionally have a substituent, and aryl group which may additionally have a substituent are preferable .
  • substituents examples include methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, methyl group, ethyl group, and phenyl group.
  • a 1 represents an oxygen atom, sulfur atom, or -N(R 21 )-
  • X represents an oxygen atom, sulfur atom or -N (R 22 ) -
  • R 21 and R 22 is exemplified by alkyl group which may have a substituent .
  • G 1 represents a divalent organic group, wherein an alkylene group which may have a substituent is preferable. More preferably, G 1 is exemplified by Ci-20 alkylene group which may have a substituent, C3-20 cycloalkylene group which may have a substituent, and C6-20 aromatic group which may have a substituent. Among them, Ci-10 straight-chain or branched alkylene group which may have a substituent, C 3 _i 0 cycloalkylene group which may have a substituent, and C6-12 aromatic group which may have a substituent are preferable by virtue of their performances related to strength, developability and so forth.
  • the substituent on G 1 is preferably a hydroxyl group.
  • each of R 7 to R 9 independently represents a monovalent substituent, preferably exemplified by hydrogen atom, and alkyl group which may additionally have a substituent, wherein each of R 7 and R 8 preferably represents a hydrogen atom, and R 9 preferably represents a hydrogen atom or methyl group.
  • R 10 to R 12 independently represents a monovalent substituent.
  • substituents include hydrogen atom, halogen atom, dialkylamino group,
  • hydrogen atom, alkoxycarbonyl group, alkyl group which may additionally have a substituent, and aryl group which may additionally have a substituent are preferable.
  • a 2 represents an oxygen atom, sulfur atom, or -N(R 21 )-, where R 21 is exemplified by hydrogen atom and alkyl group which may have a substituent.
  • G 2 represents a divalent organic group, which is preferably an alkylene group which may have a substituent. More preferably, G 2 is exemplified by Ci-20 alkylene group which may have a substituent, C3-20 cycloalkylene group which may have a substituent, and C6-20 aromatic group which may have a substituent. Among them, Ci-10 straight-chain or branched alkylene group which may have a substituent, C3-10 cycloalkylene group which may have a substituent, and C 6 _i 2 aromatic group which may have a substituent are preferable by virtue of their performances related to strength, developability and so forth.
  • the substituent on G 2 is preferably a hydroxyl group.
  • Y represents an oxygen atom, sulfur atom, -N(R 23 )-, or phenylene group which may have a substituent.
  • R 23 is exemplified by hydrogen atom, and alkyl group which may have a substituent.
  • each of R 13 to R 15 independently represents a monovalent substituent, which is exemplified by hydrogen atom, and alkyl group which may have a substituent.
  • each of R 13 and R 14 preferably represents a hydrogen atom
  • R 15 preferably represents a hydrogen atom or methyl group.
  • Each of R to R independently represents a monovalent substituent, wherein each of R 16 to R 20 is exemplified by hydrogen atom, halogen atom, dialkylamino group,
  • hydrogen atom, alkoxycarbonyl group, alkyl group which may additionally have a substituent, and aryl group which may additionally have a substituent are preferable. Examples of the substituent which may be introduced herein are similar to those represented by the formula (1) .
  • a 3 represents an oxygen atom, sulfur atom, or -N(R 21 )-
  • Z represents an oxygen atom, sulfur atom, or -N(R 22 )-.
  • R 21 and R 22 are similar to those represented by the formula ( 1 ) .
  • G 3 represents a divalent organic group, which is preferably an alkylene group which may have a substituent.
  • G 3 is preferably exemplified by Ci_ 2 o alkylene group which may have a substituent, C3-20 cycloalkylene group which may have a substituent, and C6-20 aromatic group which may have a substituent.
  • Ci-10 straight-chain or branched alkylene group which may have a substituent, C3-10 cycloalkylene group which may have a substituent, C6-12 aromatic group which may have a substituent are preferable by virtue of their performances related to strength, developability and so forth.
  • the substituent on G 3 is preferably a hydroxyl group.
  • the polymer having in the side chain thereof an acid group and a polymerizable group in the present invention is preferably a compound which contains in the molecule thereof 20 mol% or more and less than 95 mol% of the structural units represented by the formulae (1-1) to (3-1) , from the viewpoint of improving the curability and of reducing residue in development.
  • the content is more preferably 25 to 90 mol%, and furthermore preferably 30 mol% or more and less than 85 mol%.
  • Preferable examples of the structural unit having an ethylenic unsaturated bond and an acid group include polymer compounds 1 to 17 listed below.
  • the polymer having in the side chain thereof an acid group and an ethylenic unsaturated bond in the present invention necessarily has a photopolymeri zable unsaturated bond, from the viewpoint of improving photo-sensitivity, and necessarily has an acid group such as COOH, S0 3 H, P0 3 H 2 , OS0 3 H, OP0 2 H 2 , from the viewpoint of making it alkali-developable.
  • the polymer containing in the side chain thereof an acid group and an ethylenic unsaturated bond in the present invention preferably has an acid value of 20 to 300, preferably 40 to 200, and more preferably 60 to 150, from the viewpoint of harmonizing dispersion stability, developability and sensitivity.
  • the polymer having in the side chain thereof a
  • polymerizable group is also preferably a polymer having, in the side chain thereof, an ethylenic unsaturated bond and an urethane group (occasionally referred to as "urethane polymer”, hereinafter) .
  • the urethane polymer is a polyurethane polymer having, as the basic skeleton thereof, a structural unit represented by a reaction product formed between at least one species of diisocyanate compound represented by the formula (4) below, and at least one species of diol compound represented by the formula (5) below (properly referred to as "specific polyurethane polymer", hereinafter) .
  • each of X° and Y° independently represents a divalent organic residue.
  • polyurethane polymer having the group (s) represented by the formulae (1) to (3) introduced into the side chain thereof, is produced as a reaction product of the diisocyanate compound and the diol compound.
  • the specific polyurethane polymer in the present invention may readily be manufactured, more easily than by a method of replacing or introducing a desired side chain after reaction and production of the polyurethane polymer.
  • the diisocyanate compound represented by the formula (4) is exemplified by compound obtained by addition reaction of a triisocyanate compound, and one equivalent of a
  • the triisocyanate compound is exemplified by those listed below, but not -limited thereto.
  • the monofunctional alcohol or monofunctional amine compound having an unsaturated group are exemplified by those listed below, but not limited thereto.
