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WO2013008631A1 - Composition photosensible - Google Patents

Composition photosensible Download PDF

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Publication number
WO2013008631A1
WO2013008631A1 PCT/JP2012/066431 JP2012066431W WO2013008631A1 WO 2013008631 A1 WO2013008631 A1 WO 2013008631A1 JP 2012066431 W JP2012066431 W JP 2012066431W WO 2013008631 A1 WO2013008631 A1 WO 2013008631A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
ethylenically unsaturated
acid
photosensitive
unsaturated group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/066431
Other languages
English (en)
Japanese (ja)
Inventor
林　利明
保田　貴康
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to KR1020137028561A priority Critical patent/KR20140034776A/ko
Priority to CN201280028561.1A priority patent/CN103597407A/zh
Publication of WO2013008631A1 publication Critical patent/WO2013008631A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • the present invention relates to a photosensitive composition, and a photosensitive dry film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board using the photosensitive composition.
  • a liquid resist or a photosensitive film in which a photosensitive composition is formed by applying a photosensitive composition on a support and drying it has been used.
  • a method for forming a permanent pattern such as a solder resist for example, a laminate is formed by laminating a photosensitive layer using a liquid resist or a photosensitive film on a substrate such as a copper-clad laminate on which a permanent pattern is formed.
  • a method of forming a permanent pattern by exposing the photosensitive layer, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like is known.
  • the photosensitive composition that can be used for the solder resist, it is important to improve the resolution of pattern formation and the insulation, impact resistance, folding resistance, flame resistance, etc. after pattern formation. It is one and various studies have been made.
  • photopolymerizable epoxy (meth) acrylate resin for example, photopolymerizable epoxy (meth) acrylate resin, photopolymerizable urethane (meth) acrylate resin, and photopolymerization having one terminal (meth) acrylate group having a molecular weight of 250 to 650 and no carboxyl group.
  • a photocurable solder resist ink containing a functional compound has been proposed (see Patent Document 1).
  • a photosensitive resin composition comprising (A) an acrylic resin, (B) a polyurethane resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a phosphorus-containing compound.
  • the (B) polyurethane resin is a photosensitive resin that is a reaction product of an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group.
  • a composition has been proposed (see Patent Document 2).
  • the ethylenically unsaturated group-containing acrylic resin is a copolymer of a (meth) acrylic ester, a compound having an ethylenically unsaturated group and at least one acid group, and the copolymer ⁇ 1>
  • the photosensitive composition according to ⁇ 1> which is a modified copolymer obtained by adding an epoxy group-containing (meth) acrylate to some of the acid groups.
  • the acid-modified ethylenically unsaturated group-containing polyurethane resin has a mass average molecular weight of 5,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 2.
  • L UE has a partial structure of any one of the following general formulas (1) to (3), and —NHC ( ⁇ O) O— or —OC ( ⁇ O ) Represents a divalent linking group containing no NH-;
  • R 1 to R 3 each independently represents a hydrogen atom or a monovalent organic group.
  • X represents an oxygen atom, a sulfur atom, or —N (R 12 ) —.
  • R 12 represents a hydrogen atom or a monovalent organic group;
  • R 4 to R 8 each independently represents a hydrogen atom or a monovalent organic group.
  • Y represents an oxygen atom, a sulfur atom, or —N (R 12 ) —.
  • R 12 represents a hydrogen atom or a monovalent organic group;
  • R 9 to R 11 each independently represents a hydrogen atom or a monovalent organic group.
  • Z represents an oxygen atom, a sulfur atom, —N (R 13 ) —, or an optionally substituted phenylene group.
  • R 13 represents a hydrogen atom or a monovalent organic group.
  • ⁇ 6> The photosensitive composition according to any one of ⁇ 1> to ⁇ 5>, wherein the ethylenically unsaturated group of the acid-modified ethylenically unsaturated group-containing polyurethane resin is an acryloyloxy group or a methacryloyloxy group.
  • the ratio of the acid-modified ethylenically unsaturated group-containing polyurethane resin in the total amount of the acid-modified ethylenically unsaturated group-containing polyurethane resin and the ethylenically unsaturated group-containing acrylic resin contained in the photosensitive composition is 55.
  • the photosensitive composition according to any one of ⁇ 1> to ⁇ 6> which is not less than 95% by mass and not more than 95% by mass.
  • a photosensitive dry film having a photosensitive layer containing the photosensitive composition according to any one of ⁇ 1> to ⁇ 7>.
  • a photosensitive laminate having a photosensitive layer containing the photosensitive composition according to any one of ⁇ 1> to ⁇ 7> on a substrate.
  • a flexible wiring board having a resist pattern obtained by photocuring a photosensitive layer containing the photosensitive composition according to any one of ⁇ 1> to ⁇ 7> on a base material.
  • ⁇ 11> Production of a flexible wiring board, comprising: transferring a photosensitive layer of the photosensitive dry film according to ⁇ 8> onto a substrate; and exposing and developing the transferred photosensitive layer to form a resist pattern.
  • Method. ⁇ 12> A method for forming a permanent pattern, comprising exposing a photosensitive layer containing the photosensitive composition according to any one of ⁇ 1> to ⁇ 7>.
  • the photosensitive composition of the present invention is excellent in resolution of pattern formation by exposure / development, and is excellent in all of insulation, folding resistance, and flame retardancy after pattern formation.
  • the photosensitive film and photosensitive laminate of the present invention are excellent in resolution of pattern formation by exposure / development and excellent in insulation, folding resistance, and flame retardancy after pattern formation. Having a layer. Further, according to the method for forming a permanent pattern of the present invention, an extremely fine pattern can be accurately formed on the photosensitive layer, and any of insulation, folding resistance, and flame resistance of the cured layer after pattern formation can be achieved. Also excellent.
  • the printed circuit board of the present invention has high pattern shape accuracy and excellent durability.
  • the photosensitive composition of the present invention includes an acid-modified ethylenically unsaturated group-containing polyurethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a metal phosphate. And at least a salt.
  • the photosensitive composition of the present invention may contain other components such as a curing accelerator.
  • the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and can be appropriately selected according to the purpose.
  • the acid-modified polyurethane resin having an ethylenically unsaturated bond in the side chain Is preferred.
  • the side chain is a chain that is connected by substituting from a chain of atoms constituting the main chain of the polyurethane resin with a branched or substituted atom constituting the main chain, and has an ethylenically unsaturated group in the side chain.
  • an ethylenically unsaturated group is contained in such a side chain, or an atom constituting the main chain is directly substituted with an ethylenically unsaturated group.
  • a polyurethane resin obtained only by reaction of a diol of HOCH 2 CH ⁇ CHCH 2 OH and OCN (CH 2 ) 6 NCO contains an ethylenically unsaturated group in the main chain.
  • the ethylenically unsaturated group is a group having an ethylene bond that is consumed in the measurement of bromine value and iodine value, and is not a group showing aromaticity such as benzene.
  • the ethylenically unsaturated group is preferably a vinyl group which may have a substituent.
  • the mass average molecular weight of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably 5,000 to 60,000, preferably 5,000 to 50 5,000 is more preferable, and 5,000 to 30,000 is particularly preferable.
  • the weight average molecular weight is less than 5,000, when the photosensitive composition of the present invention is used for a photosensitive solder resist, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained. If it exceeds 60,000, coating suitability and developability may be deteriorated.