  • a method of introducing an unsaturated group into the side chain of the polyurethane polymer is preferably such as using, as a source material for manufacturing the polyurethane polymer, a diisocyanate compound having an unsaturated group in the side chain thereof.
  • the diisocyanate compound obtained by addition reaction of a triisocyanate compound and one equivalent of a monofunctional alcohol or monofunctional amine compound having an unsaturated group, and having an unsaturated group in the side chain thereof is exemplified by those listed below, but not limited thereto.
  • the specific polyurethane polymer used in the present invention may, for example, be co-polymerized with a diisocyanate compound other than the above-described diisocyanate compound having an unsaturated group, from the viewpoint of improving the compatibility with the other components in the polymerizable composition, and of improving the shelf stability.
  • the diisocyanate compound to be co-polymerized is exemplified by those listed below.
  • a diisocyanate compound represented by the formula (6) below is preferable.
  • L 1 represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. As necessary, L 1 may have other functional group non-reactive with an isocyanate group, such as ester, urethane, amide and ureido group .
  • the diisocyanate compound represented by the formula (6) specifically includes those listed below.
  • aromatic diisocyanate compound such as 2,4-tolylene diisocyanate, dimer of 2,4-tolylene
  • diisocyanate compound such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate; alicyclic diisocyanate compound such as isophorone diisocyanate,
  • diisocyanate compound obtained as a reaction product of a diol and a diisocyante, such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.
  • the diol compound represented by the formula (5) is broadly exemplified by polyether diol compound, polyester diol compound, and polycarbonate diol compound.
  • a preferable method of introducing an unsaturated group into the side chain of the polyurethane polymer is such as using, as a source material for manufacturing the polyurethane polymer, a diol compound having in the side chain thereof an unsaturated group.
  • the diol compound may be a commercially available product such as trimethylolpropane monoallyl ether, or may be a compound readily manufactured by a reaction of a halogenated diol compound, triol compound, or aminodiol compound, with a carboxylic acid having an unsaturated group, acid chloride, isocyanate, alcohol, amine, thiol, or halogenated alkyl compound.
  • the compound is specifically exemplified by tho listed below, but not limited thereto.
  • More preferable polymer in the present invention is exemplified by polyurethane resin obtained by using, in the process of synthesizing polyurethane, a diol compound represented by the formula (G) below, as at least one of diol compounds having an ethylenic unsaturated linking group.
  • each of R 1 to R 3 independently represents a hydrogen atom or monovalent organic group
  • A represents a divalent organic residue
  • X represents an oxygen atom, sulfur atom, or -N(R 12 )-, where R 12 represents a hydrogen atom or monovalent organic group.
  • R 1 to R 3 and X in the formula (G) are synonymous to R 1 to R 3 and X in the formula (1), the same will also apply to the preferable examples thereof.
  • diol compound represented by the formula (G) which may preferably be used for the synthesis of the specific polyurethane polymer, will be listed below.
  • the specific polyurethane polymer used in the present invention may, for example, be co-polymerized with a diol compound other than the above-described diol compound having an unsaturated group, from the viewpoint of improving the compatibility with the other components in the polymerizable composition, and of improving the shelf stability.
  • Such diol compound is exemplified by the above-described polyether diol compound, polyester diol compound, and polycarbonate diol compound.
  • the polyether diol compound is exemplified by compounds represented by the formulae (7), (8), (9), (10) and (11) below, and, a random copolymer composed of ethylene oxide having a terminal hydroxy group and propylene oxide.
  • R “1"1* represents a hydrogen atom or methyl group
  • X 1 represents the groups below.
  • Each of a, b, c, d, e, f and g represents an integer of 2 or larger, and preferably an integer of 2 to 100.
  • polyether diol compounds represented by the formulae (7) and (8) are specifically exemplified by those listed below .
  • the examples include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol,
  • the polyether diol compound represented by the formula (9) is exemplified by those listed below.
  • the examples include PTMG650, PTMG1000, PTMG2000 and PTMG3000 (trade names) from Sanyo Chemical Industries, Ltd.
  • the polyether diol compound represented by the formula (10) is specifically exemplified by those listed below.
  • the examples include Newpole PE-61, Newpole PE-62, Newpole PE-64, Newpole PE-68, Newpole PE-71, Newpole PE-74, Newpole PE-75, Newpole PE-78, Newpole PE-108, Newpole PE-128 and Newpole PE-61 (tradenames) from Sanyo Chemical Industries , Ltd.
  • the polyether diol compound represented by the formula (11) is specifically exemplified by those listed below.
  • the examples include Newpole BPE-20, Newpole BPE-20F, Newpole BPE-20NK, Newpole BPE-20T, Newpole BPE-20G, Newpole BPE-40, Newpole BPE-60, Newpole BPE-100, Newpole BPE-180, Newpole BPE-2P, Newpole BPE-23P, Newpole BPE-3P and Newpole BPE-5P (trade names) from Sanyo Chemical Industries, Ltd.
  • the random copolymer composed of ethylene oxide having a terminal hydroxyl group and propylene oxide is exemplified by those listed below.
  • the examples include Newpole 50HB-100, Newpole 50HB-260, Newpole 50HB-400, Newpole 50HB-660, Newpole 50HB-2000 and Newpole 50HB-5100 (trade names) from Sanyo Chemical Industries, Ltd.
  • the polyester diol compound is exemplified by compounds represented by the formulae (12) and (13) below.
  • L 2 , L 3 and L 4 may be same with, or different from each other, each of which represents a divalent aliphatic or aromatic hydrocarbon group, and L 5 represents a divalent aliphatic hydrocarbon group. It is preferable that each of L 2 to L 4 independently represents an alkylene group, alkenylene group, alkynylene group, or arylene group, and L 5 represents an alkylene group. Each of L 2 to L 5 may contain other functional group non-reactive with
  • nl and n2 independently represents an integer of 2 or larger, and preferably an integer of 2 to 100.
  • the polycarbonate diol compound is exemplified by compound represented by the formula (14) .
  • (L 6 ) s are same with, or different from each other, and each of which represents a divalent aliphatic or aromatic hydrocarbon group.
  • L 6 preferably represents an alkylene group, alkenylene group, alkynylene group, and arylene group .
  • L 6 may contain other functional group non-reactive with isocyanate group, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom.
  • n3 represents an integer of 2 or larger, and preferably an integer of 2 to 100.
  • the diol compound represented by the formula (12), (13) or (14) specifically include (Exemplary Compound No.l) to (Exemplary Compound No.18) listed below.