  • the mass average molecular weight can be measured using a high-speed GPC apparatus (HLC-802A, manufactured by Toyo Soda Co., Ltd.). Specifically, a 0.5 mass% THF solution is used as a sample solution, a column uses one TSKgel HZM-M, a 200 ⁇ L sample is injected, eluted with the THF solution, and a refractive index at 25 ° C. It is measured by a detector or a UV detector (detection wavelength 254 nm). And a mass mean molecular weight can be calculated
  • the acid value of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 mgKOH / g to 120 mgKOH / g, and 30 mgKOH / g to 110 mgKOH / g. Is more preferable, and 35 mgKOH / g to 100 mgKOH / g is particularly preferable. If the acid value is less than 20 mg KOH / g, the developability may be insufficient, and if it exceeds 120 mg KOH / g, the development speed may be too high, and development control may be difficult.
  • the acid value can be measured in accordance with, for example, JIS K0070.
  • a sample does not melt
  • a dioxane or tetrahydrofuran is used as a solvent.
  • the acid value is the solid content acid value of the resin.
  • the ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mmol / g to 2.0 mmol / g. 0.5 mmol / g to 1.9 mmol / g is more preferable, and 0.75 mmol / g to 1.8 mmol / g is particularly preferable.
  • the ethylenically unsaturated group equivalent When the ethylenically unsaturated group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 2.0 mmol / g, folding resistance may be deteriorated.
  • the ethylenically unsaturated group equivalent can be determined, for example, by measuring the bromine number. A bromine number can be measured based on JISK2605, for example.
  • the ethylenically unsaturated equivalent is typically a vinyl group equivalent, and the number of grams of bromine (Br 2 ) added to 100 g of the resin to be measured obtained by the bromine number (gBr 2 / 100 g) is converted to the number of moles of added bromine (Br 2 ) per 1 g of resin.
  • the acid-modified urethane resin having an ethylenically unsaturated bond in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the side chain includes the following general formulas (1) to (3) What has at least 1 among the functional groups represented by these is mentioned.
  • R 1 to R 3 each independently represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group.
  • R 1 is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable in terms of high radical reactivity.
  • R 2 and R 3 are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituted group.
  • An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable.
  • a hydrogen atom, a carboxyl group, an alkoxy group are preferable because of high radical reactivity.
  • a carbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
  • X represents an oxygen atom, a sulfur atom, or —N (R 12 ) —
  • R 12 represents a hydrogen atom or a monovalent organic group.
  • R 12 is preferably an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable from the viewpoint of high radical reactivity.
  • the substituent that each of the above groups may have is not particularly limited, and may be appropriately selected depending on the purpose.
  • the groups mentioned in the above-mentioned monovalent organic groups can be mentioned, and halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups Amino group, alkylamino group, arylamino group, acylamino group, carbamoyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carboxyl group, sulfo group, nitro group, and cyano group are preferred.
  • R 4 to R 8 each independently represents a hydrogen atom or a monovalent organic group.
  • R 4 to R 8 are not particularly limited and may be appropriately selected depending on the purpose.
  • examples of the monovalent organic group include those described as R 1 to R 3 in the general formula (1). Groups.
  • R 4 to R 8 are a hydrogen atom, a halogen atom, an amino group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, or an arylamino which may have a substituent 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 , An aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. An atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
  • each of the above groups may have include the same as those in the general formula (1).
  • Y represents an oxygen atom, a sulfur atom, or —N (R 12 ) —.
  • R 12 has the same meaning as the R 12 of the general formula (1), and preferred examples are also the same.
  • R 9 to R 11 each independently represents a hydrogen atom or a monovalent organic group.
  • examples of the monovalent organic group include the groups listed as R 1 to R 3 in the general formula (1).
  • R 9 is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable in terms of high radical reactivity.
  • R 10 and R 11 are a hydrogen atom, a halogen atom, an amino group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, or an arylamino which may have a substituent.
  • Z represents an oxygen atom, a sulfur atom, —N (R 13 ) —, or an optionally substituted phenylene group.
  • R 13 represents a hydrogen atom or a monovalent organic group.
  • R 13 is preferably an alkyl group which may have a substituent, and among them, a methyl group, an ethyl group, and an isopropyl group are more preferable in terms of high radical reactivity.
  • R 1 in the general formula (1) is a methyl group from the viewpoint of forming a crosslinked cured film.
  • R 2 and R 3 are hydrogen atoms
  • R 1 to R 3 in the general formula (1) are all hydrogen atoms
  • a styryl group in which Z in the general formula (3) is a phenylene group are preferable.
  • a group in which R 1 in the general formula (1) is a methyl group and R 2 and R 3 are hydrogen atoms, and a group in which all of R 1 to R 3 in the general formula (1) are hydrogen atoms are more preferable.
  • R 1 in the general formula (1) is a methyl group and R 2 and R 3 are hydrogen atoms is particularly preferable.
  • X in the general formula (1) is preferably an oxygen atom
  • the ethylenically unsaturated group is preferably a methacryloyloxy group or an acryloyloxy group, and most preferably a methacryloyloxy group.
  • the polyurethane resin which has an ethylenically unsaturated bond in a side chain is the concept containing both polyurethane resin (i) and (ii).
  • the polyurethane resin (i) obtained by the method (i) is preferred.
  • a polyurethane resin is a resin synthesized by a reaction between a diisocyanate compound and a diol compound (a compound having at least two hydroxyl groups).
  • the polyurethane resin (i) is represented by a reaction product of at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the following general formula (5).
  • X 0 and Y 0 each independently represent a divalent organic residue.
  • At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is at least one of the groups represented by the general formulas (1) to (3). If one is present, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is generated as a reaction product of the diisocyanate compound and the diol compound. The According to such a method, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain can be easily used, rather than replacing and introducing a desired side chain after the reaction of the polyurethane resin. Can be manufactured.
  • the diisocyanate compound represented by the general formula (4) is not particularly limited and can be appropriately selected depending on the purpose.
  • the triisocyanate compound is not particularly limited and may be appropriately selected depending on the purpose. For example, compounds described in paragraphs [0034] to [0035] of JP-A-2005-250438, etc. Is mentioned.
  • the monofunctional alcohol or monofunctional amine compound having an unsaturated group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraph [0037] of JP-A-2005-250438 ] To [0040] and the like.
  • the polyurethane resin (i) is a diisocyanate compound other than the diisocyanate compound containing the ethylenically unsaturated group, from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. It can also be copolymerized.
  • diisocyanate compound to copolymerize there is no restriction
  • L ⁇ 1 > represents the bivalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L 1 may have another functional group that does not react with an isocyanate group, for example, an ester group, a urethane group, an amide group, or a ureido group.
  • the diisocyanate compound represented by the general formula (6) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4′-methylene Alicyclic diisocyanate compounds such as bis (cyclohexyl isocyanate),
  • the diisocyanate compound represented by the general formula (4) or (6) may be used in combination of different types, but the folding resistance can be improved. At least one of them is preferably an aromatic diisocyanate compound.
  • the aromatic diisocyanate compound is preferably a diisocyanate compound having a bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, or anthracene type skeleton, for example, a bisphenol A type or bisphenol F type skeleton. More preferred is a diisocyanate compound having Each of these types of skeletons is represented by the following general formula.
  • R a and R b each independently represent a substituent, and the substituent is preferably an alkyl group having 2 to 5 carbon atoms.
  • l 1 and l 2 each independently represents an integer of 0 to 4.
  • l 1 and l 2 are preferably 0 or 1.
  • l 3 represents an integer of 0 to 6.
  • l 4 represents an integer of 0 to 8.
  • l 3 is preferably from 0 to 2, and l 4 is preferably 0 or 2.
  • a plurality of R a and R b may be the same or different from each other.
  • the naphthalene type, the phenanthrene-type and anthracene type may be a substituent of any of the rings R a are constituting a condensed ring.
  • the diisocyanate compound is more preferably a combination of an aromatic diisocyanate compound and an aliphatic diisocyanate compound from the viewpoint of suppressing warping after curing and improving folding resistance.
  • an aromatic diisocyanate compound for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate are preferable, and hexamethylene diisocyanate and trimethylhexamethylene diisocyanate are more preferable.
  • diol compound represented by General formula (5) there is no restriction
  • a diol compound containing an ethylenically unsaturated group in the side chain may be used as a raw material for producing the polyurethane resin.
  • the method used can be preferably used.
  • the diol compound containing an ethylenically unsaturated group in the side chain may be a commercially available compound such as trimethylolpropane monoallyl ether, or a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound.
  • a compound produced by a reaction with an unsaturated group-containing compound such as carboxylic acid, acid chloride, isocyanate, alcohol, amine, thiol, or halogenated alkyl compound.
  • a compound represented by the following general formula (UE) is preferable, and the polyurethane resin has a partial structure represented by the following general formula (UE1). become.
  • L UE has one ethylenically unsaturated group in the side chain, and —NHC ( ⁇ O) O— or —OC ( ⁇ O) NH— And a divalent linking group having one ethylenically unsaturated group in the side chain.
  • the compounds represented by the general formula (UE) are preferably compounds represented by the following general formulas (UE-1) to (UE-6).
  • the compound represented by the following general formula (UE-7) is a preferable compound other than the compound represented by the general formula (UE).
  • E 1 represents a single bond or a divalent linking group (a divalent organic residue)
  • E 2 represents a single bond or 2 other than —CH 2 —.
  • A represents a divalent linking group.
  • Q represents any group of the general formulas (1) to (3).
  • the compounds represented by the general formulas (UE-1) to (UE-7) are preferable, and the general formulas (UE- The compound represented by 6) is more preferable.
  • the compounds represented by the general formula (UE-6) compounds represented by the following general formula (G) are particularly preferable. Note that the compound represented by the general formula (G) has a partial structure represented by the following general formula (G1) in the polyurethane resin.
  • R 1 to R 3 each independently represent a hydrogen atom or a monovalent organic group
  • A represents a divalent organic residue
  • X represents an oxygen atom
  • R 12 represents a hydrogen atom or a monovalent organic group.
  • Examples of the compound represented by the general formula (G) include compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438, and are preferable in the present invention.
  • the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.
  • the polyurethane resin (i) of the present invention is acid-modified, and examples of the acid in the acid modification include carboxylic acid and sulfonic acid, and carboxylic acid is particularly preferable.
  • the acid in the acid modification include carboxylic acid and sulfonic acid, and carboxylic acid is particularly preferable.
  • the diol compound having a carboxyl group include those represented by the following formulas (17) to (19).
  • R 15 represents a hydrogen atom or a substituent (for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.), —CONH 2 , —COOR 16 , —OR 16 , —NHCONHR 16 , —NHCOOR 16 , —NHCOR 16 , —OCONHR 16 (where R 16 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms.
  • a substituent for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.
  • R 16 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms.
  • L 9 , L 10 and L 11 may be the same or different from each other, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group, As long as it represents a divalent aliphatic or aromatic hydrocarbon group which may have an alkoxy group and a halogen atom, there is no particular limitation, and it can be appropriately selected according to the purpose.
  • a substituent for example, an alkyl group, an aralkyl group, an aryl group, As long as it represents a divalent aliphatic or aromatic hydrocarbon group which may have an alkoxy group and a halogen atom, there is no particular limitation, and it can be appropriately selected according to the purpose.
  • An alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable.
  • the L 9 to L 11 may have another functional group that does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group.
  • you may form a ring by two or three of said R ⁇ 15 >, L ⁇ 9 >, L ⁇ 10 >, L ⁇ 11 >.
  • Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose. An aromatic group having 6 to 15 carbon atoms is preferred.
  • the diol compound having a carboxyl group represented by the above formulas (17) to (19) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the diol compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0047] of JP-A-2007-2030.
  • the presence of such a carboxyl group can impart properties such as hydrogen bonding and alkali solubility to the polyurethane resin.
  • the acid value can be adjusted to the preferred range in the present invention as described above.
  • the presence of such a carboxyl group can impart properties such as hydrogen bonding and alkali solubility to the polyurethane resin.
  • the acid value can be adjusted to the preferred range in the present invention as described above.
  • the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
  • the compound obtained by ring-opening tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-2005-250438, paragraphs [0095] to [ [0101] and the like.
  • the polyurethane resin (i) is, for example, a diol compound containing an ethylenically unsaturated group in the side chain from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability.
  • a diol compound other than a diol compound containing a carboxyl group can be copolymerized.
  • Such a diol compound is not particularly limited and can be appropriately selected according to the purpose.
  • a low-molecular diol compound or a polymer diol compound such as a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, Mention may be made of polycarbonate compounds of m-dihydroxybenzene.
  • Such a diol compound is represented by the following general formula (U) and, when incorporated as a polyurethane resin, is represented by a partial structure represented by the following general formula (U1).
  • L U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group.
  • L U1 includes, for example, an alkylene group, an arylene group, and a divalent heterocyclic group, and the alkylene group includes —O—, —OCOO—, a phenylene group, and a carbon-carbon double bond in the chain of the alkylene group.
  • the low molecular weight diol compound preferably has a mass average molecular weight of less than 400, and is described, for example, in paragraph [0048] of JP-A-2007-2030. And the like.
  • a polymer diol compound is preferable and will be described in detail below.
  • polymer diol compound is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Polyether diols such as coalesced polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol; polyhydric alcohol or polyether diol and maleic anhydride, maleic acid, fumaric acid, Polyester diols that are condensates of polybasic acids such as itaconic anhydride, itaconic acid, adipic acid, terephthalic acid, isophthalic acid; reaction of glycol or bisphenol with carbonate Alternatively, polycarbonate diols obtained by reacting phosgene with glycol or bisphenol in the presence of an alkali; caprolactone-
  • L U1 in the general formulas (U) and (U1) is — (CH 2 CH 2 O) n U1 CH 2 CH 2 —, — [CH 2 CH (CH 3 ) O] n U1 —CH 2 CH (CH 3 ) —, — (CH 2 CH 2 CH 2 O) n U1 —CH 2 CH 2 CH 2 —, — [(CH 2 ) n U 2 —OC ( ⁇ O) — (CH 2 ) n U 3 —C ( ⁇ O) O] n U 4 —O (CH 2 ) n U 2 — or — [(CH 2 ) n U 5 —OC ( ⁇ O) O] n U 6 — (CH 2 ) n U7- .
  • n U1 to n U7 each independently represents a number of 1 or more.
  • the compound represented by the general formula (U) is also preferably a diol compound represented by the following general formulas (III-1)
  • the polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0068] to [0076] of JP-A-2005-250438. It is done.
  • the polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs [0077] to [0079] and paragraphs [0083] to [0085] of JP-A-2005-250438 No. 1-No. 8 and no. 13-No. 18 and the like, and the like.
  • the polycarbonate diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the paragraphs [0080] to [0081] and paragraph [0084] of JP-A-2005-250438, No. 9-No. 12 and the like, and the like.
  • a diol compound having a substituent that does not react with an isocyanate group can be used in combination.
  • the diol compound having a substituent that does not react with an isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is described in paragraphs [0087] to [0088] of JP-A-2005-250438. And the like, and the like.