  • n represents an integer of 2 or larger.
  • a diol compound having a substituent non-reactive with isocyanate group may be used in addition to the above-described diol compound.
  • examples of such diol compound include those listed below .
  • L 7 and L 8 may be same with, or different from each other, and each of which represents a divalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group, which may have a substituent (for example, alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, and halogen atom such as -F, -CI, -Br, -I) .
  • each of L 7 and L 8 may have therein other functional group non-reactive with isocyanate group, such as carbonyl group, ester group, urethane group, amide group, or ureido group.
  • L 7 and L 8 may form a ring.
  • a diol compound having a carboxyl group may be used in addition to the above-described diol compound.
  • diol compound examples include those represented by the formulae (17) to (19) .
  • R 15 represents a hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, or aryloxy group, which may have a substituent (exemplified by the individual groups of cyano, nitro, halogen atom such as -F, -CI, -Br, -I, -C0NH 2 , -COOR 16 , -OR 16 , -NHCONHR 16 , -NHCOOR 16 , -NHCOR 16 , and -OCONHR 16 (R 16 represents a Ci_i 0 alkyl group, or C7-15 aralkyl group.)), and preferably represents a hydrogen atom, Ci-8 alkyl group, or C 6 _i 5 aryl group.
  • a substituent exemplified by the individual groups of cyano, nitro, halogen atom such as -F, -CI, -Br, -I, -C0NH 2 , -CO
  • L 9 , L 10 and L 11 may be same with, or different from each other, and each of which represents a single bond, or a divalent aliphatic or aromatic hydrocarbon group which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy and halogeno groups are preferable) , preferably represents a C1-.20 alkylene group, or Ce-15 arylene group, and furthermore preferably a Ci-8 alkylene group.
  • L 9 to L 11 may have therein other functional group non-reactive with isocyanate group, such as carbonyl, ester, urethane, amide, ureido, or ether group. Any two or three of R 15 , L 7 , L 8 and L 9 may form a ring.
  • Ar represents a trivalent aromatic hydrocarbon group, and preferably a C is aromatic group.
  • the diol compound having a carboxyl group represented by the formulae (17) to (19) is exemplified by those listed below.
  • the examples include 3 , 5-dihydroxy benzoic acid, 2 , 2-bis (hydroxymethyl ) propionic acid,
  • the polyurethane polymer is preferably given a capability of forming hydrogen bond and alkali-solubility. More specifically, the
  • polyurethane polymer having in the side chain thereof an ethylenic unsaturated binding group is a polymer further having a carboxyl group in the side chain thereof. More specifically, a polyurethane polymer having 0.3 meq/g or more of ethylenic unsaturated binding group in the side chain thereof, and 0.4 meq/g or more of carboxyl group in the side chain thereof, is particularly preferable for use as the binder polymer in the present invention.
  • diol compound examples include those listed below.
  • L 12 represents a single bond, divalent aliphatic or aromatic hydrocarbon group which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy, halogeno, ester and amide groups are preferable), -CO-, -SO-, -S0 2 -, -0- or -S-, and preferably represents a single bond, Ci_i 5 divalent aliphatic hydrocarbon group, -CO-, -S0 2 -, -0- or -S-.
  • R 17 and R 18 may be same or different, each of which represents a hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, or halogeno group, and preferably represents a hydrogen atom, Ci-8 alkyl group, C6-15 aryl group, Ci-e alkoxy group or halogeno group. Any two of L 12 , R 17 and R 18 may combine to form a ring.
  • R 19 and R 20 may be same or different, each of which represents a hydrogen atom, alkyl group, aralkyl group, aryl group or halogeno group, and preferably represents a hydrogen atom, Ci-e alkyl, or C 6 -i5 aryl group. Any of two L 12 , R 19 and R 20 may combine to form a ring.
  • L 13 and L 14 may be same or different, each of which represents a single bond, double bond, or divalent aliphatic hydrocarbon group, and preferably represents a single bond, double bond, or methylene group.
  • A represents a mononuclear or polynuclear aromatic ring, and preferably represents a Ce-18 aromatic ring.
  • the compounds represented by the formula (20), (21) or (22) include those listed below.
  • the examples include aromatic tetracarboxylic
  • dianhydride such as pyromellitic dianhydride
  • the diol compound used for the ring-opening reaction is specifically exemplified by those listed below.
  • the examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1 , 6-hexanediol ,
  • the specific polyurethane polymer usable in the present invention may be synthesized by dissolving the diisocyanate compound and the diol compound into an aprotic solvent, by adding a publicly known catalyst with an activity suited to reactivity of the both, and by heating the mixture .
  • Molar ratio (M a :M b ) of the diisocyanate and the diol compound used for the synthesis is preferably 1:1 to 1.2:1.
  • Amount of introduction of the ethylenic unsaturated bond into the specific polyurethane polymer in the present invention is, on the basis of equivalent, preferably 0.3 meq/g or more, and more preferably 0.35 to 1.50 meq/g of ethylenic unsaturated binding group in the side chain.
  • the polyurethane polymer is particularly preferable as the binder polymer in the present invention, when it contains, together with the ethylenic unsaturated binding group, 0.4 meq/g or more, and more preferably 0.45 to 1.00 meq/g of carboxy group in the side chain.
  • Molecular weight of the specific polyurethane polymer in the present invention is preferably 10,000 or larger on the basis of weight average molecular weight, and more preferably in the range from 40,000 to 200,000.
  • the polyurethane polymer exerts excellent in strength of the image-forming region and will be excellent in developability of non-image-forming region with an aqueous alikali developing solution, by adjusting the weight average molecular weight in the above-described ranges.
  • the specific polyurethane polymer in the present invention is also preferably used when it has a unsaturated group at the polymer terminal or in the principal chain thereof.
  • crosslinking reaction may be enhanced between the polymerizable compound and the specific polyurethane polymer, or among the specific polyurethane polymers, and thereby strength of the photo-cured product may increase.
  • the unsaturated group herein may contain a carbon-carbon double bond, in view of readiness in the crosslinking reaction.
  • Methods of introducing the unsaturated group into the polymer terminal include those described in the next. That is, in the process of treating the residual isocyanate group at the polymer terminal with alcohols or amines, in the synthesis of the polyurethane polymer described above, it suffices to use alcohols or amines having an unsaturated group.
  • This sort of compound is specifically exemplified by those similar to Exemplary Compounds listed above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
  • the unsaturated group is more preferably introduced into the side chain of the polymer, rather than at the polymer terminal, in view of readiness of control in the amount of introduction, increased amount of introduction, and improved efficiency of the crosslinking reaction.
  • the ethylenic unsaturated binding group to be introduced is preferably a methacryloyl group, acryloyl group or styryl group from the viewpoint of formability of film hardened by crosslinking, and is more preferably a methacryloyl group or acryloyl group. Methacryloyl group is more preferable, from the viewpoint of achieving both of formability of film hardened by crosslinking and storability.
  • the amount of introduction of methacryloyl group is preferably 0.30 meq/g or more as described previously, and is more preferable in the range from 0.35 to 1.50 meq/g .
  • the polyurethane polymer having 0.35 to 1.50 meq/g of methacryloyl group introduced into the side chain thereof is a most preferable embodiment of the binder polymer in the present invention.
  • Methods of introducing the unsaturated group into the principal chain is exemplified by method of using a diol compound, having an unsaturated group in the principal chain thereof, for synthesis of the polyurethane polymer.
  • the diol compound having, in the principal chain thereof, an unsaturated group is exemplified by those described below.
  • the examples include cis-2-butene-l , 4-diol , trans-2-butene-l , 4-diol , and polybutadienediol .
  • the specific polyurethane polymer in the present invention may be used together with an alkali-soluble polymer which contains a polyurethane polymer having a structure different from that of the specific polyurethane polymer.
  • the specific polyurethane polymer may be used together with a polyurethane polymer having an aromatic group in the principal chain and/or side chain thereof.
  • styrene-based polymer having in the side chain thereof an ethylenic unsaturated bond
  • styrene-based polymer a styrene-based polymer having in the side chain thereof an ethylenic unsaturated bond
  • the styrene-based polymer more preferably has at least either one of a styrenic double bond represented by the formula (23) below (styrene and oi-methyl styrenic double bond) , and, a vinylpyridinium group represented by the formula (24) below.
  • R 21 represents a hydrogen atom or methyl group.
  • R 22 represents a substitutable arbitrary atom or group of atoms.
  • k represents an integer of 0 to .
  • the styrenic double bond represented by the formula (23) is bound to the polymer principal chain, via a linking group composed of a single bond, or, arbitrary atom or group of atoms, wherein mode of bonding is not specifically limited.
  • R represents a substitutable arbitrary atom or group of atoms .
  • m represents an integer of 0 to 4.
  • a ⁇ represents an anion.
  • the pyridinium ring may have a form of benzopyridinium condensed with a benzene ring as a substituent, examples of which include quinolium group and isoquinolium group .
  • the vinylpyridinium group represented by the formula (24 ) is bound to the polymer principal chain via a linking group composed of a single bond, or, a linking group composed of arbitrary atom or group of atoms, wherein mode of bonding is not specifically limited.
  • One possible method of synthesizing the styrene-based polymer is such as allowing monomers, having a functional group represented by the formula (23) or (24), and having a functional group co-polymerizable with other copolymeri zable component, to react thereamong, according to any of publicly known co-polymerization processes.
  • the styrene-based polymer herein may be a homopolymer composed of only one species of the functional group represented by either one of the formulae (23) and (24), or may be a copolymer composed of two or more species of the functional group represented by either one of, or both of the formulae (23) and (24).
  • the styrene-based polymer may also be a copolymer containing other co-polymerizable monomer having none of these functional groups.
  • the co-polymerizable monomer in this case is preferably a carboxyl group-containing monomer for the purpose of imparting the polymer with solubility into an aqueous alkali solution, and is exemplified by acrylic acid, methacrylic acid, acrylic acid 2-carboxyethyl ester, methacrylic acid 2-carboxyethyl ester, crotonic acid, maleic acid, fumaric acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4 -carboxystyrene .
  • a (multi ) polymer by introducing other monomer component, other than the monomer having the carboxyl group, into the copolymer.
  • the monomer possibly introduced into the copolymer in this case is properly selectable from styrene derivative such as styrene, 4-methylstyrene , 4-hydroxystyrene , 4 -acetoxystyrene ,
  • N-vinylcarbazole 4-vinylbenzyltrimethyl ammonium chloride, N-vinylimidazole quaternari zed with methyl chloride,
  • vinyl esters such as vinyl acetate, vinyl chloroacetate , vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate; vinyl ethers such as methyl vinyl ether and butylvinyl ether; N-vinylpyrrolidone , acryloyl morpholine, vinyl chloride, vinylidene chloride, allyl alcohol, and
  • ratio of repeating unit having the functional group (s) represented by the formula (23) and/or formula (24), relative to the total copolymer composition is preferably 20% by mass or more, and more preferably 40% by mass or more. In this range, a crosslinked system excellent in expressing the effect of the present invention and highly sensitive may be provided.
  • the styrene-based polymer may become water soluble by having a quaternary salt structure in the repeating unit thereof.
  • the polymeri zable composition of the present invention containing such polymer is used for a recording layer of a lithgraphic printing plate precursor, the recording layer is now developable with water after the exposure.
  • the styrene-based polymer has the functional group represented by the formula (23) in the repeating unit thereof, and has a quaternary salt structure in the linking group which links the principal chain and the functional group represented by the formula (23) (for example, specific examples P-6, P-23 and P-24), the
  • styrene-based polymer may be a homopolymer having such structure, whereas in other cases, it is preferably a copolymer with other co-polymerizable monomer listed below.
  • the examples include -vinylbenzyl trimethyl ammonium chloride,
  • the styrene-based polymer may be a homopolymer, or may be a copolymer with other co-polymerizable monomer.
  • the polymer is now also developable with an aqueous alkali solution.
  • the ratio of the repeating unit having the functional group (s) represented by the formula (23) and/or formula (24) is preferably 20% by mass or more. Introduction of any other repeating unit is arbitrarily selectable, depending on purposes.
  • Molecular weight of the styrene-based polymer is preferably in the range from 10,000 to 300,000 on the basis of weight average molecular weight, and more preferably in the range from 15, 000 to 200, 000, and most preferably in the range from 20,000 to 150,000.
  • the other polymer having an ethylenic unsaturated bond in the side chain thereof is exemplified by novolac polymer having an ethylenic unsaturated group in the side chain thereof, and specifically exemplified by polymer obtained by
  • Examples include acetal polymer having an ethylenic unsaturated bond in the side chain thereof, described in
  • Examples also include polyamide-based polymer having an ethylenic unsaturated bond in the side chain thereof described in Japanese Patent Application No. 2003-321022, and a polymer obtained by introducing an ethylenic unsaturated bond, into the side chain of the polyamide polymer cited therein, by a method described in JP-A-2002-62648.