  • the weight average molecular weight of such a polymer diol compound is preferably 400 to 8,000, more preferably 500 to 5,000, still more preferably 600 to 3,000, and 800 to 2 Is particularly preferred. If the mass average molecular weight is less than 400, sufficient folding resistance may not be obtained, and if it exceeds 8,000, the glass transition temperature (Tg) of the resulting polyurethane resin will be too low. May deteriorate.
  • the mass average molecular weight is determined using, for example, a high-speed GPC apparatus (HLC-802A, manufactured by Toyo Soda Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and one column of TSKgel HZM-M. In use, 200 ⁇ L of sample can be injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm).
  • the mass ratio of the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is preferably 10 to 60%, more preferably 20 to 60%, more preferably 25 to It is more preferably 55%, and further preferably 30 to 50%. If the mass ratio is less than 10%, it may be difficult to suppress warping after curing, and if it exceeds 60%, the photocuring sensitivity may be too low and resolution may deteriorate.
  • polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention those having an unsaturated group in the polymer terminal and main chain are also preferably used.
  • the unsaturated group has a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.
  • a method for introducing an unsaturated group into the polymer terminal there are the following methods. That is, in the step of synthesizing the polyurethane resin having an ethylenically unsaturated bond in the side chain as described above, in the step of treating with the residual isocyanate group at the polymer end and the alcohol or amine, the alcohol having an unsaturated group.
  • the alcohol having an unsaturated group Alternatively, amines or the like may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
  • the unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.
  • the ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
  • the amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 2.0 mmol / g, 0.5 mmol / g to 1.90 mmol / g is more preferable, and 0.75 mmol / g to 1.80 mmol / g is particularly preferable.
  • a method for introducing an unsaturated group into the main chain there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin.
  • the diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, cis-2-butene-1,4-diol, trans-2-butene-1 , 4-diol, polybutadiene diol, and the like.
  • the acid-modified polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention those having at least one carboxyl group at the terminal of the polymer main chain may be used as non-images by an alkaline developer. It is preferably used because it is excellent in developability of part. It has at least one carboxyl group at the terminal of the polymer main chain and preferably has 2 or more and 5 or less carboxyl groups, and having two carboxyl groups is excellent in developability and has a fine pattern forming property. Is particularly preferable.
  • the polyurethane resin has two main chain ends, but preferably has at least one carboxyl group at one end, and may have at least one carboxyl group at both ends.
  • the terminal of the main chain of the polyurethane resin has a structure represented by the following general formula (AD).
  • L 100 represents an (n + 1) -valent organic linking chain
  • n represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 2.
  • the organic linking group represented by L 100 is configured to include one or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, specifically, represented by L 100.
  • the number of atoms constituting the main skeleton of the organic linking group is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 1 to 10.
  • the “main skeleton of the organic linking group” means an atom or an atomic group used only for linking the main chain of the polyurethane resin and the terminal COOH.
  • route with the fewest number of atoms made is pointed out.
  • the method for introducing at least one carboxyl group at the end of the main chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • at least one carboxyl group is used as a raw material for producing a polyurethane resin.
  • a method using a carboxylic acid compound having a group is also included in the method for introducing at least one carboxyl group at the end of the main chain of the polyurethane resin.
  • Examples of the carboxylic acid compound include a monocarboxylic acid compound having one carboxyl group, a dicarboxylic acid compound having two carboxyl groups, a tricarboxylic acid compound having three carboxyl groups, a tetracarboxylic acid compound having four carboxyl groups, and a carboxyl group.
  • Examples thereof include pentacarboxylic acid compounds having five groups.
  • a dicarboxylic acid compound having two carboxyl groups is particularly preferable in terms of excellent developability and fine pattern formability.
  • the carboxylic acid compound is not particularly limited as long as it has at least one carboxyl group, and can be appropriately selected according to the purpose.
  • a compound represented by the following general formula (ADH) is preferable.
  • L 100 and n represent the same meaning as in the general formula (AD).
  • Y 100 represents a divalent or higher valent atom.
  • L 200 represents a single bond or an alkylene group which may have a substituent.
  • the divalent or higher atom in Y 100 include an oxygen atom, a nitrogen atom, a carbon atom, and a silicon atom. Among these, a nitrogen atom and a carbon atom are particularly preferable.
  • the atom represented by Y 100 being divalent or more means that at least Y 100 has two bonds in which the terminal —COOH is bonded via L 100 and L 200 .
  • Y 100 may further have a hydrogen atom or a substituent.
  • Examples of the substituent which can be introduced into Y 100 a hydrogen atom, an oxygen atom, a sulfur atom, a substituted group configured to include an atom selected from a nitrogen atom and a halogen atom.
  • a hydrocarbon group having 1 to 50 carbon atoms is preferable, a hydrocarbon group having 1 to 40 carbon atoms is more preferable, and a hydrocarbon group having 1 to 30 carbon atoms is particularly preferable.
  • the alkylene group for L 200 is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms.
  • substituents that can be introduced into the alkylene group include a halogen atom (—F, —Br, —Cl, —I), an alkyl group which may have a substituent, and the like.
  • the carboxylic acid compound represented by the general formula (ADH) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • An anhydride reaction product and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, malic acid is particularly preferable.
  • polyurethane resin (i) used in the present invention include, for example, polymers P-1 to P-31 shown in paragraphs [0293] to [0310] of JP-A-2005-250438. Can be mentioned. Among these, polymers of P-27 and P-28 shown in paragraphs [0308] and [0309] are preferable.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention is prepared by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent and adding a known catalyst having an activity corresponding to each reactivity.
  • the molar ratio (M a : M b ) of the diisocyanate and diol compound used in the synthesis is not particularly limited and can be appropriately selected according to the purpose, preferably 1: 1 to 1.2: 1.
  • a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention is, in particular, the aforementioned diisocyanate compound and a diol compound, a (meth) acrylate compound having two hydroxyl groups in the molecule, and two in the molecule. It is preferably obtained by reacting a carboxylic acid having a hydroxyl group with the above-mentioned polymer diol compound, and in addition, obtained by reacting a compound having one hydroxyl group and a carboxyl group represented by the general formula (ADH). Is preferred.
  • the polyurethane resin (ii) is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule.
  • the polyurethane resin (ii) is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane resin containing diisocyanate and a carboxyl group-containing diol as essential components and a compound having an epoxy group and an ethylenically unsaturated group in the molecule. It is.
  • the diol component a low molecular diol having a mass average molecular weight of 300 or less or a low molecular diol having a mass average molecular weight of 500 or more may be added as a copolymer component.
  • the polyurethane resin (ii) has excellent dispersibility, crack resistance, and impact resistance with an inorganic filler, so that it has heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties. improves.
  • a diisocyanate of a divalent aliphatic and aromatic hydrocarbon which may have a substituent, a COOH group and two carbon atoms via any one of a C atom and an N atom.
  • a reaction product comprising a carboxyl group-containing diol having an OH group as an essential component, the reaction product obtained, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule via a —COO— bond It may be obtained by reaction.
  • the polyurethane resin (ii) includes a diisocyanate represented by the following general formula (I) and a carboxyl group-containing diol compound represented by the formulas (17) to (19) described in the polyurethane resin (i). And a polymer diol having a mass average molecular weight of 800 to 3,000 represented by the following general formulas (III-1) to (III-6) according to the purpose:
  • R 1 is a divalent aliphatic which may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom is preferable) or Represents an aromatic hydrocarbon. If necessary, R 1 may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.
  • R 7 , R 8 , R 9 , R 10 and R 11 may be the same or different, and may be divalent aliphatic or aromatic. Represents a group hydrocarbon.
  • R 7 , R 9 , R 10 and R 11 are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon number having 2 to 10 carbon atoms. More preferred is 6 to 10 arylene groups.
  • R 8 represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. preferable.
  • R 7 , R 8 , R 9 , R 10 and R 11 other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups, There may be an amide group, a ureido group, or a halogen atom.
  • R 12 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group or a halogen atom.
  • a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ⁇ 6 alkyl and aryl groups having 6 to 10 carbon atoms.
  • R 12 may contain other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms.
  • m represents an integer of 2 to 4.
  • R 13 represents an aryl group or a cyano group, and preferably an aryl group or a cyano group having 6 to 10 carbon atoms.
  • n 1 , n 2 , n 3 , n 4 , n 5 , n 7 , n 8 and n 9 each represents an integer of 2 or more. An integer from 2 to 100 is preferred.
  • n 6 represents 0 or an integer of 2 or more, preferably 0 or an integer of 2 to 100.
  • R 14 represents a hydrogen atom or a methyl group
  • R 15 represents an alkylene group having 1 to 10 carbon atoms
  • R 16 represents 1 to carbon atoms.
  • 10 hydrocarbon groups are represented.
  • p represents 0 or an integer of 1 to 10.
  • a partial structure in which X, Y, or Z is connected to the polyurethane main chain has —CO 2 — ( ⁇ -position or ⁇ -position).
  • the partial structures of the general formulas (1) to (3) exist on the (*) side.
  • the polyurethane resin (ii) may further be copolymerized with a carboxyl group-free low molecular weight diol as the fifth component.
  • the low molecular weight diol compound include those represented by the general formulas (III-1) to (III). ⁇ 6) and having a mass average molecular weight of 500 or less.
  • the carboxyl group-free low molecular weight diol can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.
  • Examples of the low molecular weight diol compound include the compounds described in paragraph [0048] of JP-A-2007-2030.
  • the diisocyanate represented by the general formula (I) and at least one selected from the carboxyl group-containing diols represented by the above formulas (17) to (19) are essential components.
  • at least one selected from polymer diols having a weight average molecular weight of 800 to 3,000 represented by general formulas (III-1) to (III-6) In addition to the reaction with the low molecular weight diol containing no carboxyl group having a mass average molecular weight of 500 or less represented by (III-1) to (III-6), the compounds of the general formulas (IV-1) to (IV-16) Acid value obtained by reacting a compound having one epoxy group and at least one (meth) acrylic group in the molecule shown in any one of 20 mgKOH / g to 120 mgKOH / g An alkali-soluble photocrosslinkable polyurethane resin is preferred.
  • the general polyurethane resin (i) described above is used instead of or in combination with the compounds represented by the general formulas (III-1) to (III-6). It is preferable to use the diol compound represented by the formula (U), and the mass ratio of the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is the above-mentioned polyurethane. The same as in the case of the resin (i).
  • These polymer compounds may be used alone or in combination of two or more.
  • polyurethane resin (ii) those having at least one carboxyl group at the terminal of the polymer main chain are preferable for obtaining the same effect as the polyurethane resin (i), and are described in the polyurethane resin (i).
  • the terminal block method of the polymer main chain and the group represented by the general formula (A) are preferable, and the preferable range is the same as that of the polyurethane resin (i).
  • polyurethane resin (ii) examples include glycidyl as an epoxy group and vinyl group-containing compound in polymers U1 to U4 and U6 to U11 disclosed in paragraphs [0314] to [0315] of JP-A-2007-2030.
  • Acrylates include glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400, manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400, manufactured by Daicel Chemical Industries, Ltd.) ) And the like.
  • the acid-modified ethylenically unsaturated group-containing polyurethane resin (i), (ii) used in the present invention can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin. is there.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.
  • the content of the polyurethane resin (i) or (ii) used in the present invention in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. 80% by mass is preferable, 20% by mass to 75% by mass is more preferable, and 30% by mass to 70% by mass is particularly preferable.
  • the photosensitive resin composition of the present invention may contain both of the polyurethane resins (i) and (ii). In that case, the total amount of the polyurethane resins (i) and (ii) is within the above concentration range. It is preferable. If this content is less than 5% by mass, the folding resistance may not be kept good, and if it exceeds 80% by mass, the heat resistance may fail.
  • the ratio of the acid-modified ethylenically unsaturated group-containing polyurethane resin in the total amount of the acid-modified ethylenically unsaturated group-containing polyurethane resin and the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition is not particularly limited. However, it is preferably 55% by mass to 95% by mass, and more preferably 65% by mass to 75% by mass. If this proportion is less than 55% by mass, the thermal shock resistance may be lowered, and if it exceeds 95% by mass, the insulation may be lowered. When the ratio is within the above-described more preferable range, it is advantageous in that the insulating property and the thermal shock resistance are very excellent.
  • the ethylenically unsaturated group-containing acrylic resin used in the present invention is not particularly limited as long as it is an acrylic resin containing an ethylenically unsaturated group that can be polymerized by radicals generated by a photopolymerization initiator. It can be selected appropriately.
  • the functional group having an ethylenically unsaturated group include an acryloyl group, a methacryloyl group, an allyl group, a vinyl ether group, and a vinylphenyl group.
  • (meth) acrylic acid ester (A) a copolymer (hereinafter referred to as “(meth) acrylic acid ester (A)”) and a compound (B) having an ethylenically unsaturated group and at least one acid group.
  • (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester
  • (meth) acrylate means acrylate and / or methacrylate.
  • (meth) acrylic acid ester (A)- examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and the like.
  • (Meth) acrylic acid alkyl esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone-modified 2-hydroxyethyl (meth) acrylate (meta) )
  • (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate.
  • benzyl (meth) acrylate is preferable in terms of low water absorption.
  • the compound (B) containing an ethylenically unsaturated group and having at least one acid group for example, acrylic acid, methacrylic acid, vinylphenol, chain extended between the ethylenically unsaturated group and the carboxyl group
  • modified unsaturated monocarboxylic acids include ⁇ -carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and lactone modified.
  • examples thereof include an unsaturated monocarboxylic acid having an ester bond, and a modified unsaturated monocarboxylic acid having an ether bond. These may be used individually by 1 type and may use 2 or more types together.
  • lactone-modified unsaturated monocarboxylic acid include compounds obtained by lactone modification of (meth) acrylic acid and represented by the following formula (15). Moreover, it is a lactone modified product obtained by acid-modifying a terminal hydroxyl group with an acid anhydride, and includes a compound represented by the following formula (16).
  • R 21 represents either a hydrogen atom or a methyl group.
  • the ma R 22 and R 23 each independently represents any one of a hydrogen atom, a methyl group, and an ethyl group, and may be different from each other.
  • R 24 represents a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms, or a divalent alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms. Group, an unsaturated hydrocarbon group having 3 to 6 carbon atoms, a p-xylylene group, and a phenylene group.
  • ma represents an integer of 4 to 8
  • na represents an integer of 1 to 10.
  • Modified unsaturated monocarboxylic acid having an ether bond-- As the modified unsaturated monocarboxylic acid having an ether bond, for example, an epoxy compound such as ethylene oxide is added to (meth) acrylic acid, and the molecular terminal hydroxyl group of the adduct is an acid-modified product with an acid anhydride.
  • the compound represented by (17) is mentioned.
  • R 21 represents either a hydrogen atom or a methyl group.
  • the mb R 22 and R 23 each independently represents any of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group, and may be different from each other.
  • R 24 represents a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms, or a divalent alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms. And a divalent unsaturated hydrocarbon group having 3 to 6 carbon atoms, p-xylylene, and a phenylene group.