  • Examples also include polyimide polymer having an ethylenic unsaturated bond in the side chain thereof described in Japanese Patent Application No. 2003-339785, and a polymer obtained by introducing an ethylenic unsaturated bond, into the side chain of the polyimide polymer cited therein, by a method described in JP-A-2002-62648. [0197]
  • polymer having an epoxy group or oxetanyl group in the side chain thereof also preferably contains a polymer having an epoxy group or oxetanyl group in the side chain thereof.
  • the polymer having an epoxy group in the side chain thereof, and polymerizable monomer or oligomer having in the molecule thereof two or more epoxy groups are examples of polymers having an epoxy group or oxetanyl group in the side chain thereof.
  • bisphenol-A type epoxy resin specifically exemplified by bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin.
  • These compounds may be commercially available, or may be obtained by introducing an epoxy group into the side chain of the polymer.
  • the bisphenol-7A type epoxy resin is commercially available as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (all from Japan Epoxy Resin Co. Ltd.), EPICLON860, EPICLON1050,
  • EPICLON1051, EPICLON1055 (all from DIC Corporation) and so forth
  • bisphenol-F type epoxy resin is commercially available as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (all from Japan Epoxy Resin Co. Ltd.), EPICLON830, EPICLON835 (all from DIC Corporation), LCE-21, RE-602S (all from Nippon Kayaku Co. Ltd.) and so forth
  • the phenol novolac-type epoxy resin is commercially available as JER152, JER154, JER157S70, JER157S65, (all from Japan Epoxy Resin Co. Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (all from DIC Corporation) and so forth
  • the cresol novolac-type epoxy resin is commercially available as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (
  • EPICLON N-660 EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all from Japan Epoxy Resin Co. Ltd. ) , EOCN-1020 (from Nippon Kayaku Co.
  • aliphatic epoxy resin is commercially available as ADEKA RESIN EP-4080S, ditto EP-4085S, ditto EP-4088S (all from Adeka Corporation) , Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, ditto PB 4700 (all from Daicel Chemical Industries, Ltd.), Denacol EX-212L, EX-214L,
  • the polymer having in the side chain thereof an oxetanyl group, and the polymeri zable monomer or oligomer having in the molecule thereof two or more oxetanyl groups are specifically exemplified by Aron Oxethane OXT-121, OXT-221, OX-SQ, PNOX (all from Toagosei Co. Ltd.).
  • the introduction reaction may be allowed to proceed by using, as a catalyst, a tertiary amine such as triethylamine and benzylmethylamine ; quaternary ammonium salt such as dodecyltrimethylammonium chloride,
  • Amount of introduction of the alicyclic epoxy unsaturated compound is preferably controlled so as to adjust the acid value of the obtainable polymer to 5 to 200 KOH-mg/g.
  • the molecular weight on the weight average basis is preferably 500 to 5,000,000, and more preferably 1,000 to 500,000.
  • polymerizable compound acrylic acid ester, methacrylic acid ester, styrene-based compound, vinyl ether-based compound, etc.
  • Selection and method of use of the polymerizable compound are important factors, also in consideration of compatibility and dispersibility with other components (metal oxide, dye, polymerization initiator, etc. ) contained in the near infrared absorptive liquid composition.
  • the polymerizable compound are important factors, also in consideration of compatibility and dispersibility with other components (metal oxide, dye, polymerization initiator, etc. ) contained in the near infrared absorptive liquid composition.
  • compatibility may be improved by using a low purity compound, or by using two or more compound in combination. It is also possible to select a specific structure from the viewpoint of improving adhesiveness with a hard surface such as a support.
  • Amount of addition of the polymerizable compound to the composition of the present invention is 1 to 80% by weight of the total solid content excluding the solvent, more preferably 15 to 70% by weight, and particularly 20 to 60% by weight.
  • the polymerizable compound may be of a single species, or of two or more species. When two or more species are used, the total content is adjusted to the ranges described above.
  • the near infrared absorptive liquid composition of the present invention may further contain a binder polymer, in addition to the polymerizable compound, as necessary, for example for the purpose of improving film characteristics.
  • a binder polymer in addition to the polymerizable compound, as necessary, for example for the purpose of improving film characteristics.
  • An alkali-soluble resin is preferably used as the binder polymer. Use of the alkali-soluble resin is effective in improving the heat resistance, and in finely controlling the coatability.
  • the alkali-soluble resin is properly selectable from linear organic high polymers, having in the molecule thereof (preferably, in the molecule having an acrylic copolymer or styrene-based copolymer in the principal chain) at least one group capable of enhancing alkali solubility.
  • Polyhydroxy styrene-based resin, polysiloxane-based resin, acrylic resin, acrylamide-based resin, and acryl /acrylamide copolymer resin are preferable from the viewpoint of heat resistance, whereas, acrylic resin, acrylamide-based resin, and acryl /acrylamide copolymer resin are preferable from the viewpoint of controlling the developability .
  • the group capable of enhancing alkali solubility (also referred to as "acid group”, hereinafter) is exemplified by carboxyl group, phosphoric acid group, sulfonic acid group, and phenolic hydroxyl group. Those making the resin soluble into organic solvent and developable with a weak-alkaline aqueous solution are preferable. (Meth ) acrylic acid is particularly preferable.
  • the acid group may be of a single species, or of two or more species.
  • Examples of monomer capable of adding an acid group after polymerization include a monomer having a hydroxy group such as 2-hydroxyethyl (meth ) acrylate , a monomer having an epoxy group such as glycidyl (meth ) acrylate , and a monomer having an isocyanate group such as 2-isocyanate ethyl (meth) acrylate .
  • the group for introducing an acid group may be of a single species or of two or more species.
  • the acid group may be introduced into the alkali-soluble binder, for example, by polymerizing the monomer having the acid group and/or the monomer capable of adding an acid group after polymerization (occasionally referred to as "acid group introducing monomer", hereinafter) as a monomer component.
  • acid group introducing monomer an acid group after polymerization
  • a treatment for adding the acid group described later will be necessary after the polymerization.
  • the alkali-soluble resin may be manufactured, for example, by a publicly known radical polymerization process.
  • Conditions for polymerization regarding temperature, pressure, species and amount of radical initiator, and species of solvent are readily adjustable by those skilled in the art, and may also be determined by experiments.