  • mb and nb represent an integer of 1 to 10.
  • the (meth) acrylate (C) having an epoxy group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. Etc. Among these, glycidyl (meth) acrylate is preferable.
  • the copolymer is produced.
  • the manufacturing methods of well-known acrylic resins such as solution polymerization, are mentioned.
  • the (meth) acrylate (C) which has the said epoxy group is added to the one part acid group of the copolymer manufactured above, and the target modified copolymer is manufactured.
  • the acid value of the ethylenically unsaturated group-containing acrylic resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 mgKOH / g to 150 mgKOH / g, more preferably 50 mgKOHg / g to 150 mgKOH / g. preferable.
  • the acid value is less than 10 mgKOH / g, it may be difficult to remove the uncured film with a dilute alkaline aqueous solution, and when it exceeds 150 mgKOH / g, the water resistance and electrical characteristics of the cured film may be inferior. is there.
  • the mass average molecular weight of the ethylenically unsaturated group-containing acrylic resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5,000 to 100,000.
  • mass average molecular weight is less than 5,000, tack-free performance is inferior, and the moisture resistance of the coated film after exposure is poor, resulting in film slippage during development, resulting in greatly inferior resolution.
  • mass average molecular weight exceeds 100,000, developability may be remarkably deteriorated and storage stability may be inferior.
  • the content of the ethylenically unsaturated group-containing acrylic resin in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 30% by mass. More preferred is from 25% by weight.
  • Examples of the functional group having an ethylenically unsaturated group include (meth) acryloyl group, (meth) acrylamide group, vinylphenyl group, vinyl ester group, vinyl ether group, allyl ether group, and allyl ester group.
  • polyethyleneglycol mono (meth) acrylate polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( Acrylate), dipentaerythritol penta (meth) acrylate,
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • content in the said photosensitive composition solid content of a polymeric compound
  • 5 mass%-50 mass% are preferable, and 10 mass%-40 mass%.
  • the mass% is more preferable.
  • the content is 5% by mass or more, developability and exposure sensitivity are good, and when the content is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected according to the purpose. For example, it is sensitive to visible light from the ultraviolet region. It may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or an initiator that initiates cationic polymerization according to the type of monomer. Good.
  • the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm. The wavelength is more preferably 330 nm to 500 nm.
  • a photoinitiator a neutral photoinitiator is preferable.
  • the other photoinitiator may be included as needed.
  • a neutral photoinitiator there is no restriction
  • Examples of the photopolymerization initiator include (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime derivatives, organic peroxides, and thio compounds. Etc.
  • oxime derivatives from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, oxime derivatives, (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone Compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are preferred.
  • Examples of (bis) acylphosphine oxides, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are described in paragraph [0042] of JP 2010-256399 A, for example.
  • Examples include acylphosphine oxide, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds.
  • Examples of the oxime derivative include oxime derivatives described in paragraphs [0043] to [0059] of JP 2010-256399 A.
  • a photoinitiator may be used individually by 1 type and may use 2 or more types together.
  • the content of the photopolymerization initiator in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 30% by mass, 0.5% More preferred is 20% by mass to 20% by mass, and particularly preferred is 0.5% to 15% by mass.
  • the thermal cross-linking agent is not particularly limited and may be appropriately selected depending on the purpose.
  • an epoxy resin is used as long as it does not adversely affect developability in order to improve the film strength after curing of the photosensitive layer.
  • a compound for example, an epoxy compound having at least two oxirane groups in one molecule
  • an oxetane compound having at least two oxetanyl groups in one molecule can be used, and is described in JP-A-2007-47729.
  • An epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the ⁇ -position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a compound obtained by reacting an isocyanate group of a polyisocyanate or a derivative thereof (block) Polyisocyanate compound).
  • a melamine derivative can be used as a thermal crosslinking agent.
  • the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl or the like). These may be used individually by 1 type and may use 2 or more types together.
  • alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.
  • the content of the thermal crosslinking agent in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 50% by mass, and preferably 3% by mass to 30%. The mass% is more preferable. If the said content is 1 mass% or more, the film
  • Examples of the epoxy compound include epoxy compounds described in paragraphs [0071] to [0073] of JP 2010-256399 A.
  • oxetane compound examples include oxetane compounds described in paragraph [0074] of JP2010-256399A.
  • polyisocyanate compound examples include the polyisocyanate compounds described in paragraph [0075] of JP2010-256399A.
  • Examples of the blocked polyisocyanate compound include the blocked polyisocyanate compound described in paragraph [0076] of JP2010-256399A.
  • melamine derivatives examples include the melamine derivatives described in paragraph [0077] of JP 2010-256399 A.
  • the metal phosphate used in the present invention is preferably a metal phosphate represented by the following general formula (18).
  • the metal phosphate not only improves the flame retardancy of the photosensitive layer, but can also minimize the decrease in folding resistance of the photosensitive layer after curing.
  • a P and B P are each independently any one of a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, and an aryl group.
  • M represents any of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K.
  • m represents an integer of 1 to 4.
  • a linear alkyl group having 1 to 6 carbon atoms is preferable, a methyl group, an ethyl group, and an n-propyl group are more preferable, and an ethyl group is particularly preferable.
  • M Al is preferable.
  • m 3 is preferable.
  • metal phosphate represented by the general formula (18). Examples include phosphite aluminum exolit OP-935, exolit OP-930, exolit OP1230, exolit OP-1240, exolit OP-1312 (all manufactured by Clariant Japan).
  • the average particle size of the metal phosphate represented by the general formula (18) is not particularly limited, but is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and 0.5 ⁇ m or less. More preferably, it is particularly preferably 0.3 ⁇ m or less. If the average particle size is too large, the folding resistance is lowered and the folding resistance is insufficient. There is no restriction
  • the maximum particle size of the metal phosphate represented by the general formula (18) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and 1 ⁇ m or less. Is particularly preferred.
  • the average particle size and the maximum particle size can be measured using, for example, a concentrated particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.). Specifically, the measurement principle is a dynamic light scattering method, and the size distribution analysis method is a cumulant method and / or a histogram method.
  • the average particle size is defined as a particle size having an integrated value of 50% when expressed as an integrated (cumulative) mass percentage, and is defined as d50 (D50) or the like.
  • the maximum particle size is defined as a particle size with an integrated value of 100% and is defined as d100 (D100) or the like.
  • the content of the metal phosphate of the general formula (18) in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is 5 to 40% by mass. Preferably, 5 to 25% by mass is more preferable. When this content is less than 5% by mass, sufficient flame retardancy may not be obtained, and when it exceeds 40% by mass, folding resistance may be deteriorated.
  • ⁇ Other ingredients are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fillers, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and base materials. Adhesion promoters and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) You may use together. By appropriately containing these components, properties such as stability, photographic properties, and film properties of the intended photosensitive composition can be adjusted.
  • Adhesion promoters and other auxiliaries for example, conductive particles, fillers, antifoaming agents, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • the content of the inorganic fine particles as the inorganic filler in the photosensitive composition is preferably 0 to 20% by mass, and preferably 0 to 10% by mass, based on the solid content ratio of the photosensitive composition. More preferably it is.
  • the thermal polymerization inhibitor include thermal polymerization inhibitors described in paragraphs [0101] to [0102] of JP-A-2008-250074.
  • the thermosetting accelerator include the thermosetting accelerator described in paragraph [0093] of JP-A-2008-250074.
  • the plasticizer include plasticizers described in paragraphs [0103] to [0104] of JP-A-2008-250074.
  • Examples of the colorant include the colorants described in paragraphs [0105] to [0106] of JP-A-2008-250074.
  • Examples of the adhesion promoter include adhesion promoters described in paragraphs [0107] to [0109] of JP-A-2008-250074.
  • the photosensitive dry film of the present invention has at least a carrier film (support) and a photosensitive layer containing the photosensitive composition of the present invention on the carrier film, and, if necessary, other layers. Have.
  • Carrier film> There is no restriction
  • the photosensitive layer is peelable and has good light transmittance, and more preferable that the surface is smooth.
  • the carrier film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include supports described in paragraphs [0115] to [0117] of JP-A-2008-250074.
  • a photosensitive layer will not be restrict
  • a photosensitive composition solution of the present invention is dissolved, emulsified or dispersed in water or a solvent on a support to prepare a photosensitive composition solution, and the solution is directly applied. And a method of laminating by drying.
  • the coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of directly coating the support using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. Is mentioned.
  • the drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 ° C. to 110 ° C. for about 30 seconds to 15 minutes.
  • the thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 2 ⁇ m to 50 ⁇ m, and particularly preferably 4 ⁇ m to 30 ⁇ m.
  • the other layers are not particularly limited and can be appropriately selected depending on the purpose.
  • the photosensitive dry film may have these layers individually by 1 type, and may have 2 or more types.
  • the photosensitive dry film may form a protective film on the photosensitive layer.
  • a protective film there is no restriction
  • the protective film as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.
  • the combination of the protective film and the support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the combination described in paragraph [0118] of JP-A-2008-250074. .
  • the coefficient of static friction between the support and the protective film is preferably from 0.3 to 1.4, more preferably from 0.5 to 1.2. If the static friction coefficient is 0.3 or more, it is possible to prevent winding slippage from occurring when the roll is formed due to excessive sliding, and if it is 1.4 or less, it can be wound into a good roll.
  • the length and storage method of the photosensitive dry film are not particularly limited and may be appropriately selected depending on the intended purpose.
  • the length and storage described in paragraph [0120] of JP-A-2008-250074 are disclosed. The method etc. are mentioned.
  • the protective film may be surface treated to adjust the adhesion between the protective film and the photosensitive layer.
  • an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film.
  • the undercoat layer can be formed by applying the polymer coating solution onto the surface of the protective film and then drying at 30 to 150 ° C. for 1 to 30 minutes.
  • the drying temperature is particularly preferably 50 ° C to 120 ° C.
  • the photosensitive laminate of the present invention comprises at least a substrate (substrate) and a photosensitive layer on the substrate, and further laminates other layers as necessary.
  • the photosensitive layer is a layer containing the photosensitive composition of the present invention.
  • the photosensitive layer is, for example, transferred from the photosensitive dry film produced by the above-described manufacturing method, and has the same configuration as described above.
  • the substrate is a substrate to be processed on which a photosensitive layer is formed, or a transfer target to which at least the photosensitive layer of the photosensitive dry film of the present invention is transferred, and is not particularly limited and is appropriately selected depending on the purpose.
  • a material having a high surface smoothness to a material having an uneven surface can be arbitrarily selected, but a plate-like base material, a so-called substrate is preferable.
  • Specific examples include a known printed wiring board production substrate (printed substrate), a glass plate (soda glass plate, etc.), a synthetic resin film, paper, a metal plate, etc.
  • a polyimide film is used. Particularly preferred.
  • the method for producing the photosensitive laminate is not particularly limited and may be appropriately selected depending on the purpose. For example, at least one of heating and pressing at least the photosensitive layer in the photosensitive dry film of the present invention is performed. For example, a method of transferring and laminating can be used.
  • An example of a method for producing a photosensitive laminate is a method in which the photosensitive film of the present invention is laminated on the surface of a substrate while at least one of heating and pressing.
  • a photosensitive dry film has a protective film
  • the heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 15 ° C. to 180 ° C. is preferable, and 60 ° C. to 140 ° C. is more preferable.
  • the pressure for pressurization is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.1 MPa to 1.0 MPa is preferable, and 0.2 MPa to 0.8 MPa is more preferable.
  • An apparatus for performing at least one of heating is not particularly limited and may be appropriately selected depending on the purpose.
  • a laminator for example, VP-II manufactured by Taisei Laminator Co., Ltd., VP130 manufactured by Nichigo Morton Co., Ltd.
  • VP-II manufactured by Taisei Laminator Co., Ltd.
  • VP130 manufactured by Nichigo Morton Co., Ltd.
  • the photosensitive dry film and photosensitive laminate of the present invention can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and preferably used for forming a permanent pattern on a printed circuit board, particularly a flexible wiring board. Can do.
  • the permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps as necessary.
  • the exposure process is not particularly limited as long as it is a process for exposing the photosensitive layer formed of the photosensitive composition of the present invention, and can be appropriately selected according to the purpose.
  • the process etc. which expose with respect to the photosensitive layer in a conductive laminated body are mentioned.
  • the object of exposure is not particularly limited as long as it is a photosensitive layer, and can be appropriately selected according to the purpose.
  • the photosensitive dry film is laminated on the substrate while performing at least one of heating and pressing. It is preferable to be performed on the laminate formed as described above.
  • the exposure method is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include digital exposure and analog exposure.
  • ⁇ Other processes> Other steps are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a substrate surface treatment step, a development step, a curing treatment step, and a post-exposure step.
  • the development process is a process of removing an unexposed portion of the photosensitive layer.
  • the developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include developers described in paragraphs [0171] to [0173] of JP-A-2008-250074.
  • the curing process is a process for performing a curing process on the photosensitive layer in the formed pattern after the development process.
  • the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern
  • the permanent pattern is formed on a printed circuit board, preferably on a flexible wiring board.
  • a permanent pattern can be formed, and soldering can be performed as follows. That is, a hardened layer that is a permanent pattern is formed by development, and the metal layer is exposed on the surface of the printed board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion.
  • the permanent pattern by the hardened layer functions as a protective film or an insulating film (interlayer insulating film), a solder resist, particularly a flexible solder resist, and prevents external impact and conduction between adjacent electrodes. .
  • the flexible wiring board of the present invention has at least a substrate (base material) and a permanent pattern formed by a permanent pattern forming method, and further has other electronic members appropriately selected as necessary. .
  • the acid value, the mass average molecular weight, and the ethylenically unsaturated group equivalent in the synthesis examples were measured by the following methods.
  • the acid value was measured according to JIS K0070. However, when the acid-modified ethylenically unsaturated group-containing polyurethane resin did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
  • the mass average molecular weight was determined by using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Kogyo Co., Ltd.), a 0.5% by mass THF solution as a sample solution, a column using one TSKgel HZM-M, and 200 ⁇ L. The sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene. (Ethylenically unsaturated group equivalent) The ethylenically unsaturated group equivalent was determined by measuring the bromine number according to JIS K2605.
  • Acid modified ethylene unsaturated group-containing polyurethane resin (PU3) solution was synthesized.
  • Ethylenically unsaturated group equivalent 1 [mmol / g]
  • urethane resin 1 had a solid content acid value of 67 mgKOH / g, and a mass average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 8,000.
  • Preparation Example 8 Preparation of Phosphate Metal Salt Dispersion 13.13 parts by mass of metal phosphate salt (trade name: OP-935, manufactured by Clariant Japan Ltd.) and specific mixing of each resin prepared in each of the above Preparation Examples 75.40 parts by mass of a solution (solid content concentration: 40% by mass), 0.66 parts by mass of a dispersant (trade name: BYK-W903, manufactured by BYK Japan) and 10.82 parts by mass of cyclohexanone were weighed.
  • metal phosphate salt trade name: OP-935, manufactured by Clariant Japan Ltd.