  • alkali-soluble resin is preferably a polymer having a carboxylic acid in the side chain thereof, examples of which include methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially-esterified maleic acid copolymer, alkali-soluble phenol resin such as novolac-type resin, and, acidic cellulose derivative having a carboxylic acid in the side chain thereof, and adduct of hydroxy group-containing polymer with acid anhydride.
  • Copolymer composed of (meth) acrylic acid and other monomer co-polymerizable therewith is particularly preferable as the alkali-soluble resin.
  • the other monomer co-polymerizable with (meth) acrylic acid is exemplified by alkyl (meth) acrylate, aryl
  • alkyl (meth) acrylate and the aryl (meth) acrylate examples include methyl (meth ) acrylate , ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth ) acrylate , isobutyl (meth ) acrylate , pentyl
  • (meth) acrylate examples include styrene, -methyl styrene, vinyltoluene , glycidyl
  • N-cyclohexylmaleimide are exemplified.
  • the other monomer co-polymerizable with (meth ) acrylic acid may be of a single species, or of two or more species.
  • the alkali-soluble resin also preferably contains, as essential polymer component (A) , polymer (a) which essentially contains a compound (referred to as "ether dimer”, hereinafter) , represented by the formula (ED) below:
  • each of R 1 and R 2 independently represents a hydrogen atom or a Ci-25 hydrocarbon group which may have a substituent .
  • the composition of the present invention may form a cured coated film especially excellent in the heat resistance and translucency.
  • the C 1 -25 hydrocarbon group which may have a substituent represented by R 1 and R 2 is exemplified by, but not specially limited to, straight-chain or branched alkyl group such as methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, and 2-ethylhexyl groups; aryl group such as phenyl group; alicyclic group such as cyclohexyl, t-butylcyclohexyl , dicyclopentadienyl , tricyclodecanyl , isobornyl, adamantyl, and
  • 2-methyl-2-adamantyl groups alkoxy-substituted alkyl group such as 1-methoxyethyl , and 1-ethoxyethyl groups; and aryl group-substituted alkyl group such as benzyl group.
  • substituents having a primary or secondary carbon less eliminatable by acid or heat such as methyl , ethyl, cyclohexyl and benzyl, are preferable from the viewpoint of heat resistance .
  • ether dimer examples include
  • the ether dimer may be of a single species, or may be two or more species.
  • the structure derived from the compound represented by the formula (ED) may be co-polymerized with other monomer ( s ) .
  • the novolac resin is exemplified by condensates obtained by condensing phenols and aldehydes under the presence of an acid catalyst.
  • the phenols are exemplified by phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol , cathecol, resorcinol, pyrogallol, naphthol, and bisphenol-A.
  • aldehydes are exemplified by formaldehyde, paraformaldehyde, acetaldehyde , propionaldehyde , and benzaldehyde .
  • the phenols and aldehydes may be used independently, or in combination of two or more species.
  • novolac resin examples include condensate of metacresol, paracresol or mixture them, with formalin.
  • the novolac resin may be controlled in the molecular weight distribution thereof, typically by fractionation.
  • the novolac resin may also be mixed with a low molecular weight component having a phenolic hydroxy group such as bisphenol-C and bisphenol-A.
  • alkali-soluble resin particularly preferable are multi-component copolymer such as composed of benzyl
  • (meth) acrylate/ (meth) acrylic acid copolymer and benzyl (meth) acrylate/ (meth) acrylic acid/other monomer.
  • Other examples include copolymer having 2-hydroxyethyl methacrylate co-polymerized therein, and those described in JP-A-H7-140654 including 2 -hydroxypropyl (meth) acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, and 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl
  • Acid value of the alkali-soluble resin is preferably 30 mg KOH/g to 200 mg KOH/g, more preferably 50 mg KOH/g to 150 mg KOH/g, and most preferably 70 to 120 mg KOH/g.
  • alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20, 000.
  • Content of the binder polymer contained in the composition of the present invention is 1% by mass to 80% by mass of the total solid content of the composition, more preferably 10% by mass to 70% by mass, and furthermore preferably 20 to 60% by mass.
  • the composition of the present invention contains 50 to 80% by mass, relative to the whole composition, of a solvent.
  • the solvent may be of a single species, or of two or more species . When two or more species are used, the total content is adjusted to the range described above.
  • the content of the solvent in the composition is preferably 50 to 75% by mass, and more preferably 51 to 70% by mass.
  • the solvent used in the present invention is properly selectable depending on purposes, without special limitation so long as it may uniformly dissolve or disperse therein the individual components of the composition of the present invention.
  • the examples include water; alcohols such as methanol, ethanol, normal-propanol , isopropanol,
  • ketones such as acetone, methyl ethyl ketone, methyl isobuty ketone, cyclohexanone , diisobutyl ketone, cyclohexanone and
  • esters such as ethyl acetate, butyl acetate, normal-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene and
  • halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene , chloroform,
  • diethylether ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, l-methoxy-2-propanol and propylene glycol monomethyl ether; dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, and sulfolane.
  • the composition of the present invention may also contain a polymerization initiator.
  • the polymerization initiator may be of a single species, or of two or more species. When two or more species are used, the total content is adjusted to the range described below.
  • the content is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and particularly 0.1% by mass to 15% by mass.
  • the polymerization initiator is properly selectable depending on purposes, without special limitation so long as it can initiate polymerization of the polymerizable compound with the aid of light and/or heat, and is preferably a photopolymerizable compound.
  • the polymerization initiator When the polymerization is triggered by light, the polymerization initiator preferably shows photosensitivity over the region from ultraviolet radiation to visible light.
  • the polymerization initiator is preferably decomposable at 150°C to 250°C.
  • the polymerization initiator preferably has at least an aromatic group, and is exemplified by acylphosphine compound, acetophenone-based compound, a-aminoketone compound, benzophenone-based compound, benzoin ether-based compound, ketal derivative compound, thioxanthone compound, oxime compound, hexaaryl biimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazonium compound, iodonium compound, sulfonium compound, azinium compound, benzoin ether-based compound, ketal derivative compound, onium salt compound, metallocene compound, organic borate compound, and disulfone compound.
  • oxime compound acetophenone-based compound, a-aminoketone compound, trihalomethyl compound, hexaaryl biimidazole compound and thiol compound.
  • acetophenone-based compound examples include 2, 2-diethoxyacetophenone,
  • the trihalomethyl compound is more preferably an s-triazine derivative composed of at least one mono-, di-, or tri-halogen-substituted methyl group (s) bound to an s-triazine ring, exemplified by 2,4, 6-tris (monochloromethyl ) -s-triazine, 2,4, 6-tris (dichloromethyl ) -s-triazine,
  • hexaaryl biimidazole compound is exemplified by various compounds described in the specifications of
  • the oxime compound is exemplified by various compounds described in J.C.S. Perkin ll (1979)1653-1660, J.C.S. Perkin II (1979)156-162, Journal of Photopolymer Science and
  • JP-A-2007-231000 and JP-A-2007-322744 are preferably used.
  • Most preferable examples include oxime compounds having specific substituents described in JP-A-2007-269779, and oxime compounds having a thioaryl group described in
  • the oxime compound is preferably a compound represented by the formula (1) below.
  • the oxime compound may be of (E) -isomer, or of (Z) -isomer, or of a mixture of the (E) -isomer and the (Z) -isomer.
  • each of R and B independently represents a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.
  • the monovalent non-metallic atomic group is exemplified by alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic group, alkylthiocarbonyl group, and
  • arylthiocarbonyl group Each of these groups may have one or more substituents.
  • the substituent may further be substituted by other substituent.
  • substituents examples include halogen atom, aryloxy group, alkoxycarbonyl group or aryloxycarbonyl group, acyloxy group, acyl group, alkyl group, and aryl group.
  • the oxime compound may be referred, for example, to those described in paragraphs [0515] to [0538] of JP-A-2012-208494 (paragraphs [0636] to [0659] in the correspondent U.S. Patent No. 2012/0235099), the contents of which are incorporated herein by reference.
  • the oxime compound preferably has a maximum absorption wavelength in the range from 350 nm to 500 nm, more preferably from 360 nm to 480 nm, and particularly from 365 nm and 455 nm.
  • the oxime compound preferably has a molar absorption coefficient in the range from 365 nmor 405 nmof 3,000 to 300,000 from the viewpoint of sensitivity, more preferably 5,000 to 300,000, and particularly 10,000 to 200,000.
  • the molar absorption coefficient of the compound is measurable by any of publicly known methods, and is preferably measured using, for example, a UV spectrophotometer (Carry-5 Spectrophotometer, from Varian Inc.) , and an ethyl acetate as a solvent at a concentration of 0.01 g/L.
  • a UV spectrophotometer Carry-5 Spectrophotometer, from Varian Inc.
  • an ethyl acetate as a solvent at a concentration of 0.01 g/L.
  • a compound selected from the group consisting of oxime compound, acetophenone-based compound, and acylphosphine compound is more preferable as the photopolymeri zation initiator. More specifically, for example, also
  • JP-A-H10-291969, acylphosphine oxide-based initiator described in Examined Japanese Patent No. 4225898, the oxime-based initiator described above, and other oxime-based initiators described in JP-A-2001-233842 are usable.
  • the acetophenone-based initiator is commercially available as IRGACURE-907 , IRGACURE-369 and IRGACURE-379 (trade names: all from BASF Japan Ltd.).
  • the acylphosphine -based initiator is commercially available as IRGACURE-819 and DAROCUR-TPO (trade names: the both from BASF Japan Ltd.) .
  • the composition of the present invention may contain a surfactant.
  • the . surfactant may be of a single species, or of two or more species in combination. Amount of addition of the surfactant, relative to the total mass of the composition of the present invention, is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass, and furthermore preferably 0.01 to 0.1% by mass.
  • Various surfactants such as fluorine-containing surfactant, nonionic surfactant, cationic surfactant, anionic surfactant, silicone-based surfactant are usable.
  • composition of the present invention is improved in liquid characteristics (especially in fluidity) when prepared as a coating liquid, by containing the fluorine-containing surfactant, so that uniformity in thickness of coating and liquid saving property may further be improved.
  • the film is formed by using a coating liquid prepared by using the composition containing the fluorine-containing surfactant, interfacial tension between the surface to be coated and the coating liquid is reduced, thereby wetting on the surface to be coated is improved, and coatability over the surface to be coated is improved.
  • This is advantageous in view of forming, in a more appropriate manner, the film only with a small irregularity in thickness, even when a small amount of liquid is used to form a thin film of several micrometers thick or around.
  • Fluorine content in the fluorine-containing surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly 7% by mass to 25% by mass.
  • the fluorine-containing surfactant having the fluorine content adjusted to these ranges is effective in terms of uniformity in thickness of coating and liquid saving property, and is also excellent in solubility into the near infrared absorptive liquid composition.
  • fluorine-containing surfactant examples include Megafac F171, ditto F172, ditto F173, ditto F176, ditto F177, ditto F141, ditto F142, ditto F143, ditto F144, ditto R30, ditto F437, ditto F475, ditto F479, ditto F482, ditto F554, ditto F780, ditto F781 (all from DIC Corporation), Fluorad FC430, ditto FC431, ditto FC171 (all from Sumitomo 3M Ltd.), Surflon S-382, ditto SC-101, ditto SC-103, ditto SC-104, ditto SC-105, ditto SC1068, ditto SC-381, ditto SC-383, ditto S393, ditto KH-40 (all from Asahi Glass Co. Ltd.), PF636, PF656, PF6320, PF6520, and
  • nonionic surfactant examples include glycerol, trimethylolpropane , trimethylolethane and
  • ethoxylate and propoxylate thereof for example, glycerol propoxylate and glycerin ethoxylate
  • polyoxyethylene lauryl ether for example, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate,
  • cationic surfactant examples include phthalocyanine derivative (trade name: EFKA-745, from
  • organosiloxane polymer KP341 from Shin-Etsu Chemical Co. Ltd.
  • (meth) acrylic acid-based (co)polymer Polyflow No.75, No.90, No.95 from Kyoeisha Chemical Co. Ltd.
  • 001 from Yusho Co. Ltd.
  • anionic surfactant examples include 004, W005 and W017 (from Yusho Co. Ltd.).
  • silicone-based surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DCllPA”, “Toray Silicone SH21PA”, “Toray Silicone SH28PA”, “Toray Silicone SH29PA”, “Toray Silicone SH30PA”, and “Toray Silicone SH8400” from Dow Corning Toray Co. Ltd.; “TSF-4440", “TSF-4300”, “TSF-4445”, “TSF-4460” and “TSF-4452” from Momentive Performance Materials Inc.; "KP341", “KF6001", “KF6002” from Shin-Etsu Chemical Co. Ltd.; and “BYK307", “BYK323” and “BYK330” from BYK Chemie.