  • the average particle size and the maximum particle size were measured by the following methods.
  • a solution obtained by diluting the above metal phosphate dispersion by a factor of 50 was measured using a concentrated particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.).
  • the measurement principle was a dynamic light scattering method, and the size distribution analysis method was measured as a cumulant method and / or a histogram method.
  • the average particle size is defined as a particle size of 50% integrated value when expressed in terms of integrated (cumulative) weight percentage, and is defined as d50 (D50), etc.
  • the maximum particle size is 100% integrated value And is defined as d100 (D100) or the like.
  • Example 1 ⁇ Production of photosensitive dry film> A photosensitive composition solution having the following composition was applied onto a polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m as a support, and dried to form a photosensitive layer having a thickness of 30 ⁇ m on the support. . On this photosensitive layer, a 20 ⁇ m thick polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated as a protective layer to produce a photosensitive dry film.
  • a polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.
  • a 20 ⁇ m thick polypropylene film manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200
  • the pigment dispersion (G-1) was 0.42 parts by mass of phthalocyanine blue, 0.12 parts by mass of anthraquinone yellow pigment (CI PY24), 12.85 parts by mass, and 86.62 of cyclohexanone. After mixing with parts by mass in advance, the mixture was prepared by motor mill M-250 (manufactured by Eiger) using zirconia beads having a diameter of 1.0 mm and dispersing at a peripheral speed of 9 m / s for 3 hours.
  • the metal phosphate dispersion used in the photosensitive composition solution was prepared in the manner shown in Table 1 below in which the PU 1 of Preparation Example 1 and the ethylenically unsaturated group-containing acrylic resin 1 of Preparation Example 4 were used in the photosensitive composition. It was prepared so as to be contained at the ratio shown in Example 1.
  • a substrate was prepared by subjecting the surface of a copper-clad laminate (no through-hole, copper thickness 12 ⁇ m) to chemical polishing treatment.
  • a vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was used while peeling the protective film on the photosensitive dry film so that the photosensitive layer of the photosensitive dry film was in contact with the copper clad laminate.
  • the pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure time of 10 seconds.
  • a predetermined pattern can be obtained from a polyethylene terephthalate film (support) side through a glass mask having a predetermined pattern with a parallel light exposure machine (ultra-high pressure mercury lamp). In this way, irradiation was performed at an energy amount of 60 mJ / cm 2 to cure a part of the photosensitive layer. This exposure process was defined as a standard exposure process.
  • a laminate was obtained.
  • the obtained laminate for evaluation was cut into 5 mm ⁇ 10 cm squares, bent 180 ° in the long side direction with the wiring pattern on the outside, a predetermined weight was placed on the bent part for 3 seconds, and the folding resistance was evaluated according to the following criteria. .
  • the produced photosensitive laminate was allowed to stand at room temperature (23 ° C.) at 55% RH for 10 minutes.
  • the pattern forming apparatus 60 mJ / cm so that a round hole with a width of 30 ⁇ m to 100 ⁇ m of the diameter of the round hole can be formed on the polyethylene terephthalate film (support) of the obtained photosensitive laminate. 2 was exposed.
  • the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
  • the entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight aqueous sodium carbonate solution at 30 ° C.
  • ⁇ Flame retardance> Etching a substrate for flexible printed wiring boards (made by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX” M series), which is made by laminating a copper foil (copper foil thickness 12 ⁇ m) on a polyimide substrate (polyimide thickness 12.5 ⁇ m), and removing the copper foil As a result, a polyimide substrate having a thickness of 12.5 ⁇ m was obtained.
  • the photosensitive layer (thickness 38 ⁇ m) of the photosensitive dry film prepared above was adhered to both surfaces of this polyimide substrate by lamination.
  • a composite sample was obtained by cutting the polyimide substrate on which the cured photosensitive layer obtained above was formed into a size of 20 cm ⁇ 5 cm.
  • the obtained composite sample was wound around a cylindrical rod having a diameter of 1 cm ⁇ 20 cm, and the position of 12.5 cm from the end of the composite sample was fixed with heat-resistant tape, and then the rod was removed to obtain a length of 20 cm and a diameter of 1 cm.
  • a flame retardant test sample was obtained.
  • the obtained flame retardant test sample was hung with a clamp, and a flame test was conducted by indirect flame with a 3 cm flame for 3 seconds.
  • Example 1 While maintaining the total content of the acid-modified ethylenically unsaturated group-containing polyurethane resin and the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition, the type of resin and the acid-modified ethylenically unsaturated group were maintained. Except having changed the content ratio of a saturated group containing polyurethane resin and an ethylenically unsaturated group containing acrylic resin into the ratio of Table 1, it carried out similarly to Example 1, and the photosensitive composition, the photosensitive dry film, and A photosensitive laminate was obtained. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 (Comparative Example 1) In Example 3, a photosensitive composition, a photosensitive dry film, a photosensitive laminate, and the like were obtained in the same manner as in Example 3 except that PU1 in the photosensitive composition was replaced with urethane resin 1. Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.
  • Example 2 (Comparative Example 2) In Example 3, except that PU1 in the photosensitive composition was changed to the ethylenically unsaturated group-containing acrylic resin 1, a photosensitive composition, a photosensitive dry film, and a photosensitive laminate were obtained in the same manner as in Example 1. Etc. Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.
  • Example 3 (Comparative Example 3)
  • the photosensitive composition, the photosensitive dry film, and the photosensitive property were the same as Example 3 except that the acrylic resin 1 was used instead of the ethylenically unsaturated group-containing acrylic resin 1 in the photosensitive composition.
  • a laminate was obtained. Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.
  • Example 4 (Comparative Example 4) In Example 3, except that the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition was replaced with the acrylic resin 2, the photosensitive composition, the photosensitive dry film, and the photosensitive laminate were the same as in Example 3. I got a body. Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.
  • the numerical values in Table 1 indicate the ratio (mass%) of each resin when the total amount of urethane resin and acrylic resin in the photosensitive composition is 100 mass%.
  • Comparative Example 1 using a urethane resin other than the urethane resin defined in the present invention, and Comparative Examples 3 and 4 using an acrylic resin other than the acrylic resin defined in the present invention, insulation, folding resistance and resolution are provided. It became inferior result. Moreover, in Comparative Example 2 in which no urethane resin was used, the folding resistance was inferior. In contrast, Examples 1 to 6 using the photosensitive composition of the present invention were excellent in all of insulation, folding resistance, resolution and flame retardancy.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une composition photosensible contenant : une résine de polyuréthane contenant un groupe à insaturation éthylénique modifié par un acide ; une résine acrylique contenant un groupe à insaturation éthylénique ; un composé polymérisable ; un photo-initiateur ; et un sel métallique d'acide phosphorique.
PCT/JP2012/066431 2011-07-11 2012-06-27 Composition photosensible Ceased WO2013008631A1 (fr)

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TWI687769B (zh) * 2015-05-12 2020-03-11 日商三菱製紙股份有限公司 噴砂用感光性樹脂組成物及噴砂處理方法
KR102019581B1 (ko) * 2015-06-09 2019-09-06 아사히 가세이 가부시키가이샤 터치 패널용 수성 수지 조성물, 전사 필름 및 경화막 적층체, 그리고 수지 패턴의 제조 방법 및 터치 패널 표시 장치
TWI591119B (zh) * 2016-06-16 2017-07-11 臻鼎科技股份有限公司 感光性樹脂組合物、覆蓋膜及電路板
JP7111301B2 (ja) * 2018-03-27 2022-08-02 リンテック株式会社 剥離シート

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