  • Examples of the other components usable herein include binder polymer, dispersion aid, sensitizer, crosslinking agent, curing accelerator, filler, heat curing accelerator, thermal polymerization inhibitor, and plasticizer, and further include adhesion enhancer for the surface of base, and other components
  • auxiliaries for example, electroconductive particle , filler, defoaming agent, flame retarder, leveling agent, releasing promoter, antioxidant, perfume, surface tension modifier, and chain transfer agent.
  • the target near infrared cut filter is now adjustable in terms of stability, and properties such as film characteristics.
  • JP-A-2012-003225 paragraphs [0101] to [0102], paragraphs [0103] to [0104] and paragraphs [0107] to [0109] of JP-A-2008-250074 , the contents of which are incorporated herein by reference.
  • the near infrared absorptive liquid composition of the present invention has a liquid form, and is therefore readily formed into a film by a simple process such as spin coating, to thereby readily manufacture the near infrared cut filter. Accordingly, the above-described insufficient
  • the near infrared absorptive liquid composition of the present invention include, but not limited to, near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device (for example, near infrared cut filter for wafer-level lens), and near infrared cut filter disposed on the back side (on the side opposite to the light receiving side) of the substrate of solid state image sensing device, wherein application to the light-shielding film disposed on the light receiving side of the substrate of solid state image sensing device is preferable.
  • the near infrared absorptive liquid composition is preferably used for forming, by coating, the film over an image sensor of solid state image sensing device.
  • the near infrared absorptive liquid composition of the present invention preferably has a viscosity of 1 mPa-s or larger and 3,000 mPa's or smaller, more preferably 10 mPa-s or larger and 2,000 mPa-s or smaller, and furthermore preferably 100 mPa-s or larger and 1,500 raPa-s or smaller.
  • the viscosity preferably 10 mPa-s or larger and 3,000 mPa ⁇ s or smaller, more preferably 500 mPa-s or larger and 1,500 mPa-s or smaller, and most preferably 700 mPa-s or larger and 1,400 mPa-s or smaller, from the viewpoint of thick film formability and uniformity of coating.
  • the present invention also relates to a near infrared cut filter obtained by using the above-described near infrared absorptive liquid composition of the present invention.
  • Such near infrared cut filter formed by using the near infrared absorptive liquid composition of the present invention, is excellent in the light shielding performance in the near infrared region (near infrared shielding performance), excellent in the translucency in the visible light region (visible light transmittance ) , and, excellent in
  • the present invention is beneficial as the near infrared cut filter for a wavelength range from 700 to 2,500 nm.
  • the present invention further relates to a method of manufacturing the near infrared cut filter, having a process of coating (preferably spin coating, slit coating, screen printing, or applicator coating) the near infrared absorptive liquid composition of the present invention, on the light receiving side of the substrate of solid state image sensing device.
  • a process of coating preferably spin coating, slit coating, screen printing, or applicator coating
  • the film is formed using the near infrared absorptive liquid composition of the present invention.
  • the film is not specifically limited so long as it is formed while containing the near infrared absorptive liquid composition, wherein the thickness and layered structure and so forth are properly selectable depending on purposes.
  • a method of forming the film is typically such as directly applying (preferably coating), on the support, the near infrared absorptive liquid composition of the present invention (the coating liquid having the solid content of the composition dissolved, emulsified or dispersed into the solvent), followed by drying.
  • the support may be the substrate of solid state image sensing device, or another substrate provided on the light receiving side of the substrate of solid state image sensing device (for example, a glass substrate 30 described later) , or a layer such as a planarizing layer provided on the light receiving side of the substrate of solid state image sensing device .
  • the near infrared absorptive liquid composition may be coated over the support by using, for example, a spin coater, slit spin coater or the like.
  • Conditions for drying the coated film will vary depending on species and ratio of use of the individual components and solvent, and generally at 60°C to 150°C, for 30 seconds to 15 minutes or around.
  • the film thickness is properly selectable depending on purposes, without special limitation, wherein it is preferably 1 ⁇ to 300 ⁇ , more preferably 1 ⁇ to 200 ⁇ , more preferably 1 ⁇ to 100 ⁇ , furthermore preferably 1 ⁇ to 50 ⁇ , and particularly 1.0 ⁇ to 4.0 ⁇ .
  • the method of manufacturing the near infrared cut filter using the near infrared absorptive liquid composition of the present invention may include other processes.
  • the other processes are properly selectable depending on purposes, without special limitation, and are exemplified by surface treatment of the base, preheating process (prebaking) , curing process, and postheating process (postbaking) .
  • Heating temperature in the preheating process and the postheating process is generally 80°C to 200°C, and preferably
  • Heating time in the preheating process and the postheating process is generally 30 seconds to 240 seconds, and preferably 60 seconds to 180 seconds.
  • the curing process is provided, as necessary, for curing the formed film.
  • the mechanical strength of the near infrared cut filter may be improved.
  • the curing process is properly selectable depending on purposes, without special limitation.
  • Preferable examples include whole exposure and whole heating. Note that the word
  • Exposure in the context of the present invention is used not only for exposure by light of various wavelength, but also for exposure by electron beam, and irradiation of radioactive ray such as X-ray.
  • the exposure is preferably effected by irradiation of radioactive ray.
  • radioactive ray include electron beam, and ultraviolet radiation and visible light such as KrF, ArF, g-line, h-line and i-line.
  • KrF, g-line, h-line and i-line are preferable.
  • Method of exposure include exposure using a stepper, and exposure using a high-pressure mercury lamp.
  • Exposure energy is preferably 5 mJ/cm 2 to 3,000 mJ/cm 2 , more preferably 10 mJ/cm 2 to 2,000 mJ/cm 2 , and most preferably
  • Apparatus for implementing the whole exposure is selectable depending on purposes, without special limitation.
  • Preferable examples include a UV exposure apparatus typically using ultra-high pressure mercury lamp.
  • Methods of whole heating process is exemplified by method of heating of the entire surface of the formed film. By the whole heating, strength of the patterned film may be enhanced.

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PCT/JP2013/063613 2012-05-08 2013-05-07 Near infrared absorptive liquid composition, near infrared cut filter using the same, method of manufacturing the same, and camera module and method of manufacturing the same WO2013168824A1 (en)

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US10745541B2 (en) * 2015-09-24 2020-08-18 Nippon Sheet Glass Company, Limited Composition for infrared-absorbing layers, infrared-cut filter, and imaging apparatus
